The PAH World Discotic polynuclear aromatic compounds as a mesophase scaffolding at the origin of life S. N. Platts nickplatts{*at*}yahoo.com "...

le hasard ne favorise que les esprits pr par s " (chance only favors prepared minds) !ouis Pasteur "#$%%&#$'() The *PAH World* is a novel chemical structural model for the plausi+le formation of oligomeric proto&informational templating materials on the early ,arthpresuma+ly progenitors of the .idely e/pected RNA World in chemical evolution theory. The model is +ased on the self&assem+ling discotic mesogenic +ehaviors of polynuclear aromatic compounds0 their photochemical edge&derivati1ations0 and the selectivity of such stac2ed supramolecular *aromatic core* scaffolds for the edge&on +inding and 3 4.56 nm plane&parallel spacing of essentially random collections of small pre+iotic heterocycles0 ta2en up and concentrated directly from the presumed and surrounding *dilute primordial soup.* The constrained "o+lig7) inter&+ase separation distance .ould select for oligomeri1ing *lin2ers* "enlan1antes) of fairly "+astante) specific si1e0 such as small methanal oligomers0 .hich .ould also +e ta2en up from the pre+iotic chemical environment0 condensing .ith the small heterocycles and also .ith each other to form the fle/i+le structural +ac2+one of a first generation of proto& informational oligomeric material0 sta+ili1ed against +oth hydrolytic and photolytic degradations +y its association .ith the parent discotic mesophase. A transient local pH decrease "e.g.0volcanic S8%"aq.)) .ould disrupt the hydrogen +ond interactions anchoring the oligomer to the discotic scaffold0 there+y releasing segments or portions of oligomeric material to e/plore intramolecular degrees of motional freedom out in solution0 perhaps folding "plega+le) +ac2 on themselves to match up "empare9ar) fortuitous +ase residue pairings via familiar Watson&:ric2&li2e complementarities. Segments rich in such chance complementarities .ould li2ely persist +y virtue of the com+ined cooperative strength deriving from "i.) the multiple intramolecular hydrogen +ond interactions +et.een paired +ases0 and "ii.) the attractive pi&pi stac2ing van der Waals interactions occurring +et.een neigh+oring and stac2ed +asepairs. This com+ination of interactions esta+lishing the domains of essentially hydropho+ic quasi& discotic mesophases in the secondary and tertiary structures of these oligomeric proto&informational materials- +ase mismatchings "mal empare9adas) .ithin such domains naturally leading to point replacements selecting to minimi1e conformational potential energies. The ne. *PAH World* model is pleasing to chemical intuition0 and provides the first satisfying structural ans.er to the pro+lem of a li2ely origin for the phenomenon of life. The figures +elo. provide the details for this model.

;igure# Diagram illustrating a stac2ed and self&assem+led mesophase&type arrangement of discotic polynuclear aromatic molecules0 in .hich the aromatic cores of these molecules have +ecome associated and the system has self&organi1ed +y virtue of the .ea2 inter&molecular van der Waals forces of attraction operating +et.een the < molecular or+itals of nearest& neigh+or PAHs- these .ea2 nett attractive forces often simply +eing termed <&< stac2ing interactions . The stac2ed PAHs are disposed plane& parallel and are necessarily separated +y ca. 4.56 nm "cf. the 4.56 nm interplanar spacing seen in the ideal crystal structure for mineral graphite0 and the 4.56 nm inter&+asepair helical rise in the classic #'(5 Watson&:ric2 structural model for the = crystallographic form of DNA)- this inter&PAH distance essentially reflecting the characteristic si1e of the %p1 atomic or+itals of the Period % atoms "i.e.0 mostly car+on0 and occasionally nitrogen) comprising the aromatic core s2eleta of these e/ogenous polynuclear aromatic compounds. >llustrated at right are three stac2ed molecules of an e/emplar discotic polynuclear aromatic compound? he/a& peri&+en1ocoronene ":6%H#$ 0 he/a+en1o@+c0ef0hi02l0no0qrAcoronene0 H=: ). This particular PAH core has +een of some considera+le interest in the recent optoelectronics materials literature0 .here the field of discotics is advancing rapidly at the present time.

;igure % Barious e/emplar edge structures for partially derivati1ed PAH&type andCor graphene&type polynuclear aromatic molecules. The edges are sho.n vertically do.n the righthand side "el lado derecho) of each of the si/ PAHCgraphene fragments illustrated0 and hydro/y functionalities have +een added into the edge structures at random0 simply to +e illustrative of photochemical andCor geohydrothermal derivati1ations at the edges of polynuclear aromatic species. 8ther types of organic functionali1ationCderivati1ation "e.g.0 &:88H0 D8) are certainly possi+le0 especially given the 2no.n productive richness "rique1a) of organic photochemistry. The PAHCgraphene edges sho.n are partially hydro/ylated and are thus also partially o/idi1ed relative to the parent aromatic

hydrocar+ons. There are clearly many more possi+le polynuclear edge structures than those +eing sho.n here0 and the variety of conceiva+le edge structures is further increased +y the various chemical functionalities that are possi+le. All common edge functions "e.g.0 hydro/yl0 2eto0 car+o/ylic acid0 etc.) can engage "captar0 engranar) in hydrogen +onding0 and the planar dispositions of such functions around the edges of individual PAHs arranged in stac2ed discotic arrays offers immediate potential for the edge&on "vista lateral) +inding and ca. 4.56 nm plane&parallel spacing of small sp%& hy+ridi1ed heterocyclic molecules0 moving firmly to.ards the first physicochemically plausi+le mechanism for the selection and concentration of pre+iotic nucleo+ases and other similar small molecules out of the long presumed dilute pre+iotic soup . The ne. PAH World structural model directly addresses the long recogni1ed dilution and selection pro+lems inherent in all dilute pre+iotic soup models of the past0 these pro+lems having hitherto constituted t.o of the ma9or chemical "trope1ones) stum+ling&+loc2s in the origins&of&life field during the no. fifty&t.o years since Stanley !. Eiller s +rea2through discoveries in pre+iotic chemistry.

;igure 5 This figure is purely diagrammatic and is simply meant to help convey the essential features of the ne. PAH World model system. Three pre+iotic nucleo+ases are sho.n hydrogen +onded to hydro/y functions in the edge structures of some derivati1ed and neigh+oring PAHtype molecules0 .hich are themselves disposed in a stac2ed and discotic array. The e/emplar polynuclear aromatic compound +eing envisaged "previsto0 imaginado) here is #05&dihydro/y he/a&peri&+en1ocoronene ":6%H#$8% 0 #05&dihydro/y he/a+en1o@+c0ef0hi02l0no0qrAcoronene0 H=:&#05&diol ). The hydro/y functionalities0 and their #05 dispositions0 are merely meant to +e

illustrative of the general chemical principle of photochemical andCor hydrothermal derivati1ation at the edges of PAH&type and graphene&type molecules. The three nucleo+ases are +eing sho.n in their 2eto tautomeric forms0 so as to +e consistent .ith the seemingly reasona+le assumption that pre+iotic Hadean "i.e.0 F ca. 5.$( Ga) surface and rain .aters .ere pro+a+ly acidulous. The 2eto tautomers +ear "cargan) the pro&glycosidic purine and pyrimidine secondary amine nitrogens "i.e.0 the NH functions at N"') and N"#)0 respectively) disposed "dispuestos) out.ards "hacia afuera)0 and thus chemically accessi+le to the surrounding solution. T.o unspecified pre+iotic oligomers of formaldehyde0 "H:H8)n 0 are sho.n +et.een neigh+oring heterocyclics0 and it seems li2ely that the fairly "+astante0 equitativa) constrained inter+ase spacing "espaciada) .ould lead to the system selecting for oligomeri1ing lin2ers .hich are themselves of similar si1e. The derivati1ed PAHCgraphene edge structures can no. effectively +e seen to represent something of an electronic phase +oundary "lHmite0 frotera) +et.een the discotically arrayed aromatic cores of the PAHs and the presumed surrounding aqueous media of Dar.in s .arm little pond "laguna0 estanque) . The phenomenon of life might no. +e seen as deriving from .hat is effectively a phase separation +et.een the discotic aromatic cores of the PAHs versus the surrounding aqueous+ased phase. >t seems pro+a+le that the essentially regular "%p1) inter&+asepair plane&parallel spacing distance of ca. 4.56 nm .as inherited +y molecular +iology as a chemical memory of this unique mode of origin0 and that this structural molecular fossil has +een conserved to us in the essentially quasi&discotic mesophase regions of heterocyclic nucleo+ase pairings in the secondary and higher order structures of e/tant nucleic acids.

;igure 6 The pyrimidyl and imida1ole NH functions of the three nucleo+ases are no. sho.n condensed via N&glycosidic&type covalent lin2ages to the presumed "H:H8)n oligomers0 and the formaldehyde oligomers are

themselves no. sho.n having condensed together to produce an e/tended oligomeric +ac2+one for the primitive proto&informational molecular materialal+eit that this earliest +ac2+one material is pro+a+ly li2ely to have +een +ranched in structure0 rather than straightfor.ardly linear as depicted in the figure. At this stage0 the nucleo+ase residues remain hydrogen +onded to the stac2ed and scaffolding array of functionali1ed PAH&type molecules0 and the co&operative effects of these multiple hydrogen +onds together .ith the multiple <&< stac2ing interactions serves to sta+ili1e and maintain the proto&informational oligomeric material against +oth hydrolytic and photolytic degradations during further gro.th. The N&glycosidic&type covalent +onds are not dra.n to scale in the figure0 and the methanalderived oligomeric +ac2+one is simply indicated here +y a 1ig1ag line.

;igure ( Diagram sho.ing the e/pected effect of a sudden "sI+ita) decrease in am+ient pH causing disruption of the inter& molecular hydrogen +onding interactions hitherto e/isting +et.een sections of proto& informational oligomeric material and the stac2 of discotic and derivati1ed PAHs. A sudden decrease in local pH0 such as .ould +e caused +y a volcanic release of acidic gases "e.g.0 S8%"g) and :8%"g))0 .ould lead to significant degrees of protonation of the hydro/y0 2eto0 and amino functions +oth in the PAHCgraphene edge structures and in the heterocyclic +ases0 thus setting up strong :oulom+ic forces of inter&molecular repulsion +et.een the positive electric charges .hich .ould +e almost instantaneously resident on the o/ygen and nitrogen functionalities in the PAHCgraphene edges and also in the proto&informational oligomer s heterocyclic +ase residues. Sections of primitive proto&informational oligomeric template material .ould thus +e released to e/plore conformational degrees of freedom out in solution. The sections of oligomer

might +e either totally freed of the PAHCgraphene stac2 altogether0 or might perhaps remain tethered to the discotic stac2 at one or +oth ends via some sort of structural +ranchingCcross&lin2ing. 8nce the pH catastrophe had passed0 the levels of protonation of the heterocyclic +ase functions .ould decrease as the am+ient pH returned to normal0 and the sections of ne.ly released oligomer .ould then +e free to fold +ac2 on themselves to +ring electrically neutral heterocyclic +ase residues into hydrogen +onding pro/imities0 perhaps to match up adventitious Watson&:ric2&li2e complementarities.

;igure J T.o representations of a single section of ne.ly released proto& informational oligomeric material .hich0 having +ecome dissociated from a stac2ed and scaffolding array of derivati1ed polynuclear aromatic species0 has +een free to e/plore conformational degrees of freedom out in solution. The ca. 4.56 nm inter&heterocyclic +ase&residue plane&parallel separation constraint0 structurally inherited from the discotic derivati1ed PAHCgraphene scaffold0 .ould +e e/pected to readily favor the intra&molecular matching up "i.e.0 hydrogen +onded +asepairing) of complementary small heterocyclic +ase residues0 as segments of protoinformational material came upon one another in the essentially +lind process of e/ploring their individual availa+le conformational parameter spaces. >n the ideali1ed and simplified e/ample +eing sho.n here0 involving a single molecule of an oligomer having an entirely linear "i.e0 un+ranched +ac2+one) primary structure0 a single strand of nascent proto&informational oligomer is sho.n having folded +ac2 upon itself0 .hen it at once +ecomes intuitively conceiva+le that fortuitous Watson&:ric2&li2e +asepaired complementarities .ould +e matched up.

;urther0 that in the case of a single oligomeric molecule folding +ac2 on itself to form a stem&loop type secondary structural motif li2e that sho.n here0 the +ac2+one chains of the presumed intramolecular proto&duple/&li2e structure .ould thus +e set to run anti&parallel0 this +eing immediately reminiscent of a crucial and recurring secondary structural feature of e/tant nucleic acids0 originating .ith the famous anti&parallel chain +ac2+ones descri+ed +y Watson K :ric2 in their classic #'(5 dou+le helical structural solution for the =&form of DNA0 and +eing very evident in the higher&order structures of ri+osomal LNA and transfer LNA molecules. Having formed fortuitous Watson&:ric2&li2e +asepairs0 it is entirely physicochemically conceiva+le that the co&operative reinforcing strengths of the multiple intra& molecular inter&heterocyclic hydrogen +onds and inter&+asepair <&< stac2ing interactions .ould lead to the persistence of complementarity&rich segments of proto&informational material. Such complementarity&rich regions might themselves no. usefully +e considered as constituting quasi&discotics and to +e e/hi+iting a mesophase&li2e +ehavior0 .ith the nascent mesophase +eing sta+ili1ed against dissociation +y virtue of the presence of the locali1ing and reinforcing oligomeric +ac2+one. Given the seeming pre+iotic implausi+ility of an oligomeri1ed sugar&phosphate +ac2+one at such an early stage in chemical evolution0 it .ould seem that practically any pre+iotically plausi+le and fle/i+le +ac2+one material could have initially sufficed to.ards fulfilling the primary requirement of sta+ili1ing these complementarity&rich regions of proto&informational quasidiscotic mesophase material against dissociation andCor hydrolyticCphotolytic environmental degradation. The maintenance of the characteristic ca. 4.56 nm inter&+asepair spacing distance through geologic and evolutionary time to the present day0 together .ith the structural and mechanistic chemistries of 2no.n ri+o1ymic activity supporting an LNA World scenario0 .ould suggest that the sugar&phosphate +ac2+ones of e/tant nucleic acids .ere selected for early in the history of life on ,arth0 +oth to.ards sta+ili1ing and securing these quasi&discotic mesophase regions0 and for the presumed chemical evolutionary advantages accruing at the essentially +lindly& stum+led&upon origin of ri+o1yme&li2e chemical activities0 e/tant e/amples of .hich crucially involve +oth the ri+ose&residue and the phosphate& residue moieties of the oligomeric +ac2+one material itself in their ri+o1ymic activities. >n further regard to the etiology "+orro.ing Al+ert ,schenmoser s use of this term) of the oligomeric +ac2+one0 it .ould seem reasona+le that the configurational loc2ing&in of stereochemical chiral informational specificities at asymmetric car+on centers in the earliest +ac2+one materials could certainly have moved these early systems to.ards minimi1ing the conformational potential energies of these first segments of proto&informational oligomeric material- this chiral loc2 in configurational parameter space presuma+ly representing the long&e/pected and contingent fro1en accident of causation of +iological homochirality0 and thus an early chance chemical evolutionary step in the do.nstream direction of something more nearly resem+ling a recogni1a+le progenitor of the .idely e/pected LNA World milestone in origins&of&life science. The conformational&potentialenergy& lo.ering selection for the conservation of complementarity&rich regions of protoinformational oligomeric materials may .ell +e the single most important physicochemical and etiological factor

to.ards a narro.ing do.n of the informational possi+ilities in terms of the su+set of small pre+iotic nitrogenous heterocycles from .hich .as eventually to +e derived the +iological genetic code of nucleo+ase residues for all life on ,arth.

;igure M T.o&dimensional representation of some possi+le secondary structures for portions of nascent proto&informational oligomeric material ne.ly released from attachment to discotic polynuclear aromatic functionali1ed PAHCgraphene scaffolding0 perhaps o.ing to a transient decrease in the local pH resulting from a sudden volcanic release of an acidic o/ide "e.g.0 S8%"aq.)). The 1ig1ag lines represent oligomeric +ac2+one material "e.g.0 "H:H8)n )- the short straight lines represent individual pre+iotic heterocyclic residues oriented .ith their 1&a/es in the plane of the paper "i.e.0 individual +ase residues are oriented edge&on to the vie.er)- and the longer straight lines represent hydrogen +onded pairs of complementary +ase residues. Note that the edge&on perspective has +een maintained throughout for simplicity and ease of illustration. Whereas the previous figure ";ig. J) sho.ed the ideali1ed case of a single molecule of a linear proto&informational oligomer0 here are sho.n pro+a+ly more li2ely e/amples of +ranched +ac2+one primary oligomeric structures0 sho.ing regions of +oth intra& and inter&molecular inter+ase hydrogen +onding and <&< +ase stac2ing associations0 in .hich fortuitous Watson&:ric2&li2e

+asepairs have matched&up o.ing to chance complementarities of sequence. The essential planarity of the various +ase pairings0 com+ined .ith degrees of rotational freedom in the +ac2+one material itself0 has led to the +asepairs +eing a+le to +ehave as quasi&discotic mesogens0 .ith the consequent formation of mesophase&li2e regions in .hich sta+ili1ing <&< stac2ing van der Waals interactions are a+le to operate at the ca. 5.6 NngstrOm plane&parallel separation distances +et.een neigh+oring and stac2ed +asepairs. At the present stage of the model s development0 formaldehyde "i.e.0 methanal0 H:H8) oligomers appear to offer the simplest pre+iotically accepta+le solution to the pro+lem of the li2ely original +ac2+one materials0 and the small varia+ilities in the inter&residue spacings sho.n in the figure reflects varia+ility in the admissi+le si1es of the small lin2er molecules originally selected from the pre+iotic chemical environment during the formation of the proto&informational oligomeric materials at the discotic scaffolds "i.e.0 reflecting degrees of inter&discotic lateral and rotational freedom in the supramolecular scaffolding structures). =ranching and cross&lin2ing in the +ac2+ones seems li2ely in terms of the primary structures of the oligomeric products +eing envisaged here0 versus the linear primary structures of ri+o1ymic oligonucleotides called for in the conte/t of the .idely regarded LNA World hypothesis. ;urther development of the ne. PAH World model in the do.nstream direction of something more strongly resem+ling the .idely e/pected LNA World seems to a.ait a full etiological e/planation of the structural0 chemical0 and stereochemical reasons +ehind the chemical evolutionary selection for the sugar&phosphate oligomeric +ac2+ones o+served in e/tant nucleic acids. The formation of quasi&discotic mesophase regions in such secondary structures as are +eing sho.n in the figure .ould +e essentially independent of the precise chemical identities of the +asepaired small heterocycles0 and this feature of the model immediately suggests collections of essentially random sequence starting points at the origin of an incipient and +lind informational potential and capacity. We+page Design? :hris Ec:arthy exoplanet{+}gmail{o}com

GLOSARIO DE TRMINOS.Polycyclic aromatic hydrocarbon The simplest PAHs0 as defined +y the >nternational Pnion on Pure and Applied :hemistry ">PPA:) "G.P Eoss0 >PPA: nomenclature for fused&ring systems)0 are phenanthrene and anthracene0 .hich +oth contain three fused aromatic rings. Smaller molecules0 such as +en1ene0 are not PAHs. PAHs may contain four&0 five&0 si/& or seven&mem+er rings0 +ut those .ith five or si/ are most common. PAHs composed only of si/&mem+ered rings are called alt rnant PAHs. :ertain alternant PAHs are called "+en1enoid" PAHs. The name comes from +en1ene0 an aromatic hydrocar+on .ith a single0 si/& mem+ered ring. These can +e +en1ene rings interconnected .ith each other +y single car+on&car+on +onds and .ith no rings remaining that do not contain a complete +en1ene ring.

The set of alternant PAHs is closely related to a set of mathematical entities called polyhe/es0 .hich are planar figures composed +y con9oining regular he/agons of identical si1e. PAHs containing up to si/ fused aromatic rings are often 2no.n as "small" PAHs and those containing more than si/ aromatic rings are called "large" PAHs. Due to the availa+ility of samples of the various small PAHs0 the +ul2 of research on PAHs has +een of those of up to si/ rings. The +iological activity and occurrence of the large PAHs does appear to +e a continuation of the small PAHs. They are found as com+ustion products0 +ut at lo.er levels than the small PAHs due to the 2inetic limitation of their production through addition of successive rings. Additionally0 .ith many more isomers possi+le for larger PAHs0 the occurrence of specific structures is much smaller. PAHs possess very characteristic PB a+sor+ance spectra. These often possess many a+sor+ance +ands and are unique for each ring structure. Thus0 for a set of isomers0 each isomer has a different PB a+sor+ance spectrum than the others. This is particularly useful in the identification of PAHs. Eost PAHs are also fluorescent0 emitting characteristic .avelengths of light .hen they are e/cited ".hen the molecules a+sor+ light). The e/tended pi&electron electronic structures of PAHs lead to these spectra0 as .ell as to certain large PAHs also e/hi+iting semi&conducting and other +ehaviors. Li!"id cry#tal# "!:s) are a state of matter that has properties +et.een those of a conventional liquid and those of a solid crystal.@#A ;or instance0 an !: may flo. li2e a liquid0 +ut its molecules may +e oriented in a crystal&li2e .ay. There are many different types of !: phases0 .hich can +e distinguished +y their different optical properties "such as +irefringence). When vie.ed under a microscope using a polari1ed light source0 different liquid crystal phases .ill appear to have distinct te/tures. The contrasting areas in the te/tures correspond to domains .here the !: molecules are oriented in different directions. Within a domain0 ho.ever0 the molecules are .ell ordered. !: materials may not al.ays +e in an !: phase "9ust as .ater may turn into ice or steam). !iquid crystals can +e divided into thermotropic0 lyotropic and metallotropic phases. Thermotropic and lyotropic !:s consist of organic molecules. Thermotropic !:s e/hi+it a phase transition into the !: phase as temperature is changed. !yotropic !:s e/hi+it phase transitions as a function of +oth temperature and concentration of the !: molecules in a solvent "typically .ater). Eetallotropic !:s are composed of +oth organic and inorganic molecules- their !: transition depends not only on temperature and concentration0 +ut also on the inorganic&organic composition ratio. ,/amples of liquid crystals can +e found +oth in the natural .orld and in technological applications. Eost modern electronic displays are liquid crystal +ased. !yotropic liquid&crystalline phases are a+undant in living systems. ;or e/ample0 many proteins and cell mem+ranes are !:s. 8ther .ell&2no.n !: e/amples are solutions of soap and various related detergents0 as .ell as to+acco mosaic virus

Li!"id cry#tal $ha# # The various !: phases "called mesophases) can +e characteri1ed +y the type of ordering. 8ne can distinguish positional order ".hether molecules are arranged in any sort of ordered lattice) and orientational order ".hether molecules are mostly pointing in the same direction)0 and moreover order can +e either short&range "only +et.een molecules close to each other) or long&range "e/tending to larger0 sometimes macroscopic0 dimensions). Eost thermotropic !:s .ill have an isotropic phase at high temperature. That is that heating .ill eventually drive them into a conventional liquid phase characteri1ed +y random and isotropic molecular ordering "little to no long&range order)0 and fluid&li2e flo. +ehavior. Pnder other conditions "for instance0 lo.er temperature)0 an !: might inha+it one or more phases .ith significant anisotropic orientational structure and short&range orientational order .hile still having an a+ility to flo.. @$A@'A The ordering of liquid crystalline phases is e/tensive on the molecular scale. This order e/tends up to the entire domain si1e0 .hich may +e on the order of micrometers0 +ut usually does not e/tend to the macroscopic scale as often occurs in classical crystalline solids. Ho.ever some techniques0 such as the use of +oundaries or an applied electric field0 can +e used to enforce a single ordered domain in a macroscopic liquid crystal sample. The ordering in a liquid crystal might e/tend along only one dimension0 .ith the material +eing essentially disordered in the other t.o directions. @#4A@##A M #o% n is the fundamental unit of a liquid crystal that induces structural order in the crystals. Typically0 a liquid&crystalline molecule consists of a rigid moiety and one or more fle/i+le parts. The rigid part aligns molecules in one direction0 .hereas the fle/i+le parts induce fluidity in the liquid crystal. This rigid part is referred to as mesogen0 and it plays a crucial role in the molecule. The optimum +alance of these t.o parts is essential to form liquid&crystalline materials. Di#cotic $ha# # Dis2&shaped !: molecules can orient themselves in a layer& li2e fashion 2no.n as the discotic nematic phase. >f the dis2s pac2 into stac2s0 the phase is called a di#cotic col"mnar. The columns themselves may +e organi1ed into rectangular or he/agonal arrays. :hiral discotic phases0 similar to the chiral nematic phase0 are also 2no.n. Naphthalene ":#4H$ constituent of moth+alls)0 consisting of t.o coplanar si/& mem+ered rings sharing an edge0 is another aromatic hydrocar+on. =y formal convention0 it is not a true PAH0 though is referred to as a +icyclic aromatic hydrocar+on. Aqueous solu+ility decreases appro/imately one order of magnitude for each additional ring. Stac&in% in supramolecular chemistry refers to a stac2ed arrangement of often aromatic molecules0 .hich is adopted due to interatomic interactions. The most common e/ample of a stac2ed system is found for consecutive +ase pairs in

DNA. Stac2ing also frequently occurs in proteins .here t.o relatively non&polar rings overlap. Which intermolecular forces contri+ute to stac2ing is a matter of de+ate. Stac2ing is often referred to as '-' int raction0 though effects due to the presence of a Q&or+ital are only one source of such interactions0 and in many common cases appear not to +e the dominant contri+utors. >n supramolecular chemistry0 an aromatic int raction "or '-' int raction) is a noncovalent interaction +et.een organic compounds containing aromatic moieties. Q&Q interactions are caused +y intermolecular overlapping of p& or+itals in Q&con9ugated systems0 so they +ecome stronger as the num+er of Q& electrons increases. 8ther noncovalent interactions include hydrogen +onds0 van der Waals forces0 charge&transfer interactions0 and dipole&dipole interactions. Q&Q interactions act strongly on flat polycyclic aromatic hydrocar+ons such as anthracene0 triphenylene0 and coronene +ecause of the many delocali1ed Q& electrons. This interaction0 .hich is a +it stronger than other noncovalent interactions0 plays an important role in various parts of supramolecular chemistry. ;or e/ample0 Q&Q interactions have a large influence on molecule& +ased crystal structures of aromatic compounds. >n DNA0 $i #tac&in% occurs +et.een ad9acent nucleotides and adds to the sta+ility of the molecular structure. The nitrogenous +ases of the nucleotides are made from either purine or pyrimidine rings0 consisting of aromatic rings. Within the DNA molecule0 the aromatic rings are positioned nearly perpendicular to the length of the DNA strands. Thus0 the faces of the aromatic rings are arranged parallel to each other0 allo.ing the +ases to participate in aromatic interactions. Through aromatic interactions0 the pi +onds0 e/tending from atoms participating in dou+le +onds0 overlap .ith pi +onds of ad9acent +ases. This is a type of non&covalent chemical +ond. Though a non&covalent +ond is .ea2er than a covalent +ond0 the sum of all pi stac2ing interactions .ithin the dou+le&stranded DNA molecule creates a large net sta+ili1ing energy. Gra$h n is a one&atom&thic2 "gruesa) planar sheet "lRmina) of sp%&+onded car+on atoms that are densely pac2ed in a honeycom+ crystal lattice "enre9ado0 entramado). >t can +e visuali1ed as an atomic&scale chic2en .ire made of car+on atoms and their +onds. The name comes from graphite S &ene- graphite itself consists of many graphene sheets stac2ed together. The car+on&car+on +ond length in graphene is a+out 4.#6% nm. Graphene is the +asic structural element of some car+on allotropes including graphite0 car+on nanotu+es and fullerenes. >t can also +e considered as an infinitely large aromatic molecule0 the limiting case of the family of flat polycyclic aromatic hydrocar+ons called graphenes.

Allotro$y or allotro$i#m is a +ehavior e/hi+ited +y some chemical elements? these elements can e/ist in t.o or more different forms0 2no.n as allotropes of that element. >n each allotrope0 the element*s atoms are +onded together in a different manner. Allotropes are different structural modifications of an element. @#A Allotropes should not +e confused .ith isomers0 .hich are chemical compounds that share the same molecular formula +ut have different structural formulae. ;or e/ample0 car+on has 5 common allotropes? diamond0 .here the car+on atoms are +onded together in a tetrahedral lattice arrangement0 graphite0 .here the car+on atoms are +onded together in sheets of a he/agonal lattice0 and fullerenes0 .here the car+on atoms are +onded together in spherical0 tu+ular0 or ellipsoidal formations. Ta"tom r# are isomers of organic compounds that readily interconvert +y a chemical reaction called ta"tom ri(ation. >t is common that this reaction results in the formal migration of a hydrogen atom or proton0 accompanied +y a s.itch of a single +ond and ad9acent dou+le +ond. The concept of tautomeri1ations is called ta"tom ri#m. Tautomerism is a special case of structural isomerism and can play an important role in non&canonical +ase pairing in DNA and especially LNA molecules.