Quantum Yields for the Photosensitized Formation of the Lowest Electronically Excited Singlet State of Molecular Oxygen in Solution Francis Wilkinson Deparment of Chemis, Uniersiyof Technolgy, Loughborough, Leicestershire, LEI STU, UK and W. Phillip Heiman and Alberta B. Ross Raaiaion Chemistry Data Center, Rodation Laboratory, Univesiy of Notre Dame, Nore Dame, IN 46556 Received June 5,199; revised manuscrip receed September 18, 1992 Quenching of excited singlet and trptet states of many substances by ground state molecular oxygen produces singlet oxygen, the lowest electronically excited singlet state of molecular oxygen, Ox('4,). The fractions of singlet and wilt states ‘quenched which produce singlet oxygen and the quantum yields of formation of singlet oxygen in fluid solutions have been critically compiled. Methods for deter- mining yield parameters have been reviewed. Data have been compiled from the Itcrature through 1991. Photoscnsitizers such as aromatic hydrocarbons, aromatic ketones and thiones, quinones, coumarins, floresceins, transition metal complexes, and heterocyclcs are inchuded in Table 1. Porphyrins and phthalocyanines are ine Cinded in Tale 2. Other materials which have heen investigated for singlet oxygen production, such as dyes and drugs, are collected in Table 3 along with heteroge- neous systems such as polymer-bound photosensitizers. Key words data compilation energy transfer; excited states; eygen photesensization; quantum yes, ‘quenching singlet exygen: singlet sates, soltion; triplet states. Contents 1. Introduction. 114 4 Methods for Determining the Sensitized Yields 2. Photosensitized Production of Singlet Oxygen ‘of Singlet Oxygen Production 320 in Solution ..... ns 4.1. Photo-oxidation Studies. 121 2.1. Senstized Production by Pused Radiohsis.. 117 4.1.1. Steady-State Irradiation. 121 3. Methods for Studying Kinetics of the Reactions 412, Pulsed Studies of ‘Acceptor of Singlet Oxygen. . psneeneeetare 117) Disappearance........ - 122 3.1. Phosphorescence De nv 42. Photothermal Methods... see 13 32. Time Dependent Th 42, Steady-state Fhotocaiorimetric Singlet Oxygen Decay. 8 Methods 123 3.3, Time Dependent Acceptor ns 42.2. Time Dependent Thermal Lensing.. 123, 241, Following Pulsed Excitation of = 423. Laver Induced Photosoouetiee ... 123 Sen 18 43. Luminescence Intensity Measurements... 124 33.2, Monitoring Sensitized Photo: 44, Thplet ‘Enevgy Transfer and Singlet oxidation “by Consumption of, Onvgen Yields. 124 Reactants or Appearance of 44,1. Using Triplet -Caroiene as a Products Under Steady-State Probe. 104 Conditions .| cee 1B 442. Using Luminescence Measurements. 125 39.9 Separation oF ky aNd Kye secs LY 44.5. Using Pulsed Studies ot Acceptor Disappearance. .... ws 5. Quantum Yieks of Singlet Oxygen Production = Comments on Tables 126 eect cman acie Gus see eevee ee 5.1. Contents of Tables 1-3 126 tnd the American Chemial Society. 52. Relative Measurements and. Standard Reorins availble fom ACS see Reprints List at beck of ase Values 176 (047-2689/93/010119-1501826.00 113 J. Phys. Chem. Ret. Data, Vol. 22, No. 1, 198814 6. List of Abbreviations and Symbols. 128 7. Acknowledgements .. : 130 8, References to Text ...... 130 9. References to Tables 212 10. Molecular Formula Index 220 11, Chemical Name Index «+++ 24 12, Appendix 1, Reverse Energy Transfer and Geminate Reactions ........ 259 10.1. Reverse Energy Transfer 250) 12.1.1. Derivation of $4 According 10 Scheme 1, ie. without Energy ‘Transfer for Self-sensitized Photo- oxidation. 259 12.12. Derivation of in the Presence of Back Energy Transfer........ 259 412.2. Geminate Keaction zu 13, References to Appendix 1. 260 14, Append? Self Consistent Averages of and i 261 1, Introduction Ground state molecular oxygen, Ox, is well known to be. highly reactive and essential for animal respiration. Its properties have been actively studied for more than 200, years. However the properties of its lowest electronically excited state have only heen actively investigated during the last three decades. This is illustrated in the book en- titled Singlet Molecular Orygen' where Paul Schaap col- lects 28 Benchmark papers covering the period 1924-1973 which tell the story of the ‘discovery’ of singlet ‘oxygen and many of the key steps taken towards present ay understanding, There is strong evidence for the in- volvement of single oxygen, a powerful oxidant, i pho sensitized oxidations, in photodynamic inactivation of ses and cells, in phototherapy for cancer, in photocar- onicic, in tho photodegradation of dyes and poly. ‘mers and in the dye sensitization ofthe photodegradation of polymers. Much current interest in the chemical reac- tions of sinelet oxvgen stems from its potential as a pho- tochemo-therapeutic agent ‘The ground electronic state of molecular oxygen, which has zero angular momentum about the internuclear axis and contains two unpaired p electrons, has the group the- ‘retical symbol 3} . The two electronically excited singlet states which arise from this same electron configuration bbut with spin pairing of the two clectrons are the "4, and the "Sj states which lie 94 and 157 kI mol” respectively above the °S; ground state (see potential energy curves shown in Fig: 1). The electronic transitions 'A, "3; and "37 < "Sp although highly forbidden are readily ob- served in absorption and emission in the upper atmo- sphere with zer0-zero transitions at 1,269 and 762 nm and estimated radiative lifetimes of 64 min and 10 s, respec- WILKINSON, HELMAN, AND ROSS: List of Tables 1. Quantum yields of photosensitized production of singlet oxygen... 132 2. Quantum yields of photosensitized production ‘of singlet omygen, from porphyrins and related species 1m 3. Quantum yields of photosensitized production af singe nen, fra dees de, pers ete. . 196 A2.1. Average values for 9, and fl 262 List of Figures 1, Potential energy curves for molecular oxygen. 114 2. Singlet state transitions ana simuttaneous pair- state transitions in molecular oxygen. 3. Pictorial representation of full kinetic scheme for photosonsitized oxidation involving singlet ‘oxygen ... 4, Diagram showing connections between relative #X measurements for photosensitizers in ben- zene .. ee eee eee us 47 127 tively ‘The measured lifetimes in the gas phase and in solution are very much shorter than this. In fact, in con- densed media, the lifetime of O;*('3) is so short that ‘virtually nothing is known about its properties, and thus the term singlet oxygen is used throughout this review to refer to the dy state. oem orn yap, tage tome tay Fp tage OM 010 aus 020 “Intemucear Distance nm Fc. 1. Poten 3 energy ures for molecu ongen. In 1963 Khan and Kasha interpreted the red cher rminescence of the hypochlorite-oxygen reactions as due to liberated singlet oxygen. Following the work of Ogryzlo, val **, Khan and Kasha’ gave a full spectroscopic corre- lation of the absorption and emission spectra in terms of the simultaneous transitions between the states shown in Fig. 2. Obviously the long-lifetime of "A, even at one at- mosphere pressure is such that two excited states collideQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN econ States CED CED Cag czy Capcap esperp Cay CEp) og sl gf qs a sl 3 ° exper Fie 2, Singlet state wanstons and simultaneous par-state transitions fn molecular oxygen. coften enough for the simultancous transition "Sy "Sy —> 83,72, + hy to be seen, ‘Although singlet oxygen had been proposed as a possi- hie intermediate in dye-sensitized photo-oxygenations by Kautsky as early as 1931" this was only firmly established following publications by Foote and Wexler and Corey ‘and Taylor" in 1964. A few years later a method for measuring the lifetime of singlet oxygen in solution was ‘developed by Adams and Wilkinson" which made direct time measurements of the reaction of singlet oxygen with a reactive sulsiate, diphenslinubensoturen following nanosecond laser photolysis enabling rate constants to be obtained for reactions of singlet oxygen. In 1976 Kras- novely? used » mechanical piznephoraceape to detect the weak luminescence from O2*(‘4,) at 1270 nm, thereby ‘obtaining kinetic information concerning the reactions of singlet oxygen_on millisecond timescales. However the development in the eighties of sensitive germanium photodiodes means that direct kinetic and relative yield studies of the phosphorescence of singlet oxygen are now routinely possible on timescales down 10 1 ps. Numerous reviews! and several books®* have re- cently been published on singlet oxygen and the field con- inves to grow dramatically. In 1981 we published a critical comprehensive compilation* on ‘Rate Constants for the Decay and Reactions of the Lowest Electronically Excited State of Molecular Oxygen in Solution’ which re- ported first order solvent deactivation rate constants for 50 different solvents and second order rate constants for the deactivation and chemical reaction of singlet oxygen 115 for 690 different compounds, from available data up to the end of 1978, including a few papers for 1979. We are in the process of updating this published compilation which we shall refer to as Paper I." A considerable num- ber of studies on singlet oxygen properties have been published in the last decade yielding hundreds of rate ‘constants for reaction, quenching and decay but also ir creasingly hundreds of reports of the quantum yields of singlet oxygen production, s, for many sensitizer-solvent systems, Since we did not collect data on quantum yields in Paper P* we have concentrated in this compilation on 44 values. We have endeavored to keep the treatment consistent with Paper I* by using identical equation num- bers and symbols wherever possible. In order to avoid too much duplication much reference is made to Paper I es- pecially when discussing singlet oxygen kinetics and reac- tions. It is important to stress that photo-oxidation can arise as a result of several different mechanisms. Two major lasses uf plrotoscnsitived exygenations have been desig nated as Type I and Type II" In the former, the sensi tizer interacts directly with the substrate resulting, for ‘example, in either H-atom or electron transfer. The rad- icals so produced from the sensitizer react in the pres- fence of oxygen to regenerate the sensitizers, whi radicals produced from the substrate, for example, ini tiate free radical chain reactions, as observed in auto-ox- ‘dations, etc. Type I reactions involve the direct interaction of the excited sensitizer with oxygen which can give upon energy transfer singlet oxygen, which reacts with various substrates yielding Type I photosensitized 2, Photosensitized Production of Singlet Oxygen in Solution ‘The method most frequently used for producing singlet ‘oxygen in the laboratory is photosensitization (see Scheme 1). Both continuous irradiation and pulsed exci- tation studies have made much use OF dls method oF px duction which also frequently occurs in nature. In this mechanism (Scheme 1) the lowest excited singlet and triple Ty respectively and the ground electronic state by Ss. Any substrate which deactivates singlet oxygen by physical or chemical quenching is represented by M in Scheme 1. However, when quenching is known to be mainly by chemical reaction we shall use A to represent a reactive substrate and when a second ‘reference’ reactive sub- strate is employed we shall use A’. When the molecule is known to be a physical quencher with negligible reaction ‘Quill be used in place of M. The singlet oxygen sensitizer ‘even if it quenches singlet oxygen will be represented by S in place of M. When measurements are made relative 10 a teference sensitizer we shall label this S'. Thus M is 1 general symbol in Scheme 1 which may be replaced by A, A’, Q, Sor 8! or any combination of these. ‘scheme 1 is easily modified for self-sensitization also called photo-autoxidation where a substrate sensitizes its tator of the kentitizers are represented af S,, and J. Phys. Chom, Ret. Data, Vol. 22, No.1, 1992116 WILKINSON, HELMAN, AND ROSS = Seen Waa od Rosine Pabaae rare ioe 2 amt he i fede sce B} te eo ares t o-Bs ‘3 S140: Th +10" AS PR= KRIS, 6 § 40:57, +40, | oe JP = 0 + KVR 7 Si +02» Se #70 AG PR = KAO: V(kiso + KEAO2)) BS, +0; — products: RE 1 PR = (1 + KSGrlO2]) § hash & | , 0 1am be km = (8) IL Ty +02 Sy +403* cy fl KPI ‘12 T, +02 So +°O: Ra RR B RISc ase 8 rnmnguiner#engoy Bee i . 1 n= 701 = ethan oon scueen ec Meas, ee peoara = tina 5, qn wich sO f¥ = fraction of S; quenched by O2 which gives T; eee eta ane FEY proportion ofS; quenched by O: PP proportion of T, quenched by Os ‘own photo-oxidation. However Scheme 1 does not in clude any of the possible reactions between the substrate M with the sensitizer singlet or triplet states $; or Ty e.g. s+MSsem som S14 M 5, + M 2% Products aM gam ny + rious 18 19 20 a 2 ‘These steps are not included in Scheme 1 since in most studies these reactions have been shown to be absent. In fact a major criterion for choosing a sensitizer isthe ab- sence of such complications. Other possible complica- tions are the quenching or reaction ofS, T; and 'O3* by products and other bimolecular reactions for example be- tween '0;* and T; etc. These possibilities should be borne in mind especially when experimental conditions are varied markedly by using dilterent types of sensitizers, or highly reactive substrates, high concentrations, high light intensities ete. Fig. 3 shows pictorially the reaction scheme including all the steps 1-22 J. Phys. Chem, Ret. Data, Vo. 22, No.1, 1993, ‘The quantum yield of singlet oxygen production, via sensitization bu, is given by the sum of contributions due to oxygen quenching of §, and 7) ie 3 = $5 (8) + 65 (TD. 4s depends on the concentration of oxygen and in the presence of oxygen quenching of both S; and’T, it follows from the steps shown in Scheme 1 (see Appendix 12.1.1 for derivation) that bs = PRL + OPPRAL = PRL + PRP PPLE + bx PRPPAT which can be written as ba = ouPPYl + PYAR + PRIOR — dn). When Es, ~ Er, < Ba, K& > 0 and thus sensitization is just by the triplet state, Eq. (1) becomes OPPRGT = Or PEPE IE + PR IPE TE ‘When the lifetime of S, is such that ksp > k93[O3] a fur- ther simplification occurs and @ osQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN S200} ES RSMO) gM ie aS Products Products Products "7 Hep 30, 4 hv (singlet oxygen erphorsrene) ee) lot \ HIM oy or oer produts 451M 20, (physical quenching by My Fic. 3. Pictorial representation of ull kinetic scheme [stp I to 22, se text] for photosensitzed cation involving singlet oxygen. S = Sense, M = Substrate ba = bP. For many molecules, triplet lifetimes are long and oxygen quenching is very efficient. Thus even air saturated sotu- tions have PP = 1. In this ease, in the absence of singlet state quenching by oxygen, on of Various methods are available for measuring the quan- ‘tum yield of singlet oxygen production and these will be discussed in Section 4. 2.1, Sensitized Production by Pulsed Radiolysis, ‘When @ high energy electron beam is passed through Tiquid benccne aid syne wiles sulvenis @ high yiehd of ‘excited states can be formed. Since the lifetimes of singlet and triplet states of benzene are only a few nanoseconds in neat benzene, quenching by direolved atygen doce not produce much singlet oxygen. However, in the presence ‘of a high concentration of a triplet energy acceptor, en- ergy transfer to and then from its triplet state to oxygen yields singlet oxygen. For example, on pulsed radiolysis of benzene containing 10-? mol L~* naphthalene, triplet benzene is intercepted by naphthalene to give triplet napnthatene whien 1S quenched by oxygen ana enough singlet oxygen is produced to enable its properties to be probed using the technique of pulsed radiolysis” 3. Methods for Studying Kinetics of the Reactions of Singlet Oxygen. 3.1. Phosphorescence Decay Although the phosphorescence from singlet oxygen is highty forbiddon and it oooure in tho infrared rogion of the spectrum which presents many difficulties for experi- mentalists itis now possible to detect the decay of singlet ‘ween luminescence from very dilute solutions of sensi tizers""" These kinds of measurements have enabled ‘much more direct determinations of the lifetime of set oxygen than the indirect methods reported earlier. If the logarithm of the phosphorescence intensity is plot- ted asa function of time then the slope equals the decay constant, given by: kp = ke + SknlM) , @ where M represents any malecula inching the censitionr ‘which quenches singlet oxygen (via a physical process or a chemical reaction) Several workers” have measured kp asa function of sensitizer concentration which enables both ks and the bimolecular rate constant for singlet oxj- gen quenching by the sensitizer ks tobe obtained. When 2 decay constant for singlet oxygen is measured in the presence or a sensitizer We shall USE ky = Ky + Ks [8] fOr the decay constants. Its often assumed or demonstrated that under many experimental conditions ki = ks; how- J. Phys. Chem. Ref. Data, Vol. 22, No.1, 1903,118 WILKINSON, HELMAN, AND ROSS: ‘ver this is not always the case. Occasionally the value of ks is obtained by measuring ka as a function of [S] and extrapolating to [S] = 0.¥ This procedure is to be recom- mended 3.2, Time Dependent Thermal Lensing due to Singlet Oxygen Decay ‘The absorption of even part of the energy in a laser pulse gives rise to local temperature changes in gases or liguids. This leads to changes in density and refractive i dex which causes the system to act as a diverging lens. ‘Tie sesolved thetmal lensing (TL) due to release of en= ergy by decaying excited states can be used to measure lifetimes of singlet oxygen in the range 0.1 to 100 ps. A. continuous Taser beam used a¢ a prohe eqnene ie die. ppersed by the thermal lens reducing the light reaching photodiode through a pinhole. The photodiode signal gives the relative magnitudes of heat contributions (U) for fast and slow non-radiative processes relative to the acoustic transit time. The time dependence of the slow process gives rate information. The TL signal at time ris ‘etined as ue) 6) where V(0) is the time dependent voltage generated by the detector and Vs isthe value before excitation by the pump laser. Following the sensitized production of '0.*, AU = Usoi ~ Vine decays exponentially with the decay constant ko given by Eq, (2) (See also Section 4.22). 3.3 Time Dependent Acceptor Disappearance 4.3.1. Following Pulsed Excitation of a Sensitzor ‘This method is discussed in detail in Paper 1> To sum- rarize according to the mechanism given in Scheme 1, in thie eace with M= A, since we are dicenssing a reactive substrate, it follows that 4A) _ yapo.n TA — astairo.. Following pulsed excitation in aerated solutions most sin- let and triplet states have decayed within 1 ys and then — MO]. (ey + kAADEOI and thus ~alA] = RAIL} fexp—Cea +55 AIH. (4) Equation (4) has been treated slightly differently by ‘Adams and Wilkinson", by Young etal‘! and by Merkel and Kearns" as explained in Paper 1. However for very small changes in [A] (ie. less than 10%) al ofthese treat- rents effectively put [A] = [A]m, the average value of IA], and integrate Eq. (4) taking ky = ke + kalAle to sve ‘J. Phys. Chom, Ret. Data, Vol 22, No. 1, 1993 (ap-[ale = 2 LOrbedAle e-r —s) ‘Since the change in concentration of. ‘AA, the change in absorbance by the oxi at some convenient wavelength; ie. [A]. - [Ale = ‘AA/el, where ¢ is the extinction coefficient and ! the an- alyzing path-length. It follows from Eq, (5) that naa kof +eonst © and a plot of —In AA vs. ¢ should have a slope equal to ky = ka + kal] Thus by varying [Alo values of ky and zka.can be determined. If kx is only partly due to chemical quenching and partly due to physical quenching, the value af Zs abtained will he the rate conetant die t combination of both processes; ie. ka = kd + kj. Thus when A acts both as a physical and as a chemical quencher, the value of ka obtained is the total rate con- stant for quenching due to both processes. The acceptor used in most studies of this type isthe original one chosen by Adams and Wilkinson,” namely 1,3-diphenylisoben furan, DPBF. In the presence of several posstble singlet conygen quenchers (ie. Scheme 1 with M = A, $ and Q), wwe have ky = ky + ks[S] + kolQ] + kalA]. o Measurement of ko as a function of [Q] keeping [S] and [A] constant allows values of koto be obtained. N.B. If ko only partly due to physical quenching and a small part ‘due to reaction, the value of ko obtained will be the total rate constant for quenching due to both processes. A variation on this method has been reported by Matheson, et al. in which singlet oxygen is directly generated by absorption of the output at 1065 nm of a pulsed Nd-glass laser by oxygen dissolved under pressure (up to 130 atm) in 1,1,2-tichlorotrifluoroethane (Freon 113) and the disappearance of the singlet oxygen accep- tor DPBF was monitored. Farmilo and Wilkinson® have developed a method for measuring singlet oxygen decay which monitors absorption by triplet B-carotene, *C*, formed by energy transfer from singlet oxygen in aerated solutions containing a sensitizer and a low concentration ‘of B-carotene. Under appropriate conditions the decay of absorption at 320 un due w °C mints dhe singlet oxy- ‘gen decay yielding values of ko. Paper I describes these methods in detail (see Eqs. (7)-(12) given there). 32.2, Monitoring Senstized Photo-oxldations by Consumption fof Reactant or Appesrance of Products ‘Under Steady-State Condhions. Many photosenstized reactions of a single substrate A have been carried out under conditions such that no ‘quenching by A of the sensitizer singlet or triplet states, ‘ceurs, in which case the mechanism is as given in Scheme 1, with M = A, For eontinvous iraQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 424 97) po, ~ 4A) = - 1a =F -sepo;"}1A] 7 (a3) and the steady-state approximation can be applied to Si, Ti and 10;* (See Appendix 1, Sec. 12.1.1) to give on a) where ps is the fraction ofthe O:"(',) formed which re- acts with A. The rate of oxygenation may be followed by ‘determining the rate of production of some product and! ‘oF the rate of disappearance of either the substrate A ‘and/or of oxygen. All three have been used. N.B. It fol lows from Eq, (14) that when ke > ka[A] or kafA] > ke the rate of oxygenation will be frst or zero order respec- tively with reepect to.A. Equation (Id) can he rearranged togive rb = (eda) [i +EAl (05) where ft = Kk Singlet oxygen by A. Mos reacve substrates (A) reset with shige! unygen with unit stoichiometry as implied in Eqs. (13) 10 (15) which apply when each time a molecule of 'O:* reacts it Toads tothe conmumption af ane mnlerale af A vt ne of Or and produces one molecule of the product P. If there are stoichiometry factors a different from unity, i. the overall reaction is given by the equation he fraction of reactive quenching of, ash + 00,03 5 oP 1A] 1.doy _ 1 aF] a a ao, tay dr and Eqs. (14) and (15) still apply. If however the rate of the reaction is monitored by observing the rate of con- sumption of a reactive substrate such as thiourea where ‘= 2 and this rate is not divided by a = 2, then aff instead of {> appears in Eqs. (14) and (15). This adjust- ‘ment needs to be made whenever unit stoichiometry does not apply ‘According to Eq. (15) linear plots of ra oF di! ¥s [AJ should give slope__ ks _ Fnteroept ~ ka ~ Pe where Ba = kulka represents the concentration at which the decay of singlet oxygen in the solvent sensitizer sys- tem equals the decay due to quenching by A by both physical and chemical paths (steps 16 and 17);i.c. itis the half-quenching concentration. N.B. Eq, (15) only predicts, a linear relationship if there is (i) constant light intensity, ‘anstant abyurpdon Uy the sessed wis wy ab sorption by A although this could be allowed for, and ( 4 constant oxygen concentration in the solution. For ex- 119 samples see Refs. 4648 and Papes Pw B values are given. Several modifications on this theme are possible in- cluding the addition of quenchers which allow values of Bo = kulko to be obtained. (For details see Paper I* and Eqs. (16) ~ (26) given there), If values of ky are available B values can be converted into rate constants ka and ko. Usually the rate constant obtained in this way isthe sum of ky and k, contributions; however these can be sepa- rated as discussed below. 1 hundreds of 33.3. Separation ofk and ke Methods which have been used to separate ky and ky values usually involve the direct measurement of the ‘quantum yields of oxygenation, d.~. For example at high Concentrations of A such that kx [A] > ka it follows from Eg. (14) that (odin = = daft en Alternatively at low values of [A] when ks ka[A] Eq. (14) gives BATA) oy = SAL (28) ‘Thus measurement of relative valves of du OF ra, under identical conditions at either of these limits allows the evaluation of relative values of &?. It follows from Eqs. (27) and (28) that measurement of du: together with 2 Knowledge of $s, and ke or Bq allows values of kor #10 be determined. Often the limiting yield of oxygenation of avery reactive acceptor (e.g, a-terpinene or 2,5-dimethyl- furan (2,5-DMF = A’)) for which ff" is close to unity (isi k2 mh) ic weed a a reference clbctrate to give val ues of and hence A for other additives.” Gollnick and Griesbeck" have for example measured the rates of ‘oxygen consumption of various substrates relative to that (of 25-DMF at concentrations greater than 4 x 10°? mol L-"in methanol. Since KY > KS, ff" = Land the concen- tration is such that ky{A'] > Ke and thus 2 = Ing, and (kt + KAYA] + kefS] + ko malay a-bé)+ lee da Plots ofr /rAversus [A]-" are linear and values of Kk ‘can be determined from the intercepts. Variations in the slope of such plots as a function of the sensitizer concen- tration allow values of ksk* and klk to be determined. 16h iy vows den Af, As ad Ag van be determined, ex. see Ref. 50 and also Paper I and Eqs. (30)-(37) given there for various other methods. ae or e) ‘J. Phys. Chem. Ref. Data, Vol 22, No.1, 1903,120 4. Methods for Determining the Sensitized Yields of Singlet Oxygen Production ‘According to Scheme 1, as outlined in Sec. 2 and as derived in Appendix 1, Sec. 12.1.1, the quantum yield of singlet oxygen prochiction from quenching of both singlet ‘and triplet states of the sensitizer is given by Eq. (1); ie. ba = bP fl + PR LA) PRALGP on). 1) It follows from Scheme 1 that there would be two molecules of *0;* produced for every photon absorbed if ‘oxygen were to quench all the singlet states ofa sensitizer to give '0;* and if in addition all triplet states were quenched by onygen with 100% efficiency to give 10," ‘This is apparent from Eq. (1) since gs = 2 when PP? PR = fi = fi = f% =1. This limit is approached for some systems (see some of the limiting values for Entry ‘numbers 1.19 and 1.25 in Table 1) at high oxygen concen- trations. At room temperatures air-saturated solutions of ‘most organic solvents contain (1~3) x 10"? mol L? of dissolved oxygen, while in water, ethylene glycol and giye- ero, the values are much less:29, 1.2 and 0.7 x 10-* mol 1“ respectively. Typically the rate constants for quench- ‘of eacited singlet states by oxygen in nonviscous sol- vents are in the range (2—4) x 10" L mol” s~!. Thus 83 [0,] = 6 x 10’s“fand 3 x 10"s""inair-and oxygen-sat- trated solutions. It follows that singlet states with life- times of 16.7 ns and 3.3 ns for air and oxygen saturated solutions will have P& = 0.5; ie. half the excited singlet states would be quenched by oxygen. Compounds with singlet state lifetimes twenty times longer or shorter than these will have P@? = 0.95 and 0.05 respectively. In gen- ‘eral therefore when excited singlet state lifetimes are less than 0.15 ns P&* < 0405. This soften the eae for example for aromatic ketones with lowest singlet states which are rj states. However the singlet states of aromatic hydro- crbone are often euch that J? ic critially dependent on ‘oxygen solubility and thus on solvent, viscosity, tempera- ture, ete, as are therefore ds values. As far as oxygen ‘quenching of triplet states is concerned, 4% values are usually one order of magnitude less than k&5, 0 when the triplet state lifetimes are >33 ys or > 16.6 ws then PF? 0.95 for oxygen and air saturated solutions respectively. ‘When Pf = 1, kg. (I) becomes ba = drfl + PRY + AIP — ox} (38) ‘or equally well in terms of [03] and the Stern-Volmer constant for singlet quenching by Os, Ksy fl + Kofi + flp?? 1 + Kel} $s 68) Since Fe Bai + kwlOl. J. Phys. Chem, Ret. Data, Vol 22, No.1, 1993 WILKINSON, HELMAN, AND ROSS. where F° and F represent the sensitizer fluorescence in- tensity in the absence and presence of oxygen another form of Eq. (38) is Fanos ar nm [E-]. This form of Eq. (38) is often combined with Eq. (14) to sive Fite = oust + on + sity [FE - 1]. sam Thus a plot of oor equally well ba(1 + Kev[Or Tips versus Kev{Os] ‘will give a straight line with an intercept equal t0 dxf and a slope of (f8 + ff f?). In addition often f?*is, per- haps too readily, assumed equal to one in order to allow the sum fl + fl to be obtained Often the contribution to the singlet oxygen yield from singlet state quenching is negligible; this is certainly so when Es, ~ Ex, € Es. In this case fi = 0 and Ea. (1) becomes: a = OPPP IL = oP Pf + PRPPAISP — or) - Ifin addition to fi = 0, PP = 1 oF if one divides ds by PP to correct for total triplet quenching, the triplet yield is still modified by O2 and a = duP? = OP FL = rfl + PRAISP — 47). (39) Although {9 has been shown in some cases to be close 10 unity, in other cases this is not so and the assumption that #9 = I should be checked. However when f??=1 Eq. (1) becomes: ba = ouPPSL + PRY + PRSICL — on} and when f® = PP = 1 (40) da = brfl + PRUE + fC - any}. When there is negligible oxygen quenching of S; which ‘occurs for short lived singlet states as explained above (ie, when PP = 0) Eq, (1) becomes bs = PPT and Eq, (41) simplifies further iin addition P= 1 and the value of s corrected for total triplet quenching is sven by (a1)QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN, O1 = OuP? = orf (42) {All the forms of Eq, (1) given above, fc. Eqs. (38)— (42) have been used in the literature. N.B. When excitation is by pulse radiolysis, yields are measured as G values, where G(’O;*) for example is the number of singlet} gen molecules produced per 100 eV of absorbed radia tion. Gorman etal.” have shown that under the appropriate conditions (e.g. when P&: = 0, and PP = 1), EG) can be wed with CC'Os") and GCS") seavenged by O: replacing of and PPiér respectively is useful to place sensitizers into one of three cate- ‘otis (as suggested in Ref. 52). We prefer not to use cat- egories I, II and IIl as suggested in Ref. 52 in order to avoid confusion with type I and type II photo-oxidations. Je nen Type far molecites where, in the range of e centration of oxygen normally employed, there is no sin- let state quenching by O2 (ie. PP: = 0) and for which therefore Eqs. (41) and (42) hold. We use Type ST for sensitizers which have singlet and triplet states which may both be quenched by oxygen to give '0;", ie. type ST sensitizers have PQ # 0 and Es, ~ Ex, > Es. Equations (1), (00), 14,90) ond 29) op at the limit when PP? AY = fh + JL YP, for ype ST sen We use Type TC for those sensitizers with singlet states which are quenched by O: but which have Es, ~ Ex, < Es and which therefore have f£ = 0 and have triplet yields (BP) and. quantom yields of singlet oxygen prodiction (6s) which depend onthe amount of singlet quenching by cnygen. The triplet yield ofthe sensitizer changes accord ing to the extent of singlet state quenching by oxygen and the extent of catalysed triplet states produced thereby. For type TC sensitizers Eq. (39) holds when P? = 1 and when in addition Pe = 1 the limiting value for [O:] > ‘OF = fl JP, for type TC sensitizers. For type TC sensitizers 6% can be greater or lower than 41 depending on whether f?* is greater or less then ér. TFor type T sensitizers where contributions duc to oxygen quenching of Si are negligible (e.g., many aromatic ke- tones), it follows from Eg. (41) that a wal! * meter | and the intercept of linear plots of 647? vs, [03] gives 64 = doflie. the value at the limit where P21. N.B. In such cases one would have to make studies at much jer onygen pressures 19 reach ne Mit where F&* also equals unity. Several workers evaluate PP? and/or P and are thus able to calculate values of $f and 6" defined above. In the tables such values are labelled with super- scripts (eg. 0.57 and 0.7) although some of these limi ing values have not been obtained in practice but only by ‘extrapolation. 121 4,1. Photo-oxidation Studies AAA. Stoady State trasoton Many authors have reported values for , obtained by ‘measuring quantum yields of photo-oxidation under steady-state conditions. Equation (14) derived from Scheme 1 with M = A can be written in several for 4sKQJA]_ _ _duftIA] be = ot kA] ~ Ba + [AT = oye (14) where pa is the proportion of 'O,* formed which reacts. ‘This equation has also been used to determine using pulged laser excitation” and in pulsed radiolysis expe: ‘ments only with G values in place of quantum yields.” ‘At high concentrations of [A] such that ke < kalA] aft Ofien it is assumed that ff = 1 for very reactive sub- strates. Certainly if several aubotrates give the same limit ing yield," it is reasonable to assume f* = 1. Unless otherwise stated in the Table ‘Comments’ ff has been as- sumed to be unity for all A. The stoichiometry of the overall reaction also needs tobe established (see Section 3.3.2). Equations (14) and (27) are often used to deter- rine ¢a(S) for one sensitizer relative to a ‘known’ value of d(S') for a reference sensitizer, S’, since for measure ‘ments under identical conditions Eq, (14) gives a(S) _ dea) $8) © ba(S' (oa @ (43) Of course the ratio of any measurement directly propor- tional t0 duc can be used in Eq. (43). When low concentrations of acceptor are used such that ke > ka(A] Eq, (14) yields — SIA) _ JanbsktA] a ke cf, Eq, (28) and a first order dependence of the disap- pearance of A with time is observed. The slopes of first order plots measired nader identical ennditinne allew relative values of és to be obtained since ais) ~ Esteala ‘A variation on this theme involves using a reference sen- Seizes ($°), 40 actus a plot energy Uomur tw taser ei ergy to another sensitizer viz. ay 2B 3g’ 41g 38h 4 IS! the presence of oxygen and an oxidizable substrate. In the absence of absorption by S, of singlet state reaction by 4. Phys. Chem. Ref. Data, Vo. 22, No.1, 1993122 WILKINSON, HELMAN, AND ROSS Sor’ and of singlet state sensi is 100% efficient, then f1(S) can be obtained relative to FA(S*) since 1 PPS’) ba(S' + 8) fis) - ASS eS where a(S’ + S) is the quantum yield of oxidation of the substrate sensitized by the mixture of S' and S. Obvi- ‘ously here again any observable directly proportional to 4ucan also be used in Eq. (45). ‘Stevens etal. have evolved a method for evaluating relative values of by the simultaneous excitation of two sensitizers one of which (S) does not react with or quench singlet oxygen whereas the other (S') does. If the ab- sorbance at the exciting wavelength by 5! and & are As and As = A — As, then the quantum yield of oxidation in terms of light absorbed by both S" and S is dba (S +8.) = pa [Sus 4 lS} | (45), ‘where s(S) and &4(S') are the quantum yields of singlet ‘oxygen production for S and S" respectively. The quan- ‘tum yield of oxidation by $' alone at the same concentra- OFS" in the absence of sensitizer da(S') = pabs(S'). NB. 8’ = A, an oxidizable substrate which undergoes self-sensitization and substitution into the equation shove givre upon rearrangement dalS +S _ |. oS) [A ous -E31E-1] oo and thus the relative values of dy have been obtained A A from plots of ba(S +8") gaSyqe ~1 versus = 1 Equation (46) needs tobe modified if energy transfer be- tween S and S' occurs Carre eral have compared the rate of disappearance of DPBF asa reference substrate A’ when sensitized with Methylene Blue as a reference sensitizer inthe presence and absence of several dys A which both quench and re- act with'O;*. When absorption is only by Sin the pres- ence of A and A’ Eq, (14) becomes - MATL Jubs(S'exfA’ a” et RslAT + + BAY since kt" = ky for DPBF. When both S" and the dye ab- sorbs atthe exciting wavelength ie. A = S,Eq, (14) gives dA] & {L(S")bs(S') + L(S)bu(S)} kalA' he + kal AT + (8 + KS] oo) Carre et al.* used integrated forms of Eq. (47) to give 4x(8) relative to x(S') and by assuming os = br (ie. that Eq, (42) holds with ff = 1) they report 64 as values for re 4.12. Pulsed Studles of Acceptor Disappearance When a sensitizer S is excited by a laser pulse in the presence of oxygen and a reactive substrate A (such as DPBF), the amount of DPBF consumed is proportional to $4(8). Thus if the change (reduction) in absorbance ‘An caused by the laser pulse is measured for excitation of optically matched solutions of S and S’, then it follows that since 6.«(S) is proportional to 444(S) substitution in Eg, (43) gives another form of that equation; ie., AS) _ AAAS) a(S) ~ BAAS)” ae ‘The decrease in absorbance of a reactive substrate fol towing citation by alas pulse nrecnuied at an aalye= ing wavelength where only A absorbs is given by Ma = POs*]' peal ‘where 0. represents the concentration of singlet oxy- gen generate by the laser ple nthe extinction cet ficient of A and / the path length. The amount of triplet state of the sensitizer produced by an identical pulse S*]° can be measured by detecting the change in absorp- Vion Jue Wo triplet state absorption Ady, Ths Ads = [S*fet where er is the triplet state extinction coefficient at an analyzing wavelength where the ground state of the se tizer does not absorb. The number of singlet oxygen molecules found per triplet state formed ns is given by n= dp = SEPP + BP _ fOr | When analysis is made at a wavelength where both the ground state and triplet state absorb, er in Eqs. (48) and (49) should be replaced by Aer = er ~ €c. Equation (48) hhas various limits e.g. Mser Baapaes 8) nan = fi when P® = 1 from type T and type TC sensitizers, moat = f+ when PR = 1 and Pe = 1, for type ST sensitizers, and m= nt = fl + ft when PP = 1, Pet = 1 and f? ‘The maximum value of nis 2 when fP = PR = P= fl = f= 1 Gee Ref. 57). Chattopadhyay eral. have reported an analogous method for measuring 6s where two solutions are flashed Ander Aleut woul with eyual aloorpton by theQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 123 sensitizer inthe presence of DPBF and oxygen on the one hand and by a triplet actinometer, AC, inthe absence of corygen and DPBF on the other. In the first case the Change in absovbanee of DPDF following excitation An {smeasured and in the second case the absorbance by the triplet state ofthe sensitizer 49 is measured, Since /,and the path length etc. are identical in the two experiments follows that Ady abe Be Which rearranges to give Mapt ele 3 = ee «) Usually it is assumed that DPBF does not physically quench singlet oxygen and thus pa —> 1 as [A] > ©. Iti also necessary that DPBF does not quench the sensitizer. ‘The method needs to be treated with care. Thus Scaiano eral.” extrapolated their data to ‘zero laser dose’ to elim- inate nonlinear effects due to the triplet state of ben- zophenone, the actinometer they used, absorbing at the laser wavelength. Due allowance also has to be made for any auto-oxidation due 10 DPBF absorbing the laser pulse and for the possibility of the excited sensitizer re- acting with singlet oxygen. In addition relative values of fI have been obtained by subjecting optically matched cells at the laser excitation ‘wavelength of one solution containing a sensitizer S and another containing a reference sensitizer S', to laser pho- tolysis, In one case this procedure was applied in the [presence of oxygen and DFT and in the our in deaer~ ated solution containing the addition ofa high concentra~ ion of a triplet acceptor TA (eg. 0.1 mol L™? -methylnaphthalene (1-MeNp) used to quench > 999% of sensitizer triplet states by energy transfer to give triplet 1-methyinaphthalene®). If AT(S) and ATMS’) represent the absorbance observed for the triplet acceptor formed by energy transfer from *S and 'S’ respectively and AAa(S) and A4,(S') the measured change in absorbance by the reactive substrate A, then (S) _ AAa(S)\AT(S')PF(S') AS - SOR 4.2. Photothermal Methods ‘A useful review of and general introduction to these methods is given by Braslvsky and Heihofl.* 42.1. Steady-State Photocalorimeiie Methods Photocalorimetrc studies have been used to measure triplet quantum yields of quantum yields involving singlet oxygen. It can be shown that heating rates of nonfluorescent sensitizer solutions nsilizess axl uvetall action in the presence and absence of a singlet oxygen acceptor, if measured over short equal time intervals, are propor- tional to AT and AT, the temperature rises without and with the additive respectively. It is shown that 61) ‘where das the quantum yield of the reaction with en- thalpy change AMTa, Nand hare Avogadros's and Planck’s constants, and vis the frequency ofthe absorbed light. Olmsted® used this technique to show that du for ‘TPP ({etraphenyiporphine) sensitized photo-oxidation of DMF, DPBF and TME (23-dimetly1-2-butene) in CCl at concentrations where duis independent of concentra: tion, are identical and equal to 0.88 = 0.02. This implies supa for TPP in CCl is > 0:88 and that du for all three acceptors isthe same and most probably therefore equal to unity. In fact, Olmsted obtained $u for DPBF and ‘TME in Freon equal to 1.00 = 0.03 implying that br, and pa all equal unity in this solvent. 422, Time Dependent Thermal Lensing ‘The fraction of heat dissipated slowly as 'O:* decays as ‘measured in thermal lensing experiments (see also Sec- tion 3.2) is BU bs Ou = We dr <>) (52) where is the average frequency of emission of let oxygen, vs is the frequency of the laser and dr is the Yleld und ts une integrated average frequency oF the sensitizer fluorescence in the aerated solution. Equa- tion (52) has been used to determine absolute values of 43 from time dependent thermal lensing experiments. 423. Laser Induced Photoacoustics It is well known that when a solid or a liquid is iradi- ated with a modulated beam of light, the fraction of the light absorbed by the sample, converted into heat, causes apreseure wave at tne surface. nis photoacoustic wave can be detected (e.g. by a microphone) and used to ob- tain absorption spectra as in a photoacousti tor. When a later excitec an abcorbing col photoacoustic peak has an amplitude H given by H= Kah, where Jy is the intensity of the light absorbed and K is a constant depending on the thermoelastic properties of the media as well as on instrumental parameters, geome- try, ete. and a is the fraction of the energy dissipated as heat within the time resolution of the experiment 1,. En- ‘ergy balance requires 1 - SP See 1 oon) 63) 4. Phys. Chom. Ret. Vol 22, No.1, 1993,124 WILKINSON, HELMAN, AND ROSS where ko is the decay constant of the slowly decaying transient, ('O;*) in this case. Experimental measure- ments can be calibrated since dissipation of all of the en- ergy in a time 1 < 7, gives @ = 1. For example, solutions of benzophenone containing a high concentration of potassium iodide can be used to give a = 1.4 In this way Eq, (53) has been used to measure ds 4.3. Luminescence Intensity Measurements ‘The quantum yield of phosphorescence of 10," is re- lated to $3 as follows oh = oat = Se, (sa) where ft is the fraction of '0;* formed which emits. For 8 discussion ofthe problems associated with the determi- nation of absolute quantum yields of phosphorescence and radiative lifetimes of singlet oxygen see Ref. 68. In snot solvents i is particulasly difficult to measure i) be- cause the values are very small (e.g. they are ~10"® and ~10"* in water and benzene, respectively). However for solvents in which there are na high energy vibrations (e& CS;, CCl, and CICE.CCLF), much higher yields are ob- served” (viz. 0.06, 0.09 and 0.15, respectively). The sin- glet_ oxygen lifetimes in these solvents are_ several nilliseconds. If +f, the radiative lifetime were indepen- dent of solvent, relative measurements of phosphores- ‘cence intensities combined with known singlet oxygen lifetimes would give relative values for 68. However since the radiative process 'A, <"%,- for the symmetrical molecule O; is highly forbidden, 2? is highly solvent-de- pendent and estimates of 4 and «tin the literature are often widely different. However relative measurements in the same solvent are directly proportional 10 ¢s and uch use has been made of this as a probe for singlet oxygen. For compounds where fi = 0, relative values of ff can be obtained from matched solutions by measurement of Telative tuminescence intensities at 1270 nm using the same solvent for $ and S’ extrapolated back to time ¢ = 0 (La(S):-0) and of the absorbance of the triplet state gen- crated from identical lasor puloee (4, (8)). The relation ship used is Hs) AS) Relative measurements of singlet oxygen luminescence decay curves following pulse laser excitation of sensitizers can also be used to obtain relative du values. Usually the luminescence intensities measured under identical condi- tions are extrapolated to time ¢ = 0 when LalSao/bn(SYer(S\POUS! LS aaSetS PS)" x8) _ La(Sheo 56) FAS) ~ LS)" ‘Sometimes this ratio is extrapolated to zero laser inten- sity thus eliminating any possible nonlinear effects.” J. Phys. Chem, Ret. Data, Vo 22, No. 1, 1993 Often La(S)-<0 is measured as a function of laser energy and the ratio of the slopes of linear plots of La(S),-0 ver- sus /, are used with Eq, (56) to give relative ou values. A. ‘comparison of values obtained by luminescence intensity ‘measurement and time dependent thermal lensing is given in Ref. 67. Alternatively the ratio ofthe intensity of phosphorescence of singlet oxygen La(S) observed from a sensitizer S relative to that observed from a suitable ref- erence sensitizer S’ (La (S')) excited and observed under jation conditions is used in Eq. (56). Thus Eq. (56) applies to steady-state measurements provided neither S nor S’ quenches singlet oxygen. It is 8 ‘good practice to extrapolate such values to infinite dilu- tion.* If luminescence intensities are compared from differ- ent solvents the measured intensity Ls must be corrected for diflerences in radiative probabilities by multiplying by +f and for differences in luminescence collection efficien- cies which often depend on n? (where m is the refractive ingen). Thus, corrected values Li have to be used in Eq, (56) where Li = Lan, 4.4. Triplet Energy Transfer and Singlet Oxygen Yields 44,1. Using Triplet p-Carotone as a Probe ‘As mentioned earlier the sensitized production and de cay of f-carotene arising from the process 10" + C4 °C? 0: can be used for measuring singlet oxygen lifetimes (see Paper I"), This reaction is very efficient and has a rate constant of 1.2 x 10" L mol~! s~" in benzene solution, producing °C* which has a strong absorption band at ~520 nm, The process of triplet energy transfer from a donor (TD) to an acceptor (TA) is also very efficient; i.e. *TD +'TA > °TA" + TD and °TA* can act as a singlet oxygen sensitizer. Gamer and Wilkincon™ wore the firet to employ thie process us ing a series of different energy acceptors to determine relative singlet oxygen yields by observing the different amounts of triplet B-carotene produced extrapolated to zero time, Matched solutions containing concentrations of reagents selected so that the following sequence of re- actions could be observed were flashed, S + hy 'S* 9 °S*(4+03) > '0*(40) Ct and compared with S + hy 'S*(+TA) > TAY +02) > los(40) 3 Ct A full kinetic analysis is given in Ref. 70. It is sufficient to observe here that when S was xanthone dissolvedQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 125 in benzene without addition of naphthalene as a triplet acceptor, the amount of absorbance by *C* at 520 nm ex- trapoiated to zero time A¥(S) was only 30% of that civserved when the extra scp of energy transfer to naph- thalene occurred AA(TA). After correcting for the frac- tions of°S* and STA* intercepted by oxygen the ratio. Ficeanthone)/ftoanhthatene) was shown to he 0155: ‘The equality sign applies if the efficiency for energy transfer from triplet xanthone to give triplet naphthalene is 100%, When energy transfer is 100% dir _ ater $308) ~ AVSVPNTA)” ‘Comparison of A§(S) values for matched solutions of $ en and’ containing equal concentration of P-arotene gives a form of Eq. (43) viz oS) _ ANS aS) 7 ARS!) eo In this technique when different triplet energy acceptors Sand S' are used with the same triplet donor, provided ihe efficioney of energy transfer is 1007 in cach casey then S S48 I #3 - Sais) 8) where Af(S) and AS(S’) are the observed amount of absorbance by°C* when TA = S and S' respectively. A similar technique using B-carotene asa probe was used in pulse radiolysis experiments to measure fl for substrates relative to that for benzophenone.” In Ref. 71 the rela tive amounts of triplet states formed in the absence of Oz and B-carotene were calculated by measuring the ab- sorbance by the sensitizer triplets Ax(S) and Ax(S') and using known extinction coefficients (er) to give AS) _ Af(S)er(S)PP(S')Ax(S') AS - FO a ‘where Af is the absorption by?C* observed at S40 nm due to energy transfer from singlet oxygen, extrapolated to zero time. 442. Using Luminescence Measurements With the development of singlet oxygen luminescence decay measurements a simpler technique is to measure the decay of singlet oxygen luminescence and the inten- sity extrapolated to time ¢ = 0 (La(S)us) following laser ‘excitation of matched solutions in which 10096 efficient energy transfer takes place. Using aromatic ketones, for which PP = 0 due to their short singlet state lifetimes as triplet donors (TD) relative values of fT can be obtained from L values measured under identical conditions. ‘The reaction sequence is as follows MED 1 Ay > EDS + ITDA(48) + 384402) > 108 = hv compared with "TD + hy > 'TD* > *TD*(+8") > 48"*(+0,) > ‘Or > how. In the absence of absorption of exciting light by $ and 'S’ and when the efficiencies of energy transfer to the sen- itizers are both unity, then relative values of ff are given ty AIS) _ La(S)asPS AS - BS 2) If the transfer efficiences (i.e. the fractional quenching of the triplet state of the "TD* by § and S’) are known to be Jess than unity, due allowance ean be made. Gorman etal.” introduced this technique and suggest using naph- thalene as the standard of choice in a variety of situa- tions, Gee alae Section 4.1.2, ‘44.3. Using Pulsed Studtes of Acceptor Disappeerence ‘An analogous method for measuring relative f& values ‘makes use ofa reactive reactant such as DPBF as a probe for singlet oxygen production. The reactive sequence is similar: “TD thy + "TD" TD*(+8) + 8*(+0,) > 'OACLA) > AO: “TD thy > TD* > *TD*(+8') +9540: > 'ON(4A) > AO. In the absence of absorption of the exciting light by A, S oS’ and when the efficiency of energy transfer is unity then under identical matched conditions fUS) _ M4A(S\PRIS' Sh" SS cD) where AA, is the decrease in the absorbance of A due to reaction with singlet oxygen. Sea also Section 411 ‘A variation on this theme uses a ketone with P&* as both triplet donor and as an actinometer by measuring the change in absorbance due to the triplet donor absorp- tion at time ¢ = 0, in which case is) = AAs See) @) ‘Again it is necessary for the energy transfer from the triplet donor to be 100% efficient ‘J. Phys. Chem. Ref. Daa, Vol. 22, No. 1, 1989126 5. Quantum Yields of Singlet Oxygen Production — Comments on the Tables 5.1. Contents of Tables 1-3 Quantitative data for photosenstized singlet oxygen production are given in thrce tables containing 1,600 zep arate entries for 750 chemical species. Tables 1-3 follow Sec. 8, The main table (Table 1) contains data for 316 ‘compounds which convert molecular oxygen into singlet ‘oxygen via their excited triplet and/or singlet states with varying efficiencies. Porphytins and related species have been collected into Table . An additional table (Table 3) has been provided for dyes, polymers and some other species which, although they are ill-defined, are of imér- est for various biomedical, environmental, and industrial “eppliations, The ansmngeinent of the (able alphabets by the chemical names of the photosensitizers. Common names have been used for afew compounds; otherwise, systematic names have heen entered. Inverted) names have been used in most cases so that substituted ace- tophenones, anthracenes,fluoresceins, etc. are grouped ‘An index of chemical names and synonyms and a formula index follow the tables (Secs. 10 and 11) and refer tothe entry numbers in Tables 1-3. ‘Oxygen concentrations are given when they have been reported ut else the column headed [Oz] contains ‘a ot “03 to indicate that the solution was air- or oxygen-satu- rated. The Solvent column gives the solvent or mixture of Colvents with the proportions (volumenciume) and the ‘pH or pD, if reported. Heterogeneous systems are identi- fied, (eg. as micellar (mic)), and the surfactant present is given in the Comments. Data for each photosensitizer are ‘grouped by solent and listed in reverse chronological or der. ‘Values in the quantum yield column may be tagged witha superscrtpUT wo denote quantum yields represen- ing 100% quenching of , or ST representing 100% quenching of both S, and 7, Most of the quantum yields tagged T are for type T sensitizers which have PP! = 0 However limiting yields of singlet oxygen production from T; have been obtained in other cases by adjusting ‘oxygen concentrations or by correcting for oxygen quenching of the sensitizer singlet states. Evaluation of PP and PP has enabled the determination of 6T and 67 (see Sec. 4). When P# has been measured for type T sen- sizers, 751s Known through gx{8) and Eqs, (41) and (42), If values of $:(S) have been used to calculate f2 from 4 (or the reverse) they are given in the commenis. Data for the ficolumn, and the column labeled Ef (ft + f8) or ng (the number of singlet oxygen molecules pro- Guced per triplet state formed) are sparse; see Sec. 4.1.2 for limits on ms for type T. type TC and type ST sensiiz- ens, Codes in the Method column combine symbols (see Sec. 6) representing the excitation technique, the mea surement technigue, and the numbers of the equations given above which have been used for analyzing the data If two measurement techniques or equations were used ‘J. Phys, Chem, Ref. Data, Vol. 22, No 1, 1993 WILKINSON, HELMAN, AND ROSS the symbols are combined. For example, PL/LI-S6,42 represents the pulsed-laser luminescence-intensity tech- nique and refers to both Eqs. (56) and (42) to obtain val- ves for oy and ff. Some details of the determination are given in the ‘Comments column. Abbreviations and symbols are listed in Sec. 6 for chemical species which have been used as reference sensitizer (S'), triplet donor (TD), triplet ac- ceptor (TA), actinometer (AC), and acceptor of singlet onozen (A). Values for bs and ff of the reference sensi- tizer which have been used to obtain the tabulated data are given. Quantum yields and extinction coefficients for the triplet states have been included when their values have been used for obtaining the singlet oxygen yields. ‘Temperature is included in the Comment if it has been reported to be outside the range of about 20~25° C. ‘Owe in the Reference voluinn are fom the Radlation (Chemistry Data Center Bibliographic Database. The first two characters ofthe reference code identify the year of publication. ‘The complete references to the tables are listed in Sec. 9 which follows the tables. 5.2, Relative Measurements and Standard Values Often ff or és have been determined relative to the known value for another sensitizer so that the values de- pend ou the standard values ehosen for the reference sensitizer. It would be desirable to obtain the best possi- ble values for ff and ¢ for the reference sensitizers bated on the mescured valuer which have been reported, Unfortunately ff for each sensitizer depends on the sok vent (on pH ett.) and 0 it is necessary to treat the values for each solvent separately, For sensitizers other than type T, values of bs depend on the concentration of oxy- gen even when PP! = 1 For those classes of sensitizer (eg. ype ST and TC) we must therefore treat separately the valles for each solvent sarurated with alr and oxygen, respectively. Values reported as ratios with respect to the value for 2 reference sensitizer (e.8. fIS)fUS') = R(SS') or 4x(S)/6(S') = Ru(S.S')) are often of greater accuracy than values obtained by methods used to measure f and 4s which do not give a ratio but may depend on other photophysical parameters (e.g. 6, er oF Sex) of relative or absolute values of 44. Although the time-dependent thermal lensing and photo-acoustie methods, in principle, ‘only depend on the standard used as a 100% heat pro- ducer to give ds, values of ér are needed, as in other methods, to convert $4 to ff in the case of type T sens: tizers. It has to be recognised that no accurate set of $1 values, however, is available. For example, the é in ben- zene for the important reference sensitizer acridine (Ac) is piven in the literature as 0-797 and 1.07%, We have cho- sen to use the average value of 0.86 for ér of Ac in ben- zene in Table 1. ‘Thus we have the situation where many values of a and f may be connected through ratios and errors of at least 10% are expected; inspection of the tables shows that agreement is often much worse than this. We haveQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 127 jerefure eatsTed Wut ap itcrative averaging process to ob- tain a limited self-consistent set of average values. Simiar procedures used to examine rate constants for reactions of singlet oxygen” and extinction enefficients for triplet- let absorption” have been described. Full details of the exact procedure used here are given in Appendix 2 ‘The procedure gives self-consistent averages for {1 and mutually self-consistent set of average values for és, where 4 is related to fl through br. These values are given in Table A.2.1 (see Appendix 2). Figure 4 shows the interconnections for the relative values of fin benzene, the solvent with the most interde- pendencies. Figure 4 demonstrates that the crucial com; pounds, the values for which are critical, are benzophenone (BP), acridine (Ac) and naphthalene (Np). Inthe case of BP, where or = 1 and ff = ¢a, the ratio Ry (Np.BP) has been indicated to be 1.9 in several careful studies." The global averages obtained for {fof Np and BP in benzene (Table A.2.1) are 0.618 and 10.346, respectively, in the ratio 1.8. The values of 0.29 for BP and0.35 for Np in benzene have been most often used in the literature ao standards, However the ial procedure has directed us to the higher value for BP and consequently, a higher value for Np. The value of 0.35 has been selected as the standard value for é and fTof BP in benzene (see the following table). The global averages for fl(Ac) = 0.99 and é4(Ac) = 0.83 are in good agree- ‘ment with recent papers!” which have preferred du = 0.84 as the standard reference value for acridine. Selected reference valves fr 4s and ff. Noe 3 Sovem [0] aT 1 EACN Gi on Osi 17 ke cn 03s 0s 18 BP GH 03s 035 11s RB MeOH 030 Le RB #0 076 tua Np Cir vse 129 Pe cH. oss 100 216 TR Ct ase "nu numbers im Tables | and Fic. Diagram showing connections between relative {{ measurement for photosensitizers in benzene. Entry numbers in Table 1 are given, Thece ratios for actophenone-benzophenone (AP-BP and for forbenzaphenone-naphthalene(BP-Np) have been measured. ‘J. Phys. Chem, Ret. Data, Vo. 22, No.128 Whenever the average values given in Table A.2.1 dif fer by more than 10% from the reference values of S’ used to caleulate either for dy from R(SS') or RASS’) we have recalculated those values. The table on p. 127 lists reference values derived from the global averaging process which have been used for recalculations. The re- calculated values have been marked with an asterisk and listed in Tables 1-3 along with the reported data. We have also recalculated some values of relative to S’ = hematoporpytin (HP) in CHSOD (e.g. see entry 1.245) where a recent paper identified in the entry has provided a value for (HP) in CH,OD. In some eases only ratios of ds have been reported. We have converted reported ratios into absolute values by us- ing the averages from Table A.2.1 when available, or us- ing apparently accepted standards from the literature, or using a standard value inferred from other reported data. Footnote b in the tables identifies reference values used in this work to calculate absolute values from reported ratios. Many authors have used gs = U./b of U./> tor Rose Bengal (RB) as the reference value in a variety of solvents. The values obtained for water and methanol in the averaging procedure (Appendix 2) are 0.76 and 0.80, respectively. We have used (RB) = 0.76 to calculate values for the 6, column for data which have been quoted ‘only as ratios in water. and au(RB) = 0.80 for data in ethanol, methanol, acetonitrile, acetone, and methylene chloride. Other values used in this work to convert ratios to ab- tute values of (S) are 0.50 for methylene blue (MB*) in ethanol, 0.77 for mesoporphyrin dimethyl ester (MPDME) in chloroform, 0.4 for HP in water, 0.6 for HP in dimethyHformamide or dioxane, and 03, 0.4 and 0.5 for riboflavine (RF) in D:O, methanol and H:O/EtOH (1:1), respectively "The nee of she = 1 fir PAMPTME a6 9 rotor sitizer has been justified (see entry 2.183). The same re- sult has been obtained by the use of s = 1 for both POMPDME and PdOEP (palladium octaethylporphine) for calculating absolute values for octaethylporphine (OEP) and ZnOEP (entries 2.73 and 2.83), therefore ds = 1 has also been used for POOEP to convert ratios to absolute values. No similar relationship was found for values relative to GaTPP (gallium tetraphenylporphine) in carbon tetrachloride so data involving that sensitizer are only ovailablo ae ratios. In thoce oazos the ratioe are given in the Comments column. Ratios also remain for 8 group of platinum and palladium complexes (see entry 3.34 and subsequent entries in Table 3). Likewise. there are a number of metallated dyes (cf. entry 3.85 and fol- lowing entries) for which there is no value in the oa column since only relative yields have been reported. 6. List of Abbreviations and Symbols Bacicution Mestus ca continuous laser photolysis co continuous photolysis wp modulated photolysis 4. Phys. Chom. Ret. Data, Vol 22, No. 1, 1988 WILKINSON, HELMAN, AND ROSS PL pulsed laser photolysis PR pulsed radiolysis ‘Measurement Methods Ac substrate consumption under steady-state Act Aactinometer triplet absorbance at end-of- pulse Ad time resolved substrate disappearance Cb Luiplet beta-carotene buildup as a probe for singlet oxygen production Hp heat produced from singlet oxygen u Tuminescence intensity at end-of-pulse oF under steady-state conditions Oc ‘oxygen consumption under steady-state conditions Pa product appearance under steady-state conditions st sensitizer triplet absorbance at end-of- pulse TAL triplet acceptor absorbance at end-of-pulse Dt triplet donor absorbance at end-of-pulse t temperature rise Other Symbols Mn change in absorption due to acceptor A ay change in absorption due to triplet state A substrate (singlet oxygen acceptor) ae ere Gate AC triplet actinometer Ba aks Bs energy of O2 ('8) above the ground state Ber difference of extinction coefficients of triplet and ground state absorption ~ extinction enefficient of triplet cate abe sorption F ‘orescence intensity of sensitizer P {orescence intensity of sensitizer in pres- ence of oxygen fA fraction of S: quenched by O: which gives singlet oxygen a fraction of T; quenched by Oz which gives singlet oxygen xf Ath # Traction of cinglot onygon which omits 7 fraction of 'O;* quenched by A which reacts fraction of S: quenched by On which gives T G radiation yield, molecules per 100 eV ke first-order decay rate of singlet oxygen in solvent ks first-order decay rate of singlet oxygen for [s]-0 ha Musiuider sadlative dtay sate of singlet oxygen haa first-order radiationless decay rate of sin- let onygenFRR Kw <> QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN rate constant for reaction of singlet oxygen with substrate rate constant for physical quenching of A rate constant for chemical reaction of A rate constant for reaction of singlet oxygen ‘with sensitizer Stern-Volmer constant for singlet quench- ing by O: luminescence intensity due to singlet oxy- gen wavelength of excitation number of singlet oxygen molecules found per triplet state formed the first excited singlet state of molecular ‘oxygen product from substrate fraction of substrate which reacts proportion of S; quenched by Oz proportion of T; quenched by O: ‘quantum yield of singlet oxygen formation quantum yield for energy transfer quantum yield of oxidation of substrate quantum yield of fluorescence {quantum Yield of fluorescence in the pres- ence of O: {quantum yield of phosphorescence of sin- alet onygen quantum yield of triplet formation (inter- system crossing yield) ‘quantum yield of triplet formation in the presence of O: sensitizer triplet relerence sensitizer triplet acceptor triplet donor radiative lifetime lifetime of singlet oxygen radiative lifetime of singlet oxygen integrated average frequency of sensitizer fluorescence in presence of oxygen tegrated average frequency of emission of singlet oxygen Reference Sensitizers, Acceptors, Triplet acceptors, Triplet actinometers Ac 2-ACN ADC ADPA AIPCS An ‘Ang Ans. AP, AQ ATU BChla Acridine 2-Acetonaphthone Anthral].9-be:4.10-b'c Idichromene 9,10-Amhracenedipropionate ion Aluminum(IN) sulfophthalocyanine Anthracene ‘Angelicin Anthracenesulfonate fon ‘Acetophenone 9,10-Anthraquinone Allyithiourea Bacteriochlorophyll 2 BDX Biph BP BRE: BR? BXP Cor Ca(tt) Dye 1 chia co cz DCA DMA 4,7-DMAPs DMBA DMDPA. 25-DMF p-MAP MB MDBH MDH 1-MeNp MOP: 2M2P MPDEE MPDME. NMTA, Np PaTPP PaTPPs'~ Per Pha PP PPDME PrPor Pr(bpy)(Ns)e 129 Benzo[1 2,-41:45,6k'1"Jdixanthene Biphenyl Benzophenone Bilirubin Bilirubin dianion Benoxaprofen P-Carotene (alo p-C) Cadmmium(I1) — 1-(-hydroxyphenylazo)-2- naphtholate Chlorophyll a ‘Camphoroguinone Chlorpromazine 9,10-Dicyanoanthracene 9120-Dimethylanthracene 4,7-Dimethylallopsoralen 9,10-Dimethylbenz{alanthracene imethoxythiobenzophenone 1,8-Dinaphthalene thiophene (Diacenaph- thofi,2-b:1',2’~d thiophene) 3-(3,4-Dihydroxyphenyl)alanine 9,10-Diphenylanthracene 1.4-Diphenyl-1,3-butadiene 1,3-Diphenylisobenzofuran 25-Diphenylfuran 1,6 Diphenyl-13,5-hexatrione 1,8-Diphenyl-1,3,5,7-octatetraene 2,5-Diser-butytfuran Eosin (Tetrabromofluorescein) Erythrosin (Tetraiodofluorescein) Ergosterol Furfuryl alcohol Fluorescein Heterocoerdianthrone Histidine Hematoporphyrin, Hypericin Imidazole 4'-Methoxvacetophenone Methylene Blue Mesodiphenylbenzhelianthrene Mesodiphenyihelianthrene 1-Methyinaphthalene Methoxypsoralen 2-Methyl-2-pentene Mesoporphyrin diethyl ester 10-Methyl-9-acridinethione Naphthalene Palladium(11) tetraphenyiporphyrin Palladium(II)_tetrakis(4-sulfonatopheny!) porphyrin Perylene Pheophytin a Protoporphyri Protoporphyrin dimethyl ester 2.7.217-Tetrapropylporphycene Piatinum(tl)diazido(2.2" bipyridine) J. Phys. Chem. Ret, Data, Vol. 22, No. 1, 1983420 WILKINSON. HELMAN. AND ROSS Pi(phen) Platinum(I1) _ (1,10-phenanthroline)ter- (BCAT) _butyleatechol) Pt(phen) _Platinum({1) (1,10-phenanthroline)(2,3- (@hn) —_naphthalenediol) Py Pyrene Pe Phenazine RB Rose Bengal (Tetrachlorotetraiodofuores- BEE Roc Benga ety! eter Ret (all-£)-Retinal RF Riboflavine RNO N.N-Dimethyl-4-nitrosoani Rub Rubrene (5,6,11,12-Tetraphenylnaph- thacene) TEMP-4-0H 2,2.66-Tetramethylpiperidin-4-ol Yetr etracene ‘T(m-HOP)P Tetra(3-hydroxyphenyl)porphyrin ‘T(p-HOP)P_Tetra(4-hydroxyphenyl)porphyrin ME 2,2-Dimethyl-2-butene (Tetra- methylethylene) HsTMpyP** Tetra(4-N-methylpyridy)porphyrin TPR ‘Tetraphenylhacteriochl TPCP —_Tetraphenyicyclopentadienone TPP Tetraphenylporphyrin HATPPS* —Tetra(4-sulfonatophenyl)porphyrin ‘Trp ‘Tryptophan uP Uroporphyrin 1 ZuTPP —_ Zinc(II) tetraphenylporphyrin idacol-2-yNaco- ‘Za(Il) Dye II Zine(I1) 2-(4,5-diphenylimidazol-2-yl)azo- ‘4:nitrophenolate ‘Medium components Aor Di(2-ethylhexy!) sulfosuccinate Brij 35 Polyoxyethylene(23) dodecyl ether BSA Bovine serum albumin ter-i500Htert-Butyl alconot crc Hexadecylpyridinium chloride CTAB —__Hexadecyltrimethylammonium bromide CAC —__Henadecyltrimethylammonium chloride DAP Dodecylammonium propionate DDAB _Didodecyldimethylammonium bromide diox Dioxane dis dispersion DMAA —_N,N-Dimethylacetamide DMF N.N-Dimethyiformamide DODAC _Dioctadecyldimethylammonium chloride DPPC —_Dipalmitoy! phosphatidylcholine DIAC Dodecyltrimethylammonium chloride EIOH Ethanol HSA ‘Human serum albumin MeOH —— Methanol mic micelles i-octane — 2,2,4-Trimethylpentane 1-PrOH —_-Propanol 2PrOH — 2-Propanol PS Polystyrene rl Pyridine SDS Sodium dodecylsulfate THE —__Tetrahyérofuran ‘Triton X-100 Polyosyethylene(10) 4-(1,1,3,-tetramethyl- Dutyl)phenyl ether ves vesicles 7. Acknowledgements ‘The Radiation Laboratory at the University of Notre Dame is operated under Contract DE~AC02~76ER0038 with the Department of Energy. The Radiation Chem- istry Data Center is supported jointly by the Office of asic Energy Sciences of the Department of Energy and the National Institute of Standards and Technology, Standard Reference Data Program. This is Radiation Laboratory Document No. NDRL-3491, The autluss wish to thank Drs. Gordon L. Hug and Ian C. Carmichael for discussions and for help in locating data for the ex- cited states of some organie maleciles which accicte this evaluation of the singlet oxygen yields. 8. References to Text "Senagp, A. Pa Sigler Molecular Ongen. Dowden, Hutchinson and Ross, Inc, Stroudsburg, PA, 1976, 385p. 2 chil, W. H.1; Mecke, RZ, Phy. 68: 344-61(1931) 2wallace, Ls Hunten, D. My J Geophys, Res. 78: 4813-34(1968). ‘an, A. Ui; Kasha, Made Chem Pip 39: 2105-61963), “Arnold, S.J; Opyalo, E, Az Witake, HJ. Chem. 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Pau, H, Ongen and Op-Radicalsn ‘Chemisty and Bist, M.A. Rodger and E L-Poweses) Aca , Naturwisenschafin 19: 1083(1931). Neuwirth, Rs Baumeister, W, Chem. Ber ‘pounds and Polymers. Wiley, New York, 1978, 331p.‘QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 131 Wasserman, H. Hl; Moray, R. Ws Singlet Ongen. Academic Press New York 197, 684. itingn, Fs Brammer, J. Gy Pls. Chem. Rf. Date 10: 805- 95150. Foe, CS, Phtacem Photbe 54: 659191. Gath eA Phooch 6: 1-122(1968. fet 8, Pre Rad Bat. Fle 2, WA. Poo), adem Ten, Now Yorks 1976p Gorman, A Az Lrg, G: Ros, M.A. J, Am. Chem Soe 003792097), 2k, A Ay ty Bal dead Sek USSR. Pls Sr 42: 365- a970) asta Wolo A Nae S88R. Son in #89 et -rknaowly, A.A, rj Neveron, K Vj Eg, S. Yus Roeder, Bi Levi, Tr Phacchem, Phil B82 245-5(1950. ‘Wc. Py Rete Bs Lands EDs Redmond RW, Prost TG Photckon, Photobiol 43117-20158, Op, Us Seikl K Schmit, Rs Braver, HD, Photochem. Pho inl, A 29-3819). pity, PRs Fone, © ym. Chem Sse $04 2069-70890) Rodgers, M.A. Js Saomden, PT re. Chem Soc. 108: 554i— 0082). Gorman, A. A; Hamble, 1; Lambert, C; Prescot, A. Lj Rodger, Gee ts ycney tt Bae Chae Si am, SOL eT Gennan Ls Noe, 3 Wen, Ty Saeler, Ey Ory. Chom 54 3561-41989) Schermann, Os Voelker, A Seitl, K; Schmit, R Braver, H. Da ‘toch G; Gar NA: Bry, SEs hehe, 91:37- 80585). “Young, RH, Brewer, Keller, And Am Chm Soe 98:35 aoe) ‘aterkl PB; Kearns, D.R. J. Am. Chem. Sz St: T2US4I972) “Matheson 1B: Ci Lee J Chom Ph Le 7: 15-6197. “Matheson, B,C: Le, 3: Vamanash B.S; Wolbarst ML J.Am Due Ba oon 905 “Famila, A; Wikio, Potachon hoi. 18: 47-5019). “Schenk, G. 0. Gani, K; Neumucler,O. A. Ann. Chem. 603: S495). “Getnch, Ads: Cham. Sor. 79: 7-301 1968), Chto, 5K Romar ©. Dan PRs Poche 24 oasee Sc: nn 2 C; MacEschero, A; Arason, 3 ‘ochen, Pt 08-9098 * Chtopatyny, 8 Romar, Vj Bas PJ Phos, 30 sre “Bray, SE Ht K, CRC Had bok of Ono Phtachen ay J. Seed) RC Pree Rt FL, 1 Va eo ole Chm Sa. 08 7180. Rona Gar N'A laa $ Phoache 3137- 608) “Redmond RW; Het, XK; Bay, Bs Tat TG Pho sche Pwto 48236 ‘co Redmond, RW By, E Rouge MS Cs Fore, A: Bemus RV, ocho Phil 81641990) “ek; Bray 8 2, Chon Pe Lat 31 803980, 9(1988). “ “mc AP: Nebr, 1 NB, LM Dron NN A ‘aha Chom. Py Let 1814-50051). mn hs pores hs arin Pie a 148 aca) camer A Wikio, F, Set One Rete with OeiCon- ‘nun od Pome, Ray snd) Raed) Jobe & cam tet nes tere 5 pice 1M Gorman A As Hob, Kon C. Ws Lambert Cs NeNceney, 8 Pe ooshon obi 48 4942989) “Kelis, A, J ps Chom 42119-8097, Pein a Ser ene Oh i ay Ve ok FJ Pipe hom Ti >Retrne 26 Ape Carmel Henan, WP Ha. .LPl Che. oD 6 nen dame, A.A Rodger M.A. J. Am. Chem So, 108 SO ‘con rm AAs Ro, M.A. J Am On. i, 58% shea, A. Meare, D. 3; Tra, Tg Lambert CRs ad 1 Chem Ss Fora Tr: 30-2099), vane RL Rte € 8m Chom St 44 SA) Morand, P; Wet, D, 4. Phys. Chem, Ret Data, Vol 22, No. 1, 1953192 WILKINQON, HIELMAN, AND NOSS ‘able 1, Quantum yields of photosenstized peeduction of sage oxygen, Hon Sonent (0) Ie SE Born, Method Comment Ret LA. 2 Acetonaphthone (2-ACN) Cale irr Oy on oat See Table Cae ie on" 087 CPLES6A2 —$'=9-Foorenone; we 1068) = 085; used 91FIDS {8} = 086, 7» fy mesared rato oft Kye) = 336 and (6) = 367 om, or oss a0 PLILLSCS542 $= Aceh I0fTS)= 10 hye = 355mm; BESTS wed 5) = 084" e4(8)= 1050 L mot fem? 2430 nm, 678) ~24,300 mol ow? 5140 nm, PP Band S)= 1 coat ao: ons? 087 PLNpS242 Yog 355 am; sed 5) s8Eu9 2073, Cal on™ 08s PULLS? S'=Pe eel WAS seas (084, Meaued cag cr os as PRAMS —_A=DPBF ued (S)=084,e4()= 105007260, 9 Lou" ca a 80 am, Memared 4°39), cop i ont CPILESS ——S'=RBjreL104y(S) = 076. P= meas, 91723 rato of, at (5) = 336 ad lS) = 547 MeoH Oy ost CPIACIS ——A=2S-DMF. Age =313 0m, PP 6101 412 Acstophenone (AP) ere ee oss PLALSS542 DPW /s%E) 028, y= 28E mm ADI os" 029 sed 68) = 1 Ca, oa? oat PLRCEAA2 S'=BP;TD=S:rch.10/,58) 035: used T6804 OxS)e 1. Measured @(S),(8) = 12 cae Oe os” om PLIp-S242 yg = 355 nm; wed OS) = 1. Measured ¢y H8EAA9 6 and GeO 03s? 036 PLILLSGA2 — S'=Pr teh QS) =O weed g(S)= 1, SEEM eases PF =U Cae Oh os PUAGTAY —S'= BP; AwDPBF:TAI-MeNp ecto 854268 3s? 035 soz IS)" 038; eas. 48)" Rae = 387 fim. Showed? (Sand $)>095. HCN Oy ost os PUAGTAL —S'ZBP:A=DPBR:TA=I-MeNp reLio _ 85A268 soa I4S)= 0537; ess. (8)= 1: Rye = 337 ‘tm, Showed P' (Sand $2095. Moon Oy 0.95. a aa fghiaemnye Tee nn. Showed PP (Sand $) 2085, 1A Acctophenone.¥-methox- Heit 03s" PULLSESS Se BP re 10f.TS)= 029; he = 355mm, $6420 027 1S Aestephonone 4 athens Cale oe PUAGTAL —S'=BP;A®DPBF,TAs I-MeNp.rehto 854268 oz on 5082 FNS) = 039; meas. 648)" 1" Pee= 337 fm. Showed 72 (Sand S) 095 HNO oak on PUAGTA- —S'=BPLASDPBF;TA=1-MeNpreLio $5428 saz $eNS)=037; es. O48) = F Dee = 337 rm, Showed P9 (Sand S) 3095.QUANTUM YIELDE FOR FORMATION OF SINGLET OXVGEN 429 ‘Table, Quantum yields of photosenstined production of singlet oxygen —Contnaed Ro Soke 10a fet f Borny Mebod Comment Ret 1.6 Acetophenone, 2nethyh biraica CHEN ie ox 038 PULLS SAG ICL10GS)=O8; tng = 397m, H9AIL {Js bse on gustan yelé of radial ration = 0.60 is san cog 1012 mol 127 Aeriine (4) Calle iron, 0x3 ase See Tbe, Cae ost PUMP S242 hae 355 nm; wed (S)=086", Measured SBEA9 OS 088, PP and Cie ost PULLS S'=PureL to g{S)=08%: wad gyS)= SEH Ci ast 07 PRIAGSL A= DPDFL ued 5) =Q86F,e5)=24300 THES yy Lot" cna 440 am. Measured G'S, coc, =e 10? oss PLAGACI9 A=DPBP,AC=BP;2og = 337 mm wed STEAIO GAO) Ise AC)= 1640 Lil cat 525am. P= Isp Hen on? PUPS Dee =354 om, wwzi35 14 9-Aerdiethione, 1meyt- (NMA) Cin 1 PUAGSE — A=DPBFLAC=Simeat.0y(5)=079: ge MEM? 39 485 um: wed hg» SOx 0h byw A OF ott, 6) = 0000 Lie ca 520m. Measures P. Ci os PUAGS —— A=DPBFLAC Si meat. OS) 085: hue HEME #39 85m wed y= 4.0% 10 bg = 80% 1 Lima", 28) =§300 Lil em at 20mm. Messed P. CHEN Oy oss PLUAMS- —-A=DPBF. AC=S: mess. 20 2 R5 ms ed fgn 2 Se W 10? Lio 1, 68) = 000 L ma 520mm. Measured PE MeOH 0; 19 PLUMS — ASDPB:AC=S;meas (9) 075 hag HEM oo Spot ey ge ete aye ane 10 Lima" eS) 800 Lm om! a 520mm. Measured FS 19° Acrdintum, 24¢dlamino- Profane) no ait a 02s CP ACASA2 S'=MB; A=25 DMF: 10 9S)" 052: 737339 ed (8) = 047, Assumed PP = 1. 140° Acrdiium,34diamtuorHoaethg: (Aerie) cH,coce, ait 1 MPLESS —S'=Paapel.toS)=08. RelwoS'in 622317 ca. _aopsorateneuro3}enaopyran7-one) Ce ose PLALS642 Sm Acre. t0 QS) 0.7% meas 4S)= —BBEIZI oo” ast O17 Rgg= 355m. P80 1.12 AnglcnFurof23.Aiemopyran--one, Ane) Cie oo” 033 PUAL642 — S'mAcrEL wg) =07% mean iS)= — SSEI2E ear ove inise HPP EL 9S) =U ge ADEM. SEBS ‘oomst boar ome? PALSS —S'=RFirL 09S)=03:2y¢=337 am, SGESSS Boia Moon air on? PLLLS6A2 —S'#RF rl t004S)= 04: 2g "337 am; S6ERSP wed 8) = 0318 ors134 WILKINSON, HELMAN, AND ROSS ‘Tobe 1, Quantum yields of photoseaszed production of singlet oxygen —Continsed Ne Solvent (Oa) te LETS (SYerm Mahod Comment Ret 1.43. Anthracene (An) ‘w-DuOH 02 an O> PULESE gl tucey yy = 0.32 are008 1BW0H 02am, PULLSS al s(oleney) = 0.26 s7E668 (Cig:0 O2amo, PULLS aloes) 0.35 s7E668 eaam os Puuise ——dalstoteneyg) = 038 s7e668 nee — 02am 05 PULLS ——u(s(olene/s) = 068 s7B668 CasCH, §—O2amo, 083 PLILS856 wed 64S) 2072. Asumed f=; wed feT TESS Tom jf=046, caecH 10 PLILS8.56 used G(5)'=0.72. Assumed P= tase fg™ STE = and f= 046, cay, anit 10 PLIAGE HE ARaby ge =247 ame wed bY) O7,—_eOFUTS 548) = 42.000 Lmao at 28 5m, re CaEN 1210 O57 PUAGSHAS —ATRUD Aye = 347 am sed gtS)=072. F075 Pe I wt 3) = 24000 Lm en Reams = O57 CHC 02am 0, PLILLSS ——dy(etluene)s)=095 78568 Clg Oa Op Fua90 ——gtyutuenry)= 089 sre008 Ci 1x10 ase? PLLLS6A2 —S'= BP: re 10 G(S)*029; tye 388m; SEAS? wed (5) 0.75. PP) <0.0 and P2099, coe 078 PLP S242 gg 397 nm, Mosned aed PO SIFID 11S}> $210" mt 1 ed Gy 022: fy $0.0 extrapolating IS] Gauthors used mes $10 ge fa = 095 bat PP #0, cae ae ut PUMPS ge = 399 0m, Assumed =O, 9 =O7E NESEY ves fa! = O78 Calle i os PLACD3 — S'= BP oG(S)=035. Meaued T6904 $4468) = LB sine P20, ot aie tiaiabe Cae xo as Chet SEA=DMArrL 10445) =052: Que" SIFSGH Se5nm. Assumed /?= Ca os Pulls? Age 388 nm wd yf S) OTE. Measured SBE 42068, P= ant 6 = 4S) and ‘Autor stun = O and = 087 ba 052 so values ofan ae ‘determinable Cie oss PLLESS ——S'= Pir. 10 0u(8)= 083, Meaured /P'= 886449 1 and = 6). Authors assume f= 0 ih 00F va 08 ans ofS tnd "ar indeterminate. Cae 07 PRAGSLA — A=DPBF used 65) =078,e45) 545300 78263 Lot" en”! a 432 nm, Meare GCS") Cae 0x1 as CAGH638 = A= DMA; 1045) 10; Que 365 SIFIAE ms wed (8) = 0.74. Assumed f= ,(8)= 1 tough coronene wing (a. mje 2am 0 PLLESS ——gy(slolueneys) 063, srE668 CC amo, PLLLSS ——_oy(tolveneys) = 0078 Test ce ae MPLS S'= TPP el to #6) ~07. 60999 ch COIS AnSi ge 365m ss7ao4 CHA, — a2amo, PALS OxGfthunei4)=037 STE CHEN o2am0, PLLISS ——_dgCtloeney) = 027 7568 cH,CocH, 2am 0, PLLESS dC stlvenen) = 045 Tess 4. Phvs. Chem Ret. Data, Vol. 22, No. 1. 1999QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN aa. ‘Table 1, Quantum yes of photosenstized production of singlet oxygen —Coninued a) & AY “Horny Mead Cone i 1.13 Antracee (An ~Comied cic, o2amo, PLIS6 eaten) oy cH, 0 CHOC AS Rage 35m sno SO on coc ssn DMF 2am op PUSS — sens) 036 e568 HOH O2amo, PLULLSS —gstienys) = 0.26 nee HCONH, 02am 0, PUNISS —g(esbciens) 0.20 sree MeOH at 0 runs Fre 0449) =04, 959 ROH 2amo PUSS —lotenvs)=03 res 2ROH —a2amo, P1156 ostoienys) 032 ss C0 02am, PULISS —euouenys)= 044 — 116 Amrcen, tore a ww crock —nesikee som enw ci, oy 066 CHOC Ae SiR 365m, sore SO 068 CHOC AeSiRgc= Sm, sno 145 Antracene tore: cu 08 croc sora a, 056 coc snot co as cme ‘srt 116 Antraene,25% SIF96 {Sot Lately = gy 04h 8 eames) 118 Antracene,810eore cu an CHOC1 AS Pog = 35m sao oH, oy 16 CHCl AS Aege 38am sot So 20 CHOC1 Kesha 38 S514 149 Antraen,910 Cae tanita PU God Bry nk we 669020) mean 4) vOEASE Os" ons 039 hog = 389 wn. PP <2 and PP 2038, 124 Anthencone,01.4Almety loth HOCic) air mts S'm An: Anim: Pu imidazole ‘snow m7 ndoperoide; meas. (iS) = 006, son con, 1% CTAB, BNO as monitor of. 1.25 Anthracene 9phens. Cay Os 11 49 30s CAC? AR2SDMP tg =313mm, PP 1; 8S sumed P= sed p= CasCHy sy x0 CHACHE38 AS. Asmmed f= 1G" =008, FIT CaO exit PUAASHAE — A=RUb:AC=Sihge = 347m ied hy= —AIEASL B2x1ts age 33x 0" Lamotte SAC) ~ 12.000 wn ot at FP = tread n= 2, ts f= Cah aie att crac 1440 a6 Coat ” Coma Aes entsbon PP emma M8 Maen ch ars CHEM ARS ss7004 Heh Oy 08 CCI ASR soos & o 8 HOE ARS sst004 126 Anthracene, -netht- nite Or ar m0 ae C8INe2T Aw 2SDMF Reg = 313. E685 ssomed = Id =| ce 3 CHE ARS:Ryg 365m, 700 HG, Oe 2 CHO AnS A= 365 37004 1.27 Amtracene,242-2-naphthyeteny (2) ae ae wae Punt 669 C nme te G0) 027s mean dyO)~ OEE ait on iarine= 38m, ch oa PS 2038 1.28 Anthracene 21242-nahih eben Cie 13x ae PULLS642 — S=BPreht0 gS) = 029; meas gyS)= SEAS? ao 04s 022 igc = 358m. PP MD and PP 2088 129) Anthracene, phen nLite Op 1 ms0 ane connext ot643 Gy Oo ass rio 14 008 cia, oy ase CHOe ASS A= 57004 o o 091 CHOC AS; 65am, sso 130 Anthracene, 42-phenylthenyt(Z- Cie 13x ae PULLS6A2 —S'= BP re to gS) = 0.29; meas. y)= EAS? coe? oa UN: ae = 385 0m, Dan PP 086, 131 Anthracene, 242-phenylethen (6) Cie axis ison Sanmawossa0rr ne oS sD 10" ast = O15 hye = 855 am, PP <0.02 ao 20s J. Phys. Chem. Ref. Data, Vol. 22, No. 1, 1963120 WII KINSON, HFIMAN, ANN RASS. ‘Tble 1, Quantum yields of photosonstzed production of singlet oxygen-—Contnued No. Solvent [03] SPSS Borg Metbod Comment ef. 132 Anthracene, 2-(L-propen)(E)- Ce 13x10 PL s642 BP; re. to y(S) "0.29; meas. oy(S)= _BBEAS2 oa" ase 0.46; dae = 355. P< ana PP 209 133. Anthracene, 26910-etracyano- CiHsand—sirandOp Ft CPI ig #365 nm, A= TME,2M2B, oF asF160 cHeN {elohexene, P= alkene hydroperonides, solvent = Clg and CR. 1.34 Anthracene, 2-ving Cae xt oe MUSA? S =D Log) = 02h mea gy) SHEA? wae" wre 054; Age S99. P< an 3099, 135 L-Anthracenesufonate on Ho 3x17 om 1 cPIACts rears 1236 2-Anthracenesfonate jon #0 3x10 070 cracls means 137 Anthral9-be:410.8¢ehromene (ADC) Hcy @5)x107 08 crAc1438 aris 138 Anthral20def6 5104 7 Wisoqunolne, HN-dimethyl- Do ° 00 PLAS ea zaTMpy eto 98 = O88: meas. 21R201 G19) 0123 2g = 355 am 139. 9:10-Antnraguinone cite ous" or Piacoa? — S'=PrirhwoS)= 085; wes oYS)= READ (090, Measured P2 = 068 cola aor 2st 029 Pup S22 85 my; used QS) =(190, Measured SEAS PP 0.5 an8 cacy, ie oT PLILLS6 'S'=MPDME; rel. 10 94(S= 0.77, PR 140 9,10-Anthraquinone,I-amino- cesar wr Fuse MLE; toga) =UIT. 2ROH ir ons PACA} S'=1.5AQINHs A=DPBF; rel 0448) #8FS82 #063) = 080; hae = 434 nm 141 9410-Anthraguinone,2amino- cH, ai 000" PULLSG —S'eMPDME; re. 0¢y(S)= 0.7%. P=. S6E640 2POH ai on" PACA) Sm L.SAQ(NHjs A=DPBFirel iogS) #80582 nye) FU ath ge = 3. 1&2 9,0-Anthraquinone,{-amino-2-hydroxy- cH, aie 02" PLILS6 ‘S'=MPDME; re. 10 9,(S)= 0.77, P= 1, 86B640 143. 9,10-Anthraguinone,1-amino-tcydroxy- ich it ooo PULLS6 = MPDME; re. 10 Meno 00s CHA F=RD;A=DegSiveh 10 $48) = 0.80; Age 8OPI04 346m, Measured PP = DROW air ons PACS DPBF:reLw oS) 8852 Ho) 144 9,10-Anthraquinone,1-amino-4ydroxy-2-phenoxy- cuca ost PULs6 -=MPDME; 10948) =0.7%, FREI. S6B640QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 139 “able 1, Quast yes of potsenstnd production of ingle oxygen-—Contnued he Soven (03) ei He Metiod Come Ret crc, ie ost PULIS = MPEE: reo AS)=O77, PP=1, SRI HOH i os? (CH0C43——S'* MPDEE: ASH,NCSNI re. 9,8) 12F681 071. Assumed = 1, PP 14S_9,10-Anthraquone, -mino-:hydroxy-24(phenlaminosuony)pbenoxy- cH, ait om PULLSS §——S'=MPDME; Lo ¢uS) 077%, F cH, ait oni? PULLS) S=MPDEE:ReL0GS)=077. Fel. 82F631 Bon it ous? (roe) S=MPDREASHLNCSI LS) BR 77. Asumes PB = 1.78 146 9,0-Anthraqunone, -mino2-methye cy aie ot MPLS S'=TPBCireL ways) =045 ase ca, ant PULLS S'=MPDME;reLi0@S)= 07% PE=1, B6EOH0 aT 9t6-antmsagainone, ttre cH, it ° PULLS = MPDME. Pi 08510 148 9,10-amtraquinone,2-coro- cic, ait ° mass MPDME. FP =1 08640 149 9.0-Anthragunone 1 2iamino- enn, ft PRLS a MONA one) wat sem Hcy ae <00s CliPié —-A=DMAP=9,10Dinetyimicne SBS endoperorie; Aye 435 rm, FP row cor Chise#S——S'=1S-AQINHYs A=DPBF e148) SHES Ron (6 ges Seam, 150 9,0-Anthragunons, 1-tiamino- car oo PILES S'=TPBCireL wo,9= 045. oases cH, ait ani" PULLS S'=MPDME:reL10¢S)= 077, PP =I, 865540 cue, ir 00s ChiRe14——A=DMA:P=9,10Dinetylancene ——SOEHE endoperoride; A= 435 nm, P= 2RoW ai ous? CPiReAS = 1.S.AQNH: AX DPBF EL 1048) SHFSED Hon O86: Ae = 588m. 4181 9.40-Anthraqunane, 1$diamino- ccs at as? FULISS —S=MPDMEreL06S)= 077, Pet, 868640 cue, aie ost ChiPet4——A=DMA;P=2,10-Dimeiylintacene SOE operon; A= 435 am. PP = anon air oxo? Cite ARDPBF A= 04 om, srs HOG 4152. 9,10-Antraquione1dhamioo- CHC, ie ox? PULLS S'=MPDME: re 1065) =0.7, Pet, $6860 cue, air ont CRAM —ASDMA:P=9,0-Dimetinlanvacene SOB emloperaie; Ro = 435 nm. FP 2ROH air os” CHiRe$ = LSAQKNH An DPBF EL 1048) SHFSED #0) = 080; ge * 45m. 153. 9,10Antraguinone,2/diamoo- 20H aie ons? CPRes $= 1S AQ AXDPBF L109) BPSD 06D 2080; gg 43tan. 1.84 9,10-Anthraqunone,1$diamino-bromo-48-dhydroxy- cic, os PULLSS —S'=MPDME:re.t09uS) "07%, Pa 1, 868540 cH, re aust FLLLSS — S'=MPDEE: nL t04y(S)=O77. =i. RO ‘J. Phys. Chem, Ref, Data, Vol 22, No 1, 19894140 WILKINSON, HELMAN, AND ROSS ‘Tbe 1, Quantum yields of photosensitized prodction of singlet oxygen —Contined No. Solver (04), ee orm Method —— Comment Ref, ne 1 S-iamine-2-bromo-43-ihydroxy Continued ca, Ps o20 MPILLS6 5 = TPBC; 1. 10 @yS) =048. eases BOH air ous P0683 MPDEE: A=H.NCSNH rel. to @y(S)_$2F5S1 (07, Assumed PP = 1, 2 1.85 9{10-Anihraquinone1,5-dlamine-48.dihydroxy= cua, air oss? PUALs6 6510 1.36 9.1-antnraguinone,13-atamino-4-sM0 TDS Biers fmm PP =O witht + hgh Ho anwar aas CHNe Aas ARTI mes 94S) =U Age =>5H TASS tiers ten Fh =0, in poem of Type ‘ood: With y= +A) emabutancie aid 2 dlamine 3hydonyton-@ Hydrexgtgmirenin) vows ar 0s PALS S'eRF.L109(6)=030)\y¢2337om. TF J. Phys. Chem. Ret. Data, Vol 22, No.1, 1988142 WILKINSON, HELMAN, AND ROSS ‘Table 1, Quantum yds of photosesitzed production of singe oxygen —Continvcd Re. Sevens (0 he Yorn, Method Comment Ret 177 Remnatutanate seit 1,9 -aminn pdeneyipaen (UHyAraeyymienine—Cotin ae ° CPPS S'=RB:AsImreL1094(8)=076 Age= RIA 360m, RNO as monitor of P PULLS S'eRFieh wo 94S) =030, F290 CPPS S'=RB: Axim reL1094(8)=076 Aye= 9IRISL PLILSG ——S'=ZaiTPR EL 1095) =O7R: ge 308 SIAM 0.05 PULLS FTP, rel. 10 0S) #073: pe = 308 91341 11. 1/-Bemeneiol (Hydroquinone) ox sie oat PULLSS S's ZsTPP teh. 1094S)=0173; Re =308 START rm. May be from quinone conamiens. SZ 14-Benzenedl chloro. ox oO; aot PLLISG ——S'eZuTPP seh. 1964872078: =308 SIAM ‘am, May be from gunone contains 183 Bent cH ast om CPLA An 1 7-Diwstyteergheroe 2 ase timed $y(9)= 092%, Be 3 Hydroxy. 12 dimetiyeytoberene,2Hydrony-2-nethy- [-methlideneyetobexane and 3 Hyaros 23-dimethyeyeohexcne 18 Ben, 44-dihioro- feo tron 023 Chel -A=12-Dimethyeyetberents A366 SSFISS “inetyleyclahaxen,2-Hydroxy.2-nethy- ‘-metyldeneyclobexae, sd Hydroxy. 23-dimaiyleyelobexne 188 Bena, 8-shmethoxy- Cae Oe oz CPP A=12Dimetiyleycloberet: Ae asFiS3 fyeony-2-metigl- ‘etnylidenecyclohexane, and 3 Hydroxy 23-dimethyleyclobexene. ChPe14 A= 12-Dimethyleyeohexene: gg =366 — SSFISS fan. Pa3.Hyarxy-12- yao 23-dimehylyelobexene. 187 Benzo(1 2441456" aivanthene(BDX) HCH, air 19 CHACI43 AS. Assumed P= 1 43fo"= sario7 1.88 Benzophenone (BP) CD air a2" 029 PLLLSGA2 — 2..=38S om: wsed ovS)=1. S'=BPin— S8E6S7 ‘zee, wed 04(8) in boaee = 029. Ci airoe 0, 035 035 SeeTabeQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 143 “ale 1, Quan is of photoes prodeton of singlet oxygen —Conina Rov Seven % ik Ham Meld Gomme ee 1.88 Berzopenon (BP)—Continued Caen wer us PUMPSEAL te S8/ 0m. Messrs fy ssumes = YIN cha osiT ast PULISTAD Se Prehi0 94S) O85 wed pS) LO. OASIS Pel, Cae oa PULA S=NETD=pMAP re wfTS)=088 TEI cast 029 Jen = 355 wed 6()= che ont 0 PUUSLSSA2 S'=AccwLW/FS)= Ug = 385mm; MESTS feed 9p) 649) = 2680 ona Sib eed) = 24300 ae 440 p78) = 096, FS) = ca tava Che SDMA Lye om Acme fe AIEL anaes SS) =, 8d 18 fr ‘= DMA, Ruband DPOF. esp stem may contain impure. um wt ws Fumps2et Aen 393 wd yy) I Meee SEE 35, F = and He os" 035 nase BL we4s)osieet oS. Ea? Mrs cu as" ax PUMGA942AODIBR AC“ Shue 38 amet hg= tS Soxtote h ty bOx IOP Lele e480) 100 Lic at soxi? ot crises Dee 36mm: wed pS) = 1.0. SIF ‘sue = I meanues ouS04S) £050, 0am 1.13 fr" = DMA eb and ca aos MUALS- ——A=DPBF wed QS) 10.e(5)= 75301 78263 oa totem 82mm. Mesure O°") ena, lab? asst ass PUAMS- — ADPBR.AC=Sttye237 mas uted ECO oa $a)= They) = 16d Ler 505 mm cH ox 037 BUMS: ATDPBRAC= Seam wot y= SSH ae SSenty heqetuiihimet $45)= 14 AO) = 6500 Lac 50mm. Shoes 9 (Sand) 9095. MoH Oy 055, 4. Phys. Chem. Ref, Data, Vol. 22, No, 1, 1993194 WILKINSON, HELMAN, AND ROSS ‘Tbe 1, Quantum yields of photosensiedprodction of singlet oxygen—Continued No. Solvent (03) STS forny Metod Comment, Ret 191 Rensophenone vere. Coy ais oor PUAGTAL —S'mBP|A=DPBE.TAI-MeNptreLto 54268 ost a8 soa $5(S)=038; meas. f8)= 15 oe = 387 1m. Showed P (Sand S) >085. cHeN 0 oa" oe PUAQTAL S's BP; AwDPBF,TA=I-MeNp: reo 854268 son $458) =037; meas. 9S)" Ve * 337 ‘in. Showed PP (Sant S)>085 4192 Benzophenone, &(trifeoromethy)- Cle ass PUAGTAL — S'=BPA=DPBR,TA=1-MENp: Lio A268 aa" 04 soa ‘ioe, mens) 1s eee 37 fo Showed #9 (Sand $7095. HN oss" 054 S'2BP:A=DPBRTA=I-MeNp: ohio SSA255 Hisy03te mens Sots eee 37 rim. Showed PP (Sand 1 2055. 193 Bemotalphenathiazine HCN; 02 PLLLSS ST PriebtogyiS) 08%: Age" 355m 91A308 1.94 emo(eipnenortazine CHONG; aus PLLISG Ste PrreLtogy(S) 08%: Aye" 355um. — 91A308 195 Reno(ciphenthazine Hen Oy an PLLIS6 —— S'= Pure w4Y(S) ORE ye 385 am 91AR08 1.96 1benzopyran-tone,23-iphengl(-Phenyiavone) cae 06 55)KI0 OT os PLAS 39 S'= BP; A= DPBF; ra 19,8) = Ou mene, S667 9119)= 0.55 ge = 97 me 197 1-Benzopyran-tone, 3nydroxy.2-phenyl-(3-Hydroxytavone) cits aI ne Flats Sot TDL WANS). Rye SEDC 35am. PEL GQ= 1 198 1 -Benzapyran-tone,2-pheny- Flavone) Cay Wos.yeW? Use PLUMES = BF AR DPE Lo gus S086 ast a7 $49)" 095 e= 7 om. 199 (U)Bemopyrano67-ifquinolinin-I-one, 2367 etrahydroS-methyl Cle ir 0.08 crt S756 1.100 14-Bemzoguinone,26ipheny- calc, 0 ul PULLS E124 1.101. 14-Renzoquinone26-dipheny complex with Triphenlamine cancH, 0 oe PULLS sae 124 1.402 14-enzoquinone,tetrachloro- (Choral) Cet ose PYLLS6A2 — S'=BReh 1998) =030; tga 355 am SIEM on ar set crc, ors" as PULESOA2 — S'eBPi rch woy(S)= 0305 A= 355 am SEA sed (8) "1, FL 10S bene, coe for salve cH, 03s" 035 PULLS6A2 — S'=BP Ie. 1994/8) =030; dae 355mm; SEAL sed (8) = 1. Fe 10 Sim benzne, coe. for salve 1.103, 14-Benzoquinone,tetrachoro, complex wit Anisole Cite 0.06 PLILLS6A2 —S'=DPire.1094(S)=0.05 ge = 355 mm SIEAAE 0st 95 sed §(8)= 1. pet ional pair.QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 145 “Table 1, Quint yield of photosnsiindprodection of singe oxygen.—Contined Ne Solvent (03) Tt I «Bformy Method Comment et 1304 14ensoquinane ttrachlor compl with Duran ce on PLLISE42 — S'= BP 10Q\(S)= 030: y= 385 am SIEHAL ai? as sed (8) = 1. Tipe oma pai 1.305 1e-tenanyuinone esac compen with Ch 2s PULLSGS2 —S'=BPireLI094(8)= 0.30; A= 355 am; IEAM 20" 020 sed (8) = 1. Tipe ional pit. 1.106 14/ttenzoquinone,etrachloro, complex wth 12$Timeamoxybenzene Cie 009 PULLS6A2 —S'= BPS eLI09S=0.0 hug = 385 0m; SIE HAE 0.087 00 sed (8) = 1. Miplet ona pai 1.107 14-Benzoquinone, tetramethyl (Duroquinone) Couey 12x10 LO PLIAGSLAB A Rot; mens. 6(9)= 10; ye = 347 ams BRITS ‘ed (8) = 71600 Li em 40 1108 Biacey CG os” ast CPA A= 12-Dimabyeylberene: hag =366 —ASFISD fm wad 8) "18, Pod Hyer 12 Alimetylcytohexene, 2 Hyetoxy-2 methyl. |-methyideneyciobexane and 3 Hydroxy 23edimetpleeloberene. 1.109, Bleyct(22.1}neptane2,3-dlone177-trimet inone,Q) Gi ast CRPsId A= 12.Dimethycytoheren: tye = 365. SSFISS| fam. Pe3Hydroxy-12- ‘Simetyleylohenees Hydroxy -mety= ‘eethydeneyelobexane and Hyaroxy 23eimenyleyeioenene 1.110 Rigel 9 Megane 2th hiner) cnc, aie iT 1 cractaaz ()09= sar LUT Biel 2. septane2-thione,33-dimethy- (hiccamphestons) cc, ait wr 10 cmacisa2 LE Dieses Mepanet hone, 19957 pentane vamp) cc, air 1h 10 crac tga 1413 wreyo(2.ct)nepane-amone, ,34FImetay-(Amorencnone) cHc, ait 110 mac tan LAMA Bleyto22.feptane-2-hione, 17,7 srimethy-(Thlocamphor) cH, at 110 crac iar LAS Biphengt Cig on PULLS Cin ae 10 P60 Cie ae ost" a) as cme 00 runases CHEN se on PLLss ‘As DTBF, used y{)=1.0. (5-10.44 (059 {8} = 001 mol L ‘A=DTBR, wed $5) 1.0. (5)-+0,05 (091 st{5}=001 mol L"! (085 at(5}= 0.01 nolL" ‘A= DTBF, used 65) 087 {S}= 0.01 mol = Pye. 1098) = O81; y= 355 am, $= Np TD= pMAP; rl 0248) 10, han om, i: TD= p MAP. rl. 10/8 ha 355mm [A= DEBE ped yO) = 08,68) ~ 27.100 Lot en at 367 am. Measired GPS). S'=DCA: eh. 10 $yS)}=2.04 ge =385 om, 38 saris 2Fi40 sors FO arms oF sore BHO suE207 EM sre sue146 WILKINSON, HELMAN, AND ROSS ‘Table 1, Quantum yields of photosensitze production of gle oxygen Continued No Salven (03) te te Te ‘Bfoemy Method Comment Re 1.118. Biphenpt—Coninued HCN ae 10 PLS) S/N TD=p MAP wh sre234 age = 385 am HOWmio 0: 10 PULL S'eN TDSBF eh. WOfTS)= 10; Ages STEISA 1.116 Bis(2.2-bipyridinebisteyano}ruhenium}) MeOH 0 ost CUOEE AR TME: mma 1.117 Bis(.10-phenanthotine)-47 sales of? up Fimanerninie cur 0 MPS S=TPFLI9GAS)*OT dyer 6S2em SERIE cuore ose PULLS S=DCA:RLIOAS)=20;}gg= 85am. ET non a90 Cnet PeMBY ARB mht qu)=050% rarAO Aoien ret 1428_chysene2romo- or : cre SeMBYARDHSMLOKS)=O5 HFS hasan 126 Chrysene,2-hloro- HOH |; i CRACKS SEM ARDY S re 9(6)= 050% TARBIS gc 2 313 nm, Pe 127 Coronene couch, 12x10? 090 PLS RIMPDME; el. 1045(8)= U0; ye= R2EDIO 370m. ce 9x10? ase CPIACHS Age =365 nm, Assos f= I; messed SIFSOH Sand 33 for A= BMA cae 90x19 a7 ans oo CRACKS Fag = 36S am; wed 6(5)=056. Assimed —SIFIOH measured 9 Se, 1.28 Coumarin D0 ae aot Pass seria Meow ait 0s Puss sora 1429 Coumarin,7lethylaming)-4smethy es nm oI AB 26S a sree 1.130 Cyeoheptatrene Cale 2x0? oxo PLULLG Se DPrL OfANS)=02 Aye =3SS mm. SARS ASL 1,3-Cyetobexaiene Cae 8x10 ose PULLS Sie BP fis) aso Measured #9. 14132 2.Cyclonexenetione,35Strimeyl- 0295 ae 285 am YARIS Cale 99:11 09" 09 Puundas39 ssa210 Cee a98.yx10? ose PUAG-3.39 sox240 L133. Cyclopentagene cal, RTO 00" PUL So BPM 0 f.NS)=020; Aye =35Sam. HADES 075 Measured 9. LAM. 7-Dedydrochotsterot Cy a 096" PLLL@® «SN TD=pMAR ih w/s%S)=055, BRESTS ass Dee 355 am, 4. Phys. Chem. Ref, Data, Vol. 22, No 1, 1989148 WILKINSON, HELMAN, AND ROSS “Table 1, Quantum yields of photosestzed production of singlet oxygen—Contnaed No Soken (03) OER ote sen torn come Ret 1.438 Diacenaphiol1.2-6:2'1"-thiophene (ONT) ca ale 046 FLAS S'= AG togA(S) =O. Supersedes O98 S2FOLS ‘quoted in (83F172, Hen et 039 PLILLSS ——S'= Acre. to gu(S) =084. Supersedes 0.62 92FOIS ‘uated in (83F172), 1136 2,-Diazapyrene,2:7-dimethyl- D0 o ou PLLLSS ——$'=2aTMpyP sre. 94(8) "088; meas. 91R201 OMS) SOIT = 55 am L137 Dibenxf,Aanthracene cacy 2x10 1.0 PLIAGS48 A Rab; mess. $(8)=09; 2g = 347 1m, SOROS = 15,000 Esa CHEN 210 023 PLIAGSt48 A= Rub; meas. y(8)=095 hye M7 nm. §3075 P= wed eS) = 10500 Emoto at Ma 028 LIMB _Dienzoldefynnolehrysene (Anthanthrene) Cis pyar 1 Chive 1438 Ao n358.mm, ASDMA ant DMBA: OFS ‘Sls come witht ccf sme foe tymeasued gysNfa +f) = 022 1.139 ibenzolaopersene,7,16-tipheny-(MesodiphenyIhelianthrene. MDH) Cin ae 033 CPIACIE AS: RgceSTHnm, Recalled wxng S305 030. MOH ie 02 CPACATS — A=Siiye=546nm. f= 030 srr CaCl, 067 CRACISS A =S;meas.O48)=052; hag 578 nm. fP STEED SP =0.30, 103] varied, (i + fa" 7?) = 12 cater, 0.5)seur 035 CHIC 1438 AWS, Asromed f= Iya = 0.6. emo cc, aie 050 CPA eS, fe 1,030, (0) vad STF cHcochs air 067 CPACAIS — A=S:hye=St6nm. f= 030 sTFs80 oc oss CAGE AS, Age STH mn Reclclaedelng f*—BIEO8 030, os ie 3s CPACIE —A=S;Age= 578m, Recalculate wsng 3406 3030. MeoH air 030 CPACAIS — A=S:hye=S46nm. ff 030 sraso ICC, 613) cauenyon ar wuss CHACAIS Am SiAge= 240mm. reso mCresol aie ase CHACAIS — AaS:hge#546nm f° 8780 1.140 Dicyanobis(.10-phenanthroting)utheniam}) MeoH Os aos CU0e1 ATM: = 488 om, ma L141 (47-Diphenyl110-phenanthrolin)bi10-phenanthrolinejsmium(l}) on Mon, axet CUOe1s ASTM: ge 8 am om LAG? Ergosterot Ca SSx10t 096" PULLS s7E0ss Cale erat Lo PULLS BP; 10f,%S)=029; hag = 355 nm. 94235 oss Measured P°.QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 149 ‘able 1, Quantum ils of photsensiized production of singlet oxypen—Contineeé ar) he Yorn, Meted| 1.143 9,10-Etnencanthracene, S-acetlony-1,12-aibenoy1910-ainyaro- cat oat oo ruaeana2 1.144, 9,10-Etnenoanthracene 11.2-ibenzay-9,10 CH air oss" 08 Puneasaz 1.146 930-Emenoanthracene 1112-tibenzoy9,10-dinyde-tamethony- Cae ait asi 09 Puaeasaz 1.147 9,10-Ethenoanthracene, 1,12-ibenzoy--thy-9,10ainydr- Cet ast” 09 Pluaeapa2 1.148 910-6thenoanhracene9carbontrile, 2- dason(PhoxnB) BOW ae ow CiAcd P= EaGASDPBERLIoOS=02, REND Hopi? ae ass CHiAcA Ewe 94S) =057. ABRNOMS BEN DPA 4 Phys, Chem. Ret. Data, Vol. 22, No.1, 1989462 WILKINON, HEI MAN, AND ROSS. ‘Tle 1, Quantum yields of photosestized prodection of singlet onygen-—Contnued No Solve (03) % fT Sah Bory Method Comnear Ret 1166 Phorescein 248.7 Aetrabromo-3456terachor dain (Phan B)~Continsed HOC) ae 03 CHikcdd — S=RBASDBFLWgyS)=076" Son {tab} =03 matt” HO (mic) aie a9 hikes S=RB:A=DPBF eho gy(S)=076, —s6N200 14167 Fhoresei, 25,7 detrachlre, anion EOH ir ons Chhedt — SwEacAS DPR LwoyS)=032. EINE HOpH=7 ae os conc ito gyS)=057. A=RNOaM SEIS ‘ADPA. 110k Rhnrerin, U4 ttrarhnen 9 4.7 Atria: (Bae Ranga tens) akcHy aie asst ines DPBF ge 546m. (Ovaries, S749 MeOH or CoWMcOH sir ont CAC ASDPBF: Age = 546m.) vated, TRIG or) CHIACIGAIS A=DPBE, sora12 trai inion (Rase Benga aio, RB) Chet Aw 94PenysufonyOoree anon; P=9- 707250 Fhoreon: tee = 558m, crn POP hac 546mm. (Onlvaed, RED ches A=DPB. 02s Chir A@DPR:P=25.Diphenyfran ero ncpeonie. etd ape alow fr Seinen, HOH at ass” os comes $Dipeayt dione: P=12- 46462 Ethane dence: rk 69) 076 4055 am ed (3) 099" REL ORD inmetino. OH a oss? 1 Chise4s2S'=Eos A=DPBF wl. 1096)=020; E113 tse) O97 Oe oot Puss HIPS: re. 1 y= 062. amin pata Independent of = 308 and 532 Roe ant DUNES bof) =078 Lio RD In OH oo OsNHHE prs2 iersanen D,OCmie) ar ons? PLAESS re 10§y(S)=0175. wLtoRBinBIOHcor,SINITE p-82 for slvet ks CPC mess i See Tables, HOpH=7 ae ost cones E113 mu 076 PLAGSH48 — A=ADPA:ige=S32mm wed dodS)= AD pe70 {500 mote at Dam assume 7 = Omi mewued 7? = Ho ost on el = S40 mm, 1686 NaChin—ASNIIO peta spine ae. Bote ao ont CHOC Axl: hge=S4Onm, L6G NsClin——_BBNITO pe74 hosp ofr ‘rosane! 0; ont 1 PLMpS342 mea. 8) 078 hae =385m, Sole SIND 066) Cont mot? AOT meas. p= 057 ‘ie ‘osama! 0, oot Tunpsea2 —g— trek eo 44S) 080, mem iS), PINIP1 #0064) {78 gc = 358 em. Sol cont lL ‘ied AT.QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 153 “Table 1, Quint yields of photornsiindprodection of singlet oxygen —Comtnued Ne Sven (Og TAS form, Method Comment we 1169 Flooreseein, 345 6-erachloro.2'4'tetralade, dlanion (Rose Bengal anion, RB)—Continued HomWon 0, onst CHL AT ge $55 s7ri0t cpp MeOH sree, x0 See Table 4 Meow i asi™ ChACI4 —-A=DPBF. oes MeoH air ont PACTS —-A=DPBF: 0F1S7 MeOH ait os” CHAGAS S'= Bos, A®DPBFireL.wo(S)= 032. 90F2Si Fel. inethano; 0g = 083 for poe’ RB re. 10 Eas: gy =O for ‘commercal” RB ro {0 os; = O81 for ‘pur’ RB el. 10 y= (076 fo commercial RB. Meo Loss? ase a CP0EA39 AMM: Ae TMF: Lingus) =050 —saRI01 so (8) = O80! Used P= 1 Meon Oy oso? AW TME hy = 488 am. ama Meon ost" A= TME: hg = 285-373 om, 708738 Meon 0; ox? A=2.SDMF ic #280373 am. TORTS Meow ir ost ‘Ac DPBF. [03] vated sr aH,CH, 73) 2ROH ar ost CRACIA A= DPBE Soaks 1.170 Floorescein,31456etrachloro2.4,8,7'tetralodo, 6-O-acetyh ey ester CH, ost CPS S'=RB;A=23.Diphenyl1dionene: P= EAF29T 12-Binanedioldbemoue 1 948)= — SSFISD (176 ge #561 nm ATL Floorescen,34(ttrachloro- 4.57-erahodo-, benzyl eter cH) oO; as CPPS S'ARB;A=23.Dipbenylltdiotene: P= ASFITI MeOH 2) 4 2-ihanedil etenzoae; 10 9418) LAT Fluorescein, 345 6tetrachloro-2 4577"-seralodo, benzyl ete, monoanion Meon ai? ass CRACKS S'= oe, A=DPBF re w9(S)= 032. 90F2S1 Meon ait ox CRACKS —S'ERB:ASDPBFrL109S)= 076. 90FDS1 Mon on CPM ST=RB;A=23.Dipbenyltstdionene; P= SSFITI 1 Piiaciat henna wt he = 6, hoy = 566 re LATS. Fuorescein, 345 terachoro-2 45,7 -etralodo, benzyl ester, benzytriphenspbesphonium salt Meo ay am 2012S RB} A=22 Dips It dienes P= 88PVED 12-thanedil dena; 10 945) 076: tee LITE Fluorescein, 456terachoro-2'45:7-tetraiod- ena eter, doheniodenium at MoH 0; a cress sari6t LATS. Fluorescein, 3456-etrachlor-2 4 S( etraado, benyl ese, mesctatat MeOH 0} ars criss B;A =23.Diphenyl-LAdioxene: Pe S8F16) 12 Phuel ster: was) = Upon =901 am 1LIT6 loorescein, 3445 (tetrachoro-2'48;7-teraioo-, benayl ester trithylammoniam salt cc, oy ast CPPS S'=RB;A=25-Diphenp-14-dioneng: Px S4F207 12Ethaedil stems; L199) SSFLSD 076; Ae = S61 mm, J. Phys. Chem. Ref, Data, Vol. 22, No, 1, 188915a WILKINSON. HELMAN, AND ROSS “Table 1, Quantum yes of photosenstzeé production of singlet oxygen. —Contnved No Solves [03] Us SM ormy Metbod Comment Ret LATE. Flurescein,345,6-tetrachloro2 4'5,7-tetraiod, benyl ester, triethylammoniom salt—Contnued MeOH Os 7 CMPLA3——-S'=RB:A=23.Diphenyl-l,-dionene; Pa §F297 12Ethanedio iberoate; 1064S) = SFIS2 0765 tee = 561 a, LITT Pivorescein, 345 6-etrachloro2 4’57-tetraldo, benzyl ester, 246-riphenyiprytm salt MeOH 0} 070 CRP «S'=RB;A=2,3Diphenyl-1Aioxene: P= S8FI61 12-Bthanediol berate rel. 10 9,5) 076: A= 55 LATS Fluorescein, 345,6-tetrachloro2 4'5'7-ttralodo bis(benylriphensiphosphonim) salt McoH Oy 078 CPPS S'=RB;A=23.Diphenpl1Adionene; Pe S9FI61 1 Dihenedil sensor rot $0) 076; Aye = 561 nm iu) sat moon 900 Chet) S'=RBGA=20-DApmenyhisulunee = Sarto! 1 2.Bthaedio ibenoae: el. 10 gS) 076; ge = 5 am bare 27 ttriede Mil iithy ammonium) salt 048 crass ara 1.2-Fihanediolibenoute: 1064) =—_S5F1S2 076; Ao = $61 am MeoH Oy on CPAs S'=RBA=2.3Diphenyl-1dioxene: P= 847297 12-Ethaneiol diberze; w.1094(8)= _8SFIS2 (076; Aye 56 1181. Fluorescein 3456terachloro-245,7-tetraiodo,complened with dicobesyLt8-crown co, ae 07% CHMAS—«S'=RB,A=2:3-Dipheny-1Adioxene; P= F462 1 2-Enanedol diberzoste; 0 @x(S) = 0175 Ae, = $50 rm. Rel oS" inmethana ccHcocH, air 70 CPPS S'=RB:A=23Diphenyl- diene; P= B6F462 1 2.ihanadioldbenzaae: rete @(S) = (076; Age = 857 am. Reto Sn methane. cacy ai 076 CPPS -S/=RB:A=23-Diphenyl-L4-dioxen; P= $6462 1.2-Etbanedialdibensone; rel 10 (8) (076; A= 559 am. Reo Sin methanol eney at 036 CHACHA DMDT Aye 200m prior MeOH ie 083 CHACI A =DPBF Ag. = $60. ‘PIO 1.182 Fluorescein 345 6tetrachloro-2,45,7-tetraldo- yl ester CHO, > asi ChPas3——S'=RB:A=23-Diphenyl-1-ionene; P= 84P297 12-Bihanedoldibenzoue 10 9y)=—_ASFIS2 (076; Age = 551 nm, ° 12-Eihanedial benzoate; 10 948)= _BSFIS2 076; Age = $61, 11K Pivorescein, 345 6tetrachloro.?A57-4eraiods, ethyl ester, trethytammaniuo sat cH, = on CPPS S/=RB;A=23Diphenyl-1d-dionene; Pm S4F297 12-Bthanedio benzoate; el. w 9S)" SSFIS2 (016; = 561, MeOH Oy on CHS S'=RBVA=23.Diphenyl-L4-dionen; P= $4F297 1 2Bihanedial dibenzoas; et 9S)= — SSFIS2 076; A= 5 am.QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 155 “ate 1 Quam yi of potouensie radon onl ony —Coninod No. Solvent 103) be we tS ‘Tforn, Method Comment Ref. 184 Moressa,34.ttrachloo 457 trad, p-sapropylbeneyl tr, protests = : ~~ Sot cong 10° mal” HO re 0 $n ert {ARG Presse, A.tracloro.57-etralado p-hapropy en eter, menanion Monae 090 CHIAcdS—SEog ARDPBF LO gS) #032. 909251 ReltoS metal Meow ae 079 Crmess —SERBIASDPBF el wqS)=075. SOFT 118% Puorcssn, 34 5fetrachlro2 457 etralodo, methyl methyl ter fix ae os0 CHikcd3 = Eog A=DPBF Lio 9(S)=032. 90251 ele inch Meow ir 70 IAA) SA RBA=DPDF rh woguS)=076 90251 Meo ir 080 CHAcA — S=EOA=DPBFeL944S)=032._90F51 ReltoS'netan 1187 Puorssn, 34 5ferachlore 4 ;7-teraodo methyl eter, protonated ex at ans CPC —_S'=0-Mety Rose Bengal my ester Ax 90FS1 Frere wot) <0. Son come 10> mal Hehe oS inet fine ass Orne S=EIGAZTICR wL0q8)=032._90Rt Sein on. 10 mL He Sin 1.188 Moorea, 34.Sfterachlore 57 tralade methyl tr, monenion Monit 030 omnes S=RB sores Meo aot Ae SHAG A DIBFLL wh sors elie neta 1.189 Moorsee, 24.S6erachlore24 57 etrslod oy eter, ibylammoniom sl coer O eu CHiedS——«SRBLA=25.DigbenylAionen: P= 84257 {2B abemcate cL io gS) ASF1S2 aati 1190 Moorsen,24;5,7-4traloe, anon (Eyton) CHCN sir aa? CP/Pa 14 ‘A=DPF; P=255-Diphenylfuran STFa40 aero, Mehod adap allow for DMF ait asst AeA) SARBASDPDF rh. oGS)=076, SFIS ‘EOH air 06st CP/AcAa ‘S'= Eos; A= DPBF; rel to $4(S") = 0.32. SENS nom-7 aie ost CHAeH Safe miogyS)=O57. NeRNO and DELI3 orn HO oat oss" 068 CrRe342 S=MB':AZ2SDMR Ln 4S)=052 TOTES mop 107 on) ruses seas neuer 1.191 Fueresceitribrome, anion 02 Ces SaEoR ANDPBFeLIo9S)H032. SENS ou CMAe# —-SaEoR EL oH{S)=UST. AFRNOSM ENTS pea 1 PUAGIMA® AxDPOF mess. 5)= O10 Aue =53 SND om 02. 4. Phys. Chem. Ref. Data, Vo 22, No.1, 1989,156 WILKINSON, HELMAN, AND ROSS Table 1, Quantum yields of photosensitized production of singlet oxygen —Contiued No Saves (03 iF fee, Mebod Comment Ret 1193 Furl? bemopyran one, 6acey-(Aectollapsorle) Cie ose PULIS6A2 — S'eAcRLw 94S) =O.7% meas gyS)= — SEIZI oss? ast O68; hoe = 358m. =. 1194 Fur(23-t benzopyran-one49-dimety)47-Dimetylalopsaalen, 4-DMARS) Cae otto? a PULLS6A2 —S'= Ac rho 9S) =O7%: mea. OyS)= TEAST ra 13 ge = 35 orl Denspyran ame, 2 imag (47. Tima algeralon) Cae gia PLAIS642 —S'=Acehw gS) =07%; meas g(S)= BAST a2 6s OU = 85am. 25104 comes Ho pHa 73 1196 Foro23,91Nfbenzopyran-7-one,34.9.rimethyl-(,74-Trimethylllopsoralen) Cae rei? 00K PLILLSG42 5’ Aci reLw(S) = 0.73: meas. oy.) 0073 026 028; Aa = 355 10 26s x10 ChPas3 $= 47-DMAPS: A= ng P= Imidzole vena edoperontos mens. (5/045) = 038 a 368 nm, RNO a monitor of. 1197 Rurol23.4](1enanpyran-2-one, 3-acety-(3-Acetoangelicin) Gi oar S'= Ae; w4y(S) = 0.73: meas. YS) = aot ars 056; Age = 385 0m, P=, L198 Furo2,3-h[1benzopyran-2one 46-dimethyl-64-Dimethylanglcia) Cae Oy oor 025 PLLLSGA2 5’ Ac; seh w (8) = 0.73; meas. 6(5)= O04; age= 880m. FE 1.199. Furo(23-]{1benaopyran-2-one 48-dimethy-(4'-Dimethylangticin) cnet om" 02s PLULISGA2 $= Aer 199468) = 0.73 meas. 645) 006: Ae =385 un. FP = mo it ot crmss——=Aog: A=tae P=Inidtate pera cope et 9S 2 02a ScS1am. Mesure 97" 0065 MeOH RNOsemenior of 4.200 Fureia2 A1banaapyran 3 ones AP dmet (4H Dimatylengetit) CeO om ous PLILISG2 1,0 o 0st CPPS Sim Ang A: pite73 edopeoxie; 10 (8) = O02 Aue $36sam. Mensred ssmonitor of; P= 0.11 in OH: RNO 1.201 url2-ilJbenzopyran-2-one,§,9-dimethy (4 -Dimethyangslicin) 0 o 0007 CPPS’ Ang: Ann: P= Imidazoe ph=73, emoperoxie; 10 GS) = O02 SS 1.202 Foro23.AMbenzopyran-2-one 69-timethyl-(64'-Dimethylangelcin) cate oor? aus PLYLISES2 Sie Ac; ew 9\(S) = 0.73; me OS) 1203. Fur(23-tIemopyran2-oe dant (Met HO ie om! Cmsy Sm Ang: Ant P=Imidnne mea nope 1 (8) = 0005 tg = 56s. Mesure = 005 MeOH RNO asmontorofP ames sTess7 ‘86121 sHE121 s8E121 saEn04 E121 seein. ETO sien sHET96 seeQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 157 ‘Tobe 1, Quantum yields of photosensitzed production of singlet oxypen—Contiued No Sovent 10a), tS “Born, Method Comment Ref, 1204 Furol23.[1}benaopyran-2-one, methyl (6-Methylangelicin) Ho - ot coms sarvou pa=73 1205 Rurf23.[1}benanpyran-2-one methyl ('Methytangelcn) Ho ie 0007 CPPS S'= Ang: A= Im; Pe Imidazole ETOH pa 73 endopeoxie 1 (5) = 002°; hae $65.am. Mesure ¢, = 008 BH: RNO semoniorofP 1.206 Furo(23-l1bemzopyran-2-one, Somethyl ("-Methylangelicn) mo oO 200" crm) Sta ang: At Pe aae eri ma endoperxie; 10 9S} "O02: Page EAETO 545 nm. Measured = 0.08 n EH: RNO as mocitor of P; PP 1207 Furo(2.3 Ail Tbenopyran2-one, 469:4rimethyl(644Trimethylangeticin) cee on om? as PLL S6.42 cs. 10 9S) = 73 mea. 6y(S)= BREN 13; 2ge= 388 nm. PP 1.208, Furo[32,l}bemzopyran-7-onelsopseudopsoralen) oe one PLALS642 — S'= Acie. 1094(S)=07%;meas. y(8)=_SHEI ou" 067 1.209. Furol32slMbemopyran-7-one, 8-aceyl (3-Accolsopseudopsoralen) Cie arse PUL S642 7 86121 6s" 099 6s: h = 3550. 41210 Furo(32-gRenzopyran-7-one, 2-acey-5,9dimethy|-('Aceto-8-timethypsoralen) (cote on ase PULLS6A2 —S'=AcreLtw 98) = 073; meas @4S)= _SEEI2I os” a72 O52: Sem. PP 1211 uro32-gt1benzapyran-7.one, acetyl Smelhyl (Ace Smethy psoralen) yy ous PULLS SeAcreLwgyS)=O7% mea QyS)= SIRI out 920 (38) Spe 285 1212. Paro(32-fl[}benzopyrans-on,7-aceyl- (3-Acttopseudolsopsoralen) Cale 0 ose PULLS642 Sw AcyreLwoy(S)=07%;mes.gyS)= —EI2T osst 098 O56 tee sas am FP 1213 Heliantrene Hy aie ase CHCA TFs80 Cac, air 036 crIACAa36 ox smRap (03) varied, (8 oe cy sie 030 rine AWS: reg = Sa6.am.[0,] ared f=, 8IRA09 cHCOCH, air 00 CPACAIE ‘sFes0 MeOH alr os CPACALS sTFa80 IOC, 15) CH,CH,OH air 02 PACA sTF80 Creal ir aus CHACAIS sTr480 LIS (EEE).AA 6 Heptariena,Smethyh7-2.46trimethyl-eycloexen-Ly0- (all-trans eC air 06s? 10 PUAd939 4. Phys. Chem. Ret. Data, Vol. 22, No.1, 1988,158 WILKINSON, HELMAN, AND ROSS ‘Table 1, Qeatum yes ofphotsensiized production of singlet oxygen Continued ‘Comment ot ans-C yaldehye)—Continaed 250x108 4,4 =34% 108 Limot 18) = 066, §AC)= 1 e,0AC)= 7600 L mol" en at 382 am. Meon air of 4 PUIAG4939 A=DPBRAC=S:2yg=337 nmi: used y= SSFOSI 210° kq = 8 108 Lmol™ 3 oy (0.41, (AC) = $7000 L mo! em a 440 McOH Oy oat 10 PUAG9A2 — A®DPBF;AC® BPtige=337 am; wind ky S4F005 5 1.0%108 Fy =8 08 Lots S)= 0", $y AC) = 1,580) = 7600. 41218. Heterocoeranthrone (HCD) GHC (150) x10 4 CPAC-I438 AS. Assumed f= 1 761510 Ga (20x10 4 CHACI438 eS. Assumed f= 761510 Cae (59 x10" a4 CPACI438 eS. Assumed f= 1 761510 Call e9)x10? 19 CRACI438 Aw DPBF:ige=578 nm, Assumed /=1, SAFI9T ‘is? 002s eck, 130x104 a4 CPAG-I438 —AwS. Assumed /? 761510 cae, (50) x10 44 CPACH43B AS. Assumed 797570 & 30.107 a4 CPACIA38 —A=S. Assumed f= 1. ‘61510 1216. 1235-Hexatriene,1,6-iphenyl- (OPH) Gilly air PUAG-#9.39 F041 eKAC: brn Oh Aft 1. C—O 10 30m 207 crise? McOH air PUAa-49.39 1217 Indole, methyl Cale sie 035 PLPO-S7 — S=BRTD=AP eh togS)=035, ——_TOFDOH Measured "SVS = 1.0, cate sit 02 PLIBC-ST —S'=BP; TD = Xanthne; rel. 10 (8) =035. 76P904 Measured fe) 0.7 bat energy transfer efcency < 100%. 1218 B-tonone atts o ease Tunasss? DRA UYDR REL wesI=Us MER EL o2s? 05 XS) = 05; he = 337 om, 41.219 sobenzofuran1,3-diphenpl-(DPBF) ett; i 02 Ax S:2qq#365 nm, Inpresene of gL 84P629 ethylene propylene--7.10-dimethoxy-(Cercosporin) C6 sirory os PULLS S'=MPDME: e098) = O81: Aye 582. S5RI23 Cet ost CPiAcds—S'=MPDME: s3R123 asi, 1235 Phanaten Ione Ce ih oss? oss crn.ss.42 sires Ce it oss" 093 CPLLS642 —_$'=-Haorenone se 0 gy(8)= O83: mes. 91FORS 6X)" 10; hye = 357 mm. Assumed PP =QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 161 ‘Tbe 1, Qeatm yields of photosnsized prodecton of singlet oxygen —Coninued Ne Solvent (03) ie Horm Mebod Comment Ref, 1235 Prenatent-one—Contnues com ow ost CPAcI—ASTME DE Nien, RS Aeon, ORE ‘MLM da Siva, personal communication, coop ait os” os CPLS642 —S'mRBjre.t04y(S) = 0.76; meas. gS) = 91FOR 1.0. P= I mess a0 of tal and (8) = 347 1236 Phenalen-t-one, 6mino- BOH ait nis CPACIS —A=DMA. Extnpolued to[DMA]->, 85501 1237 Phenanthrene Clg te ow PLANS S'=PreLto9yS)=O8 Agee 355m, S1EIIT pow te ost PUA Sto Am A=DPBF reLt04,(8)=Ir ue SERS 2otam. FP = 1. che 059 one PLipS242 yg 385 nm; wed 6yS)=070, Measured BEE 955 057, P= 097 ad Che 0s ose PYLLS6A2 Sia Preto gy(S)=O85 wed g1S)= BREAD (070. Measured P= 057. cHeN ae ost PULLSG ——S'=DCA:r.10445)= 204 yg 355 0m, 91E297 MeoH 030 cHAc4 DMF; Ae = 313, TaFOI6 1255 Phenantbro(t109.8-opgralperyene714dlone, 13468,13nerahydroxy-101I-timetyl-(yperiin, HYP) Domi) air on 1 PUAGS942 A= DPBF:AC=S: meas OS) =070: Lu. SENSO wea 0m: wd f= 2.0% 102 ky = 1 10? Laat 5" ¢,AC)= 19400 L mor! co a 640 nm. BRU3S mice, ee a. a) PUAG 1929 -A-MDH: P=Movodiphelbclamvene STFS 1239 Phenazine (2) Cale airor oss seeTable 4 Cte ae oss" 098 PLALSTA2 used OyS)=085, S'=PrinOn,QS)= _ 90AR28 083, FP = ch oss" 098 Punps242 ee 0388 wed sau Sine crc, 0; ost PUMPS? ge BZ155 Ho; Oy ost PUPS? ge 354m, 82155 foam) 0, 80 Pty #2 Age =26E mm Ge sin Oat EAGT, 91USH 1,006) es. p= <0 ‘ey 1.240 Phenothiasine HCN 20021 PLILS642 —S'=Px rel woyS) = 085; meas. y(8)= 914308 09602398 am. cH oy 046 PULLS s1A308 1242, Phenothiazing,2-methoxy- HN, oa PULLS S'=Prrel toQyS)=088; hye 355mm, — S1A308 1243 Phenothiazin,10smethy- HN ars PRLS Sta Pren maya O80 = 66mm LANE ‘J. Phys. Chem. Ref. Data, Vol. 22, No 1, 1988162 WILKINSON, HELMAN, AND ROSS “abe Quantum elds of photosnsized podction f singlet oxygen—Contiocd Ne Salven (03) he Born, Mathes Comment Ret 1244 Phenothiazine,2-(Grifuromethy CHEN 0, aus PULLSS — ST=PareLtw¢yS)*O85: Aye = 355 am, SIAM 1248 Phenothiaziium, 37-issimethylamino (Methylene Blu, MB) CaCH,ON ost ACH AwDIOM. (03) vai eres cacHy ae os” CHiAcI4 A= DPBF. (0, varie. smRa8 MeOH 5 Hc, i ost CP ACTA2 —A=2S:DMP, wed 64S) 9052, Asumed 737359 Bal. HEN ie ost CPPI¢ —A=DPR.P=25-Diphestonn RHO ooopeonce. Mets ape wallow for ‘tain eaton BOK ait ost 1 CHiAc 1442 Aw DMA; wed 9(9)=052. Assumed P= 737339 1 BOH 99x10? aso = CH106-4339A=TME;re 19S) = 050, we f(S)=_ 4FI9I (052, Used PP eto MB" in MeOH. Ho air oso? CPike27 An 2SDME. Asuned h=2: PP a1. TRL Ho aie at 1 CHrAc 1442 A=25-DMF; wed (5) 052, Assumed 737339 #0 oy ox? CPise43—S'=RB:A=Im: P=Imidazoe asR008 pena congo; 110 913)" 0.73; Ane = 40 sm. RNO ss monitor of. HO Gi) Op ox Chines S'=RB: Atm: P= ize ssRo0s pets doperonide; re 1065) = 0.75; Rae = 546 ten. RNO as monitor o 0.23 mphesg Phosphatidyicholine. Mop =10? 0708 PULLSS ——S'=HPreLweyS)=05% meas oxS)= SEATS oss O51: .ge= 30 am, Pm Teh 108 in 10H cle. ming (6) = 064 (882159, MeOH se oso" Chiscté A= DPOF. sorts? Meow ie? ast PULLSS Sake was) =06 smi Meo ict os crise DPBR, wed yS)=0.52, Assumed AP 737339 Meo 0» ot UAC A@DPBF #633 am. Assumed f= 1. STE Meow ir os? CHHAc14 Aw DPBF. [0a] varie wrra79 CahiCHs or) Z-memony> Up ows cures DH ae O55 an, AEM = 1. IRIN ‘shana Propylene Op oss? CUA Am DPOF gc 633mm. Assumed fsT= 1, STEM carbonate 1.246 Phenohasnium,37-tamino- (Tene) CHEN ir ose? crm DPR: P=25-Diphenan sTrH0 doped. Method adapted allow for ‘tain escton, mo a os? 1 CHiAe3.42S'=MBY:A=25-DMF rh 10 94S)= 052; 757389 vsed 6(8)=055. Assumed PP 1247 Pivalatiophenone Cir 1 10 PUAG339 S'@DMTBP:A=DPBF:e-10(8)=1;_ S7AM0 ss 5) Hye" 32m, cna, a 1 10 Chine 1442 A=DTBR wed G(S)=1. (S]-r0.4,= S978 (096. (8}=001 mel 1 FaoQUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 163 ‘Table 1, Quantum yields of photosnsized production of singlet oxygen —Continued ie oven (Oo Ge AE AS orm Meta Comment we 1288 Phatatiophevan,¢-" NaCl 1260 Proraten,8-methoxy-(8-MOP) cae on PLLLSG — S=BP rh mays 4020 Le OEM O1FITE Nocmisson detected Cie Oy ons PLILLSGA2 — S'=AcyreLw (8) = 0.7%; meas fy(S)= BREIL oo" 04 01; 2ee= 355 m, P= 1 RoE sir oom" MPLLS6 PP rl 10 G4(S)=07; Re = 652m. S3ESTS ie 20 MPLS S'=An Used (An) =07, waren % 003s CPAcss = HF: Am Sobilsn Carieberg rel. to_-STROIS 400) 085 ae = 309 sir 0.009 PLILSG Ft 0 64(S)= 03: hye 357 Am, SESS s6Fias “ 0007 emer Ogg 919 oori00, ao ost PULLSG —S'#RF, re. 1944/8) = 05: 2p 337 am. S6FL4S sie on™ 07 PULLS6A2 — SERFL VOgSI=NE yg AT om RSEDSS ed (8) = 0058 tories 1261 Prorat, 48rimethyt- Se one FULL S6 2 Ante fl6— 0701 menn HO) SOE O08" 038 021; Ae = 530m. P= ‘6160 1262 Pyrantheene eanen, ani O97 Pusaugeis A= RAI. gS) =O29 ge DAT TOT Rms wed e¥S)= 14,00 Lina on a Fata = 097, CHEN 12x10 045 PLIAGS48 —A=Rub; mes. (8) = 052; hag 347m. E3PO7S R= ls sed ey) = 8.000 La en et ects 045) 1263 Pyrene Py) Hexanes Os 086 crac ‘9FO16 nC o on cpiac2r 79683 cach, ax? 19 PYLISS —S'=PIMPDME:reL 1 9,(8)= 10; hq 828010 347 om. cs 12% Opin Ny ass FRILLS) S'=Npp TD=BP;reL 0 fi"%S)=055. P= 904328 Cal aie on FLAGS Si=Prir.toQyS) =O: Aye=S32am, 904528QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 165 “Table 1, Quantum yds of photseaszed production of singe oxypen-—Continwed Ne Solvent (Os) Ta Iss Bform, Metiod Comment Ret 1263. Pyrene(P))—Conined ci ane PUMPS? Agen 35am. Meanred 9, =074,06.=1 SHED ahd 9? = 086 an ge Auto asune Gan re $919) «O96 te fa = 177 ut Pim 95 10 valor offen fae indeterminate che ase PUSS S'=PrseLwgsS)=08%. Mesued = SEHD "and = 096. Andon sume /= Cand vse 99) =096 ape ye =07 ba P= Aisa waar of one! a inerinaie Cet O13 OT PLALSES6 Sim Purl ey) = 0.x S)= SOAR (29, P= i Asamed Ie Cae 19107, 90% ST 05 1S CLUAnAB BE Sm AWDMALeeL 10449) = 10. Astmed ABFLIG 1 Ral anes owas MAR Sa DCALRhw eNO) 20 Reg = 355m 91E97 MOK) O> 0 CHIAcIS——ASDPBF Age 338m, (SDS]=0.1 mol 78AITA Nome 0, 10 CPActé AS DPBR A. #388 em IDTACI=0 mel T8AITH u MoH 0; os Cfthelé As DPD Age 388, 7earte Meo 0; 078 CAC AR2SDME Ag =313 am AsenediT= TEFOIS tisha MoH 0; a CHOI A= 2S DM A= 203-373 om, ors MeoH Oy 08 COE AR TM Ag = 285.373 om, 70735 1264 Pyreneeximer Gite gsP.90% 08 OS CUA SeARDMALOGS)=10. Asumed SIG Mon 0; 04s omnes eF016 1265 1yrenecarboaenyde Cy ont PUAGASA2 — AZDPBF;AC=BPY Age = 357 am: ed €AFOOS SSoxtdiel ggn34K 10 Lmols 8) 078 $C) = 1.e4AC) = TOL Cie ast PUAUASA2 —-AZDPBF;AC=BP: e357 am: ey SFOS 40.108 ke 80% 10 Lm, $18) = 0575 C= 1 eyAC)= 700. 1.266. Pyridine, 262i) coc, x10? asst PUMGAOHS A=DIBR ACS BIn, <7 am ed | TENO Seach BL me Sam pel 1267 c-Quatertiens OHO; 02" A= DPBR meas 9(5)=020' i= 383 S5NO20 un, PP o 0 roe 08735 o 10 croc TORTS 2 sarbonlienady 4 nydrony (gmoranie sed) sie as PLaLs6 s7R290 ‘4. Phys. Chem. Ret. Data, Vol. 22, No. 1, 1983100 WILKINGON, HELMAN, AND ROSS. ‘Table 1, Quantum yields of photosenstzed production of singlet oxygen —Contineed No. Solent (03) TS Bform Matos — Comment Ret, 1.268 Quinotine-artnglc ni, Ahydony Kyron se) —Contnied 10 sir oa CPPS STeRB:AwIn: eh 1968)= 076 Aye SIRIAL para 352m. RNO as monitor of 1270 Quinoxline Cae ae 091-091 PLUMPS242 Aye =387 om, Measued gy asumed FP = SIF iS)> 5x10 mot Lg, = 073 exapoating [5] 0, 12m 1szyRetinal chk 06 MPLS S'=PPDME:reL.199(8)= 08; Aue=385 78700 1272 (all6-Ret eC, ae 1 FUAMAO39 ASDPBFAC=S:iye=d8T om edig= ASSL {G{AC) pa hen Cay Oy 006 PUAG9A2 —AwDPBF;AC=BP. ge 337 am: wed hy AAFOOS 250x108 s!,fy= 34x10" mols, 69) =a GAL) = 1 ERC) FOOL mmo! em at 532 am. chr ost MPLS S'=FPDME:re.1994(8)= 08: Aye 38578F700 BORO ce? CHike1S A225 DMF: Age = 365mm, aR201 MeOH air ast 1 PUAG.39 —AsDPBR:Aac 0337 am wed ye 110° SSFOAL Sg BIOL mot oS) O12 neat ive. Moon ooo? 1 PUAG942 Ae DPOF: AC BP ge 337 nm ied hy MUS F1OxI ety 81 10 Lol et, 4S) = 0112" GAO) = 1 eC = 600. imam at 32 am. 1273, (al-£}-Ratinl NCMy ae on PUASL — S'=NMTA;A“DPBE,TD=NMTA:reL.9 $5E190 SUS) = 1.1; Ag = 387 tm, P= oe foe ‘Suenching Che 14x 025 PURGES S' AR: As DPBF:TD=Tipbenenee. _S3EI84 ST Age = 4 mm, Ulee P= Cae on PLAd9.39 ne=387 nm wed SSEISO FAC = TA Le at 52 om PO = Tp measured f= 0.36, f° + Ua" — orf = rh used f= 075 Cohen 075 PUAGSL —S'=NMTA;ASDFBR:TD=NMTA:reL10 85EI80 ISAS7= 095; Ng 297 mm, FP 1 for S quenching, MeOH ww, 030 FUAGA939 A=DPBFLAC=BPIpg= 337m. P= S5E190 reared = 044 oni = (8 wed f," = 0.72. Moon air 078 PUAGG — Sz Roly: s8e190 Rothpy 1078) = sem Pm reat. for Bauenching 03 MPSS —S'=PhareLiog(S)=08 Reference $22317 ‘au ine 0 sie 0 Chfed3—— S'eRB:AcImrebwoyS)=O76 2c IRI para ‘45 am. RNO st monitor of.QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 167 “Table 1, Quantum yes of photosensied production of shaglet oxygen —Coatinued Ne Solvent (03) & Sie Horm Method Comment Rel 1274 Ribotayine (RF}—Continues H.OmOH ait as PLs6 tori a Meo ~10? oss PLLLse2 BsAI6s oa 079 MeoH ait os PULLS Se Br. eL.19 6,8) = 060. emR38 MeOH ait as PULLS RE 10 $48) = 03° ho seria Rel 1oRFinDO. 1.275 Riboavine Syren phosphat)(FMN) 10 ae 049 CPP S'ERB:A=ImreLt09AS)=O76: Ay = SIRISI 1216 Riboavin-23 4,5 tetraacetate CHEN ass CPPEI Aga. A= Oli line or 984 nel ats nydrpernide formation, 1277 Rubieene (Benzalindeno(123-)aceanthrslne) Cle a3 ChAct# A= MDH. ff wor Cay ae 028 CHL S'S TPL WGA! 86509 coy, ae 030 ChAcié A= MDH. f'=030, wr HCN ae aus criaccta DH. f* =030. En crc, air 031 ChACI€ —-A=MDH. f= 030. ED cs sir 086 CPAcI — ARMDH. f= 030. Em cicR,coyF air 023 CPACIé SMBH. f=030. om 41278 Rubrene (Tetracene, 511,12-4etraphenyl, Rub) ean Op 095 1A CHAGIM38S'=ADPBF ig = Siem. PO =H; TESIL ‘Assamed f= wed PP! = 087 and = CeO i 1S CHACI 38 S'=A=DIBR ig = Siem. 7 <1; ESIL Assumed (= 1 ed P= 0.78 nd =O. nCy 0 12 3a ase CRAG A=25-DMF: Age = 313m, P= I TE sesame» 1 ed Pa = ecm 0} ul 14 crac 438 PDF: ge = 546m, 7 esr Assumed f= 1 wed PP #076 and = 0 cuHCH, aie 2 MUAMSHAE An Sige 500 mun y= 3231061, gan gm 25% 10" Limo 5 7 e4S) = 26000 L sot! en a S00 nm. y= CaHLCH, 61210 CPACHAE A=SiAyg= 436 om, Meus fa" fs 156223 fie HCH 0,(00am) 8 PULLS ——S'= POMPDME; eto 9S)"1.0; Age" S2E010 Si am, cae easy as0® CHMOD ARS Age eto em. Memen TIERS 2 Cie 8x1 036 CPOs S'= MB"; A=TME:reL to 9yS)=050, S3F608 ge 535,546, S77 rm et 8 in MeOH, Cn CRACKS S=BPA=Sih 1048) 054 Age= HFRS 345 nm. Assumed = Cale ait au CRAG A=Si 2g 365 s1F017 Cee oor 19 CHAc-1440 AWS, Assumed = 1 fT fo romgy 167422 when 72 = 1; fal = when P= 0, Cie ait 2067 217 CPACHAIB A=. Assumed 767505 Cale 46x10 st crocs F608 ‘J. Phys. Chem. Re. Dat, Vol 22, No. 1, 1983100 WILKINGON, HELMAN, AND ROSS “Table 1, Quantum yes of potosensitize roduston of singlet oxygen—Conined Ne Sovew (On Sf i ‘Sern Method Comment Re 1278 Rubrene (Tetracene, §611,2-tetraphenye,Rub)—Contnued Cae 65x10? Ce AxS;Pas2-Dinyems61822 aar002 teuapheny-512-piGionyeincen; ae= 377005 Siam, cay Oe CHIR SE—A=Sihge= C258 am. ila 4/s?)= 66286 anes 088. cal, 8x10 090 Chi0c43 Se MB A= THE to y(8)=050,—S3F508 Ace 4 S46, S77 agli MeOH: OiaF = 003 FB = O51 4489 = 13 Cate 90x10 14 CHHAed—S'=BPLA= Sere 10946) = stFs6t 365 sed (5) = 005, Asses f= Ce Os ost 1S CHACH38 S@A=DPBF gem 586mm. FO =1; —T9ESIL Assumed f= ed P= 0.2 and =O. Ch ” CAC AS hye #36436, 546 nm Sart cn rr 12 Act 7RB036 cu,coct, 0; ass 1S cmncss SeAsDIBR geste Aha: Test Aen f= ised iO ok y=. cnc, @35)x10 CHAGAS AxSihge= 260m, Assumed f= 167 186223 FR: os cat, 0525)x107 CHAGAS AxSihge = 6m, Messe T+ f.4P 186228 aia ce 033)x107 CAC ASEA=S Agee 6am, Messed fT fsP 156223 cs: (059x107 crac 1438 orm, Meas fal off 156203 os east Fee tk3t ADOBE R= 546m, Anes f= 1, AIO? bust=oai 1279 (pStibene ee 008 PRPCH — SDF eh w/ANS)~035. Mewed 76904 PNSMUSS)=02, Cate Oy oa PULLED S'=DACN AL WMS) =O Agg=385 8SF291 ane am. 73096, Cte on PULLG Sa BP LOTS) = 029; Aqe=35Sam, 85291 aie P3056 1.280, Sednone.34-iohens- Caen os PUAGTDLS2 A=DPBFAC=TD=NMTA: hag =485 864380 ey 6 EH gw BOIL, teal EyAC)=95001 mo" oat oun vase 1281 Sydnone,3-4-methyipeny- Cee 038 PLUAGTDVG? A=DPBF,AC=TD=CQthge=485 nm S6A380 edge adx u's vig 8 WPL tra 24(AC) +90 moon 700 sm, P2089, 1.282 Sydoone3(4-mety phen pleagt Cie oss, PLUAGTDNG2 A=DPBF,AC=TD=NMTA: ing 485 S6AIKO ‘a sed y= 40% 1085, fy = 8% 1OPL mots, £4AC) = $300 Lor! em! a 20am, P= 078QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 169 “Table 1 Quantum yield of potosensindprodotion of singlet oxygen —Continued Nor Seven T0 te SS Horny Metod Comment et 1.283 Sydone, 3. pens cm ow PuncTDLG2 04280 1286 pTerphenyl Ge os Prndse 0263 oa 1.285. terthien! c.assxi0? oer PUSS SoM RL IONS) HOSE: yA 35AM, EES) CP. cssyxi0? oss PLLESS SAC reL10 8)" 084: ig 385m, HERP oh ost ar PULLS642 — S=Px el 19p(S)=08% mess 9xS)= 9035S “9.1 Age = 87 EN areDeIO? Oat ruts Ae t9445)= 084 hye # 350m. 06691 00 at os -07 PULSE SwAnrch10oS) =O; mens e(S)= HOES 09.1.0 gg = 357 000 ant 07 PULLSGA2 —S'eRubpy ew e(S)=086 meas. OFS habennehh ca, ir ant 07 PULSGA2 —S'=Px ee wo(S)=084 meas Oy)= OFS “a9. Age Som pa, 116x107 ast PUAGACH9 A=DPBF-AC=BPjAge=357om: wid S7E410 s{AC)= 10 Lal cat crc, ae ost 07 ruses sors cues ae as" 07 russe sors cue, ae as a7 raise SHE 55 OHO 0 PURCISA2 —-A=DPDF ne (9) 0204 Aye 359 SSNODD om PP spy 005. ponmo a wat nt CIREIAAL AIR ty = 39 A BE GA) UD. ELIS os) 1286. 2275;2"-Tertiopens,Shromo- Creare Punsacus sea 1207 221572" Teraophene, yan coe, 16x10? ast PUAGACLS® A= DPB A weno eA) = 780 ma ea 1.288 22'5/2"-Tetiophene, 5° brome. coo, 16x10? ast PuAsAces Die =337 ame wee STEAD bxACI= ef ACI THO Lin a S3Sam. pat OH ast PLAcsI442 — A=DPBF mess. fy(9)=035'he=355_sSNODO om al pg. 1209, 228.2-Tertopten, mei. coc, 16x? asst PUAGACLA9 A=DPBF:AC=BP: ie =387 area HAC) = 1.exAC)= 1640 L mol em! a Siam. J. Phys. Chem. Ref. Data, Vol. 22, No 1, 1983170 WILKINSON, HELMAN, AND ROSS “Table 1, Quantum yes of photosensitied production of singlet oxygen —Continued No SoWvent (03) % «Borg Metiod Comment, et 1290, 2218.2" -TethopheneS= sans OH a aw PULLS S'=An L004) = O55: = 3am, ssazes BOH ar ou PLLLSS —S'=ZATP re 19948) =55; b= 600m, seaase HOW) ar or Acts A=DFBF Age = Om. suet 1A) tar S8AIB4 rc esc. 226, Phialcyaing,143,118182225.otabutny rn) Che ous PULLS = Bh tnhS) "025; mea $19) =O yg = SIZ ome TASS Sain co 5 pyrite Cog oso PLALSS —S'=BP:rh100(S) = 025 meas p45) =052: hye S82 an, 9B Sain cor 0 oot. 2.27, Prmalcyaing, slo (mined dr rasa) DyoWmio ai? PULLSSA2 —S'=HYTPPSt 018) =057; em 18) =025 Age AFSL 2B om.’ = 04 asoming PO. Sol com OL mali’? TRIB Tae sie ow (ChPed3 Se RB: Aims P= Inia cndperoxide: 0 6(S)=__ 86ROGO (075 hg» 670m, RNO a moor o wed PP = Igy) a ‘ge 380 mcr 10670 om, on Crimes RET = sro aw Crs An Tp gg om emo oar PULESGA2 —S'=HP re 10 98)=05%; meas 8) = 020 = 347 om. TRIES an fo! = sing PO ed Peak, sig (8) = BTRISS {st om 421595 Monat a PAL S612 SF—HP rl 1 9(6)~0.5% men (6) 025g Od RIES fF =O suming P=, wed P= 4: Phys. Chem. Ret. Data, Vo. 22, No.1, 1988178 WILKINSON, HELMAN, AND ROSS “Table 2, Quantum yes of photosenszed production of singlet oxygen, porphyrins —Contined Ne Sven TO tah Netied Comment Ret 228 Phihaocyanine, suf ehoroalinum(}) DOptt=7 Oy ast mas H,TPPSt: re. w gS) = 052: mea. 1S)=O46; Aye 90ANID 385m, Rett "in HO sot cong. 210 mol 8R002 ‘Phosphate eter ad 16 NaC wt: PP = 229. Phihalocyaning satf coralumina H0pH=7 air 03 creas RB: A= In; P=Imidzoleendopeoxise 10 @(8)= MRO O75: ige=6T0 am. RNO as maior oP: sed PP = gS) at Nee" SB amcor 1670 am. 230 Pathaocyanine suf aluminum) MeoD ir 036 PULIS6A2 — S=HP nL gu) =N6t meas (S)=OA2: hye = MTom $12 Jae asuming FE = aims 231 Phalocyanine, sulfo(phthalimide) aluminum) ie 036 PULLS Ste HP eh 0418)" 064 tae = 347 am. oma aa ie suo nba) sie o (CHPA3 ——_S'=RB: A=Im: P=Inidaaleendoperonde re 10 9(8)=__S6ROSO (073: hoe = 610m, RNO es monitor of Ped = 1, (Sat 1ge= 8 wm, cori 670 233. Phialocyanine, ufo copper) wyog-7 ° CORAL = DRA =I D~ Idee andopervide rte flS-—___ 86D (075: igc 670m, RNO as monitor oF, wed F9"= 1, QS) a ‘gc $30 cot 670m, HOMCOH 0; on crete s7Fi08 hype 234 Pataloeyanin, suf ron) HOpH=7 air ° comes itsnl endoperxide:re10 ¢4S)= ROO (175:4ge= 670 am. RNOs monitor of wed = 1, 4S) at Sbnm,cor 1670 am. 2235 Phthaocyanine, eral, horogallium I) HOMeOH 03 oar CHP A=Tps ae 680 om. s7R108 Gaye? 236. Pitalocyanin, suo ehlorogatiam(t1) nyoMteon O; 036 Cm As Tp ge 680m Fis 5 slo, oxovanadium(T¥) sir ° Cmt3——S'=RB: Aim: P= imidazole endopeoxie: re 10 (8) = S6ROKO (078: = 670 em. RNO ss monitor of: wed #9 = 1. 5) at 1hee= Bam, coe 1670 am. 238 Pitalocyanin, tris xinet) DOpH=7 0; 036 PULLSS Se Hy TPPS"s 1 (8) = 062; meas ofS) =OST; Aug SOAIR2 355 am. Rel. Sin HO: socom 210° mel Dosprme ooner ano Ie nett ww PP = 2.39, Phtaloeyaine, suo zinc) HopH=T ar as (ChAS——S'=RB: Amt; Po Imiduole endopeoxide: rel 10 6(S)=_ SOROSO (075: ige= 670 am- RNO ss monitor of wed P= 1408) 1ge $30.06 1 670m. HoMeOH 0; on CHP AS TipH hye = 669m, s7FI08 MoD a oa PULSE $= HPL tw 44S) = 05% mess. OY) ROSE hye = ST, ETRIBE 036 foie samming PB =0. =e reaed. wing gS)=STRIBS Gis tom 82155,QUANTUM YIELDS FOR FORMATION OF SINGLET OXYGEN 179 “ile 2 Quantum yk of potosensized profusion of net yee, porphyrins —Conined No Sone 103 fF Metod Commer ter 239 hialoyaning allo sineI)—Contined MoD? 050" PULLS642 =P re 109469) 05% mess. GS) 0.56; Aug 6O4 om. ATRIES oar ‘f= sing PP = 0; sed P= Isreal ng 4) = {i om (85215) Meop at ase runisoaz teh w 4S) =038, ce oS) = 0.56, e650 BOE 032 JF =0.9 soning PP 0 rd P= I eae, ng 6 {ht om (882155 2440 Puihaleyanne etracarbonr copper) DMSO Oy aus crass PBF ndependen of (S]= (2.26) 10% mol; mere #9260 ‘edligomen my bese. 21 rumstoyanine, 210 254tranaaimenyeny) cu ase MLSS S'=TPReLw q6)=07 soroos an om ane PLAIS6 eo TIM aun fll) 02013662 a ceva ae 2.42 Phihalcyanine 29,1623etraki(.-imethylethy), cloroakominundD oe oe FAs Sa TPM huey) O70, ue zones oa 2142 Philoyaning,29,624trki mete) copper) cu ae uu Huis = TPF EL 1098) = 070: = 62 om seno4 an 24 Puialcyaing(29,16234etraki ime ety), magnesia) cyt 06 PULLSS | S'=TPP L109) = 070A 652 om. sora or 24S Phialocyanng, rake nethyentoldimethyamineymetyhéynelitrakis¥-methymethanaminumto copper teracMorie HOpIt=7 se ° Chm S=RBLA= Im; Po nial endoperovies Lio (8) = ROD 25: hee = 610m, RNO ae mono of Ped PP = Noe Sb, cori 670 am. 246 Poephine coc at oor PULLS S'= RMPDME: re. wats aso cy, air 075 PILLS ‘S'= Pha; rel. 1 94(S)=0.8. PP =I, ‘22FI61 247 Porpine 21.25, Coc it on PULLS ST RIMPDME:reL104(8)= 1: ge M7 mm, P=, SEIS 28 rong, -mi-4247-rMy 94 Ab-eramey--AMOEHOpErPIEIN CaO oss FULLSS —S'=REMPDME: re 10S) 10 aso 249 Porpin,218-be3-dimethylammonlo)propl}712-dlethy 38.1317 setramety imetaneslonate D.OwOH aie 09 PULLSS— SeTPP L109) 07; 2g "357 tm, RELIOTHPINCCle ASF os) 250 Poepin,218.s-cinthsammone)ropyl}712-dthy38,13)7Aetramety imethanesuloat, coal) ae 02 PULLSS —S'=TPP2L104(8)= 07: yg 337 am. ReltoTPPIn CCl SSF a 2.51 Parphing,2,-Adimethylammonie)prony7.12eh-A8 1,17 Ssrametyl dimethanesifonte, manganese) D,OMmOH it non PULLS S=TPPeL10(8)=07; 2 =297 om. Rel TRPIn Cle ASF @) 2252 Porphine 218 Mel aimetylammons)prepy} 743 deg 381347 ktremetyt methanol) D,OROH ie oat PULLS S= TPP eL0948)=07: Aye IT om. RetwTPPin CO, BFE a3)180 WILKINSON, HELMAN, AND ROSS “Tble 2, Quantum yes of photosenitized prodction of singlet oxygen, porphyrin —Coninsed No Solvent 103) fh Mebod Comment Ret 2.53. Porphine,21,23-dideutero-2,ihyre-5,1015,20-etrapheny-Tetraphenylhlorin) cane, at 070 PULLS S'=RBPDME: L108) 1 ue" 37 om AI, 254 Porphing 21,23-dieutero-23.7831213,1718-octathy-(Octacthyiporphyrin) ach ai ons PULESS = RIMPDME: rl 144 sess 255 Porphine21,23-dieutero-237.8,1213,1718-ctaethyh2,3-ihy dru (Octathyehorid) CasCHy ie 080 PLILLSS ——_S'= FEMPOME: el. to oS sess 2.56 Focpin,21.23-dMewero-297 121317 1Baetly Sets (oeMehylatacthypo pyri) cates ie ost PULLS Sm PIMPDME; re, 105) I Aye 347mm. PEL, OBIS 257 Porphine21,23-dideutero-2,37,8,12,3,178-oclaethyl21-methy-(V-Metylotathyporphyrinds) scsi ass PLS S'=PIMPDME: re. 1094(8)=l:hyc=347 am. Pat, SORBIS 258. Porphine,21,23+ldeutero-23741213,17.18ctactyS phenyl -Phenyloctaetyporphyrited) Hc, ae 60 PULSE S'=RIMPDAE; 10 9(8)~ Age“ HP am AP= 1, BOS 2159, Porphin,21,25-

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