Field Desorption Mass Spectrometry 1979 PDF

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Instrumentation

Field
Desorption
Mass Spectrometry
Warren D. Reynolds
National Center for Toxicological Research
Jefferson, Ark. 72079

A recent advance in the application of the molecular ion. Fragment ions


of mass spectrometry to biomedical can also be produced through thermal
and environmental research has been decomposition and field induced sur-
the development of the field desorp- face reactions.
tion ionization technique. Although
its potential has not been fully real- Emitters
ized, the simplicity of the field desorp- Early investigations by Miiller on
tion (FD) spectra, and its applicability field ionization microscopy and In-
to a wide range of analytical problems ghram and Gomer's subsequent work
t h a t encompass a multitude of com- led H. D. Beckey to a systematic study
pounds from inorganic salts to polar of the parameters required for field
metabolites has become its trademark. desorption mass spectrometry of or- To Mass Spectrometer
T h e growing use of this technique is ganic compounds (8-10). T h e intense
amply demonstrated by the increasing electric fields (10 7 -10 8 V/cm) neces-
number of publications, workshops, sary for field desorption are produced
reviews, and books during the period with positively charged emitters hav-
1971-78 (1-8,16). In this brief report, ing at their surface multipoint needles
the principles and analytical applica- of very great curvature (10 2 -10 3 Â
tions will be included for this impor- radii) on which an intense electric
t a n t mass spectrometric technique. field is established.
Field desorption mass spectrome- Emitter Properties. It will be Potential Difference
try's unique properties arise from the 10-12 kV
helpful in understanding the basis for
behavior of chemical compounds obtaining field desorption spectra of
under high potential fields. When a organic compounds to consider the de-
high field is applied to an absorbed or- velopment and limitations of the emit-
ganic layer on a metal surface, it expe- ters. Early in the development of this Figure 1. Simple model of field desorp-
riences an electrostatic force similar technique, several different emitter tion microneedle ionization source
to t h a t on the plates of a charged con- configurations were used such as thin
denser. If the metal surface (anode) metal blades, etched foils, and needle- Fo is 0.9 V/À for a normally sharp tip
has the proper geometry (sharp tip) sharp metal points (6). Sharp point of 10 3 Â radius. With increasing dis-
and under high vacuum ( 1 0 - 6 torr), emitters have the advantage over the tance from the apex of the tip, the
this force can be sufficient to eject other configurations in producing ex- field strength decreases, but the area
particles as positive ions t h a t can be tremely high field strengths. T h e local of equipotential field increases.
analyzed via a mass spectrometer microfield strength (Fo) at the tip of H. D. Beckey and colleagues (Uni-
(Figure 1). This, in essence, is the the microneedle, as defined by Speier versity of Bonn) have developed a pro-
basis for field desorption mass spec- et al. (11), is a function of the applied cedure for growing multiple ("Christ-
trometry. However, if the compound voltage ( V), radius of curvature of the mas-tree") polymeric needles, using
to be ionized reaches the anode via the tip (r) as well as the distance to the benzonitrile, from the vapor phase on
gas phase instead of being surface ap- counter electrode (d): a fine tungsten wire (10 μτη) under the
plied, the process is called field ioniza- influence of high electric fields (12)
tion. (Figure 2). Subsequent in-situ high-
1 a + SL]
In comparison with other ionization temperature carbonization resulted
F0=V in structurally strong carbonaceous
techniques, the smaller amount of
transferred energy in the FD process 2 r needles with improved efficiency of
(~0.1 eV) increases the probability of ionization. Although similar dendritic
detecting intact molecular ions. T h u s , where a = shape factor <^ 0.006. needles of other types of materials
the salient feature of field desorption For an applied voltage of 5000 V such as germanium, nickel, and other
spectra is normally the predominance and an electrode distance of ~ 2 . 3 mm, metals have been tried, these metal

This article not subject to U.S. Copyright ANALYTICAL CHEMISTRY, VOL. 51, NO. 2, FEBRUARY 1979 · 283 A
Published 1979 American Chemical Society
LJ Ci
Figure 2. Field desorption emitter hold­ Figure 3A. Scanning electron micrograph (500X) of high-temperature emitter
er and 10-μιτι tungsten emitter with car­ Tungsten wire (10 μαι) covered with carbon "microneedles" grown in benzonitrile vapor under high
bonaceous needles (arrow) field conditions

needles yield ions t h a t are less energy


homogenous than those from carbon
emitters (6).
T h e procedure for forming relative­
ly good carbonaceous emitters is de­
pendent upon a number of factors.
Cleanliness of the emitter preparation
apparatus and tungsten wire as well
as purity of the benzonitrile is impor­
t a n t for successful emitter prepara­
tion. T h e high-temperature activation
process for preparing carbonaceous
emitters is conducted in a small vacu­
um chamber under carefully con­
trolled conditions of temperature,
pressure, electric field strength, and
time. T h e temperature of the fine
tungsten wire (10 μτη), which is con­
trolled by the dc current, is adjusted
to a value sufficient to achieve a high
temperature (800-1000 °C) on the
emitter wire. T h e hot emitter wires
thermolyze the benzonitrile (~10 torr) Figure 3B. Scanning electron micrograph of high-temperature activated emitter
at various points on each wire. These at higher magnification (1000X)
points act as centers for further cat-
ionic polymerization during the high-
voltage operation (7-10 kV). By moni­ a small angle. This creates focusing
chemical and mechanical stability,
toring the field ion current on a plate problems during the subsequent re­
whereas the morphology determines
opposite to the emitters, the growth cording of FD spectra. Refocusing of
the efficiency of the microfields dur­
of the microneedles can be followed. the mass spectrometer after repetitive
ing ion production (13, 14).
Normally, after a short period of time, scans is necessary for good FD spectra.
Figures 3A and 3B show two scan­
the wire temperature is raised in a
ning electron micrographs of the mor­
programmed fashion to a specified Emitter Surface Processes
phology of the high-temperature pre­
limit (~1500 °C) as determined by di­
pared emitters. These micrographs il­ Currently, there is no quantitative
rect current during the activation pro­
lustrate the "tree-like" formation of theory for field desorption processes
cess. Activation time varies (6-10 h)
these microneedles. T h e branches ap­ of organic molecules from structural
and is dependent on the desired nee­
pear to be solidly grown together near and graphitized microneedle surfaces.
dle length. Long activation periods
the base. Electron diffraction studies T h e present theoretical understanding
with reduced field strengths generate
have shown that these needle struc­ of the dynamics of field desorption re­
long needles. Short, sharp needles are
tures correspond to an arrangement mains to be clarified due to the com­
preferred to long, blunt ones for most
of layers of graphite-like regions con­ plex nature of the emitter surface pro­
efficient ionization.
centric to the needle axis (73). cesses. However, there are several pro­
T h e ionization ability of the "acti­ Due to the nonhomogeneity of the posed mechanisms by which organic
vated" emitters is largely dependent microneedle size and directional or­ molecules can be converted to ions or
on the structural and morphological ientation, the surface ions generated ion clusters during the FD process,
composition of the microneedles. T h e during the FD process possess an en­ i.e., resonance electron tunneling and
structural ordering determines the ergy distribution and spreading over field induced surface reactions (6).

ANALYTICAL CHEMISTRY, VOL. 5 1 , NO. 2, FEBRUARY 1979 · 285 A


Figure 4A. Potential energy curve for interaction of organic Figure 4B. Potential energy curves in presence of electro­
molecule (M) with surface (A) in absence of electrostatic field static field
Ionic potential energy curve is downward, and its intersection with the
ground state curve produces a Schottky saddle, x-F-β = potential energy of
external field, F
Electron Tunneling. Tunneling Reprinted with permission from ref. 5. Copyright 1975 Verlag Chemie International
is a q u a n t u m mechanical process with­
out a classical mechanics analog. In the ( M + H ) + and (2M+H)+ ions t h a t Certain fragmentation reactions
the field desorption process, this result from a series of reactions as with relatively low activation energies
q u a n t u m tunneling involves surface shown in Figure 5. T h e fate of the have been found to be field depen­
substrate such as a metal or carbon. R O H t ion can take several pathways. dent. As an example, the elimination
T h e electron from the adsorbed organ­ If it reacts in a concerted mechanism of water to generate a C2H5 ion after
ic molecule can only enter the sub­ with a nearest neighbor and a free rad­ protonation of C2H5OH by direct
strate at or above the Fermi level, ical center on the carbon matrix, then (C2H5—ΟΗ 2 ) + bond rupture increases
since below this level there are, a t or­ a R O H j ion is generated. A secondary with increasing field strength (78).
dinary temperatures, no vacant quan­ reaction with additional nearest Other studies with acetone, acetoni-
t u m states for it to enter (15). Poten­ neighbor participation leads to clus­ trile, hydrocarbons, and others have
tial energy diagrams depicting this ter-ion formation [(ROH) 2 H+]. For yielded a number of general observa­
process are shown in Figures 4A and surface concentration depleted areas, tions concerning field-dependent pro­
4B. the R O H t is removed to give an M t cesses in the absorbed layers (78):
T h e occurrence of the field desorp­ ion current as seen in Figure 6 for eth- • Excluding emitter surface inter­
tion of an organic molecule is related anol (18). actions, the primary processes are pro­
to the tunneling probability (D) of the Field and T e m p e r a t u r e - D e p e n ­ ton transfer reactions.
nonbonding electron in the molecular dent Surface Reactions. T h e fate of • All ions formed are immediately
orbital. This probability is dependent surface generated ions and radicals is removed from the reaction zone due
on a number of factors including sur­ complex. T h e effect of the field can to the high potential gradient at the
face work function (Φ), ionization po­ play a dominant role on the mecha­ emitter surface.
tential (/), barrier potential (VR), and nism of these surface reactions. Other • Most field reactions take place
a local microfield (F) and can be writ­ factors affecting the outcome are the without activation energy.
ten (16, 17): electronic properties of the compound, • T h e products of field induced
e.g., tautomerism, temperature, and ion-molecule reactions are generated
D = exp C-V8mh 2
(eVR -E)dr surface environment. by simple bond rearrangements.

0.68 (I - Φ)3/2
iexp

Generally, for carbon emitters and


high field strengths (3-15 Χ 10 3 ap­
plied volts), the probability for " t u n ­
neling" lies in the range of 1 0 ~ 4 - 1 0 - 1
for most organic compounds. Conse­
quently, ion currents (C/g) obtained
from this type process are less by a
factor of 10-100 as compared to the 3ROH
normal 70 eV electron impact ioniza­
tion.
T h e "tunnel effect" has been attrib­ Figure 5. Upper: Diagram illustrating a three-step concerted surface mechanism
uted as the first step in many field of electron resonance tunneling and generation of protonated molecular ion,
ionization/field desorption surface re­ ROH^. Lower: Reaction indicating nonsurface interaction of RO· radical after elec­
actions. For example, alcohols (ROH) tron tunneling and cluster-ion formation (ROH) 2 H +
generally yield high ion currents for Reprinted with permission from ref. 18. Copyright 1974 Verlag der Zeitschrift fuer Naturforschung

286 A · ANALYTICAL CHEMISTRY, VOL. 5 1 , NO. 2, FEBRUARY 1979


Temperature dependence of FD
spectra is illustrated by a variety of
saturated and unsaturated carboxylic
acids containing 12 or more carbons.
At low-to-moderate anode tempera­
tures (0-8 mA), the M t and ( M + l ) +
ions dominate the spectra of the indi­
vidual acids while at higher tempera­
tures (10-20 mA), peaks representing
(M—17) + and (M—44)t are quite evi­
dent. For mixtures of acids, reactions
between constituents are possible. For
example, a 1:1 mixture of ci's-5-icosen-
oic acid (Mi) and elaidic acid (M2) be­
haved normally at low temperatures
yielding both M i t and M 2 t ions. At
higher anode temperatures (>15 mA),
both "dimer ions" and their cross
product dimer [(Mi + M2 + H—
H 2 0—COOH)+] were present (19).
An interesting class of thermally ac­
tivated, field induced reactions is the Figure 6. Pulsed field desorption mass spectrum of ethanol (—6 kV pulse, 0.1 MS,
ion attachment or "cationization" re­ emitter a t - 1 0 0 °C)
actions. The most stable "quasimolec- Reprinted with permission from ref. 18. Copyright 1974 Verlag der Zeitschrift fuer Naturforschung
ular" ions occur when cations such as
the alkali ions are attached to the ad­
sorbed organic molecules. T h e stabili­
ty of the ( M + C ) + ions is due to strong
charge localization at the alkali atom.
Thus, the charge shift by rearrange­
ment of the bonding electrons within
the ion necessary for decomposition
is prevented (20). The resulting mass
spectra display a high abundance of
cations (C) + and cluster-ions, i.e.,
( M + Q + and (nM+C)+, η = 2, 3 . ..,
at field strengths (<10 6 V/cm) that
are insufficient for ionization of ad­
sorbed organic molecules. Under FD
conditions the observed intensity dis­
tribution and maximum size of the
40 50 60~^ 240 250 260 270 280 540 550 560 570
cluster ions depend on how the mole­
cules diffuse into the ionization zone
at the emitter tip, i.e., neat or as com­
plexes. Thus, the FD mass spectra of
cationized organic molecules are sensi­
tive to the influences of the experi­ Figure 7. Field desorption mass spectrum of adenosine (1 M) with added lithium
mental conditions such as tempera­ chloride (1 M)
Water solvent. Note weak parent ion at m / e 267 and cationized m o l e c u l a r ion at m / e 2 7 4 ( 19)
ture, organic compound/cation ratio,
Reprinted with permission from ref. 20. Copyright 1975 Heyden and Son
distribution, and thickness of ab­
sorbed layer (8, 20). Figure 7 shows an using predominantly the ( M + N a ) + The excellent sensitivity of the FD
example of a L i + cationized spectrum ion group with a multichannel integra­ process toward alkali metal cations
of adenosine (1:1 mixture) (20). tion technique. Individual measure­ was discovered during early studies
ments had a mean error of ±7.2%, on organic and inorganic salts. The ion
Analytical Applications whereas the mean error of the average currents for the alkali metals are sev­
In comparison with electron impact value (100 scans) was ±0.7% (21). eral orders of magnitude more intense
mass spectra, less intense and often Mixtures of dopamine added to urine than the FD-generated organic ions.
fluctuating ion currents are generated at the 10-ng/VL level have been deter­ For example, cesium was determined
in FD. This has a limiting influence mined via the FD method using dopa- in several solvents, body fluids, and
on both the ultimate sensitivity and mine-d4 as the internal standard. water samples at the 0.3-1000-pg//uL
precision. Since nearly 100% of the After formation of the tris-bansyl de­ range with a minimum detectability
total ion current is frequently carried rivative and TLC cleanup, the relative in the low femtogram range. Since ce­
in the molecular ion group [Mt, error was 5% (22). sium is monoisotopic, an external cali­
(M+H)+, or (M-t-O+l, one has a fa­ Measurements on the degree of sta­ bration curve was used with a preci­
vorable condition for specificity with ble label isotopic incorporation can be sion of ±10% (24). FD spectra of other
minimization of disturbance due to done accurately via the FD method. inorganic salts have shown strong ions
impurities. Subsequently, the fluctu­ Glucose-1-di was determined to have suitable for trace quantitative analy­
ating ion currents require integration 97.4% deuterium incorporated at sis. K F gave (KF)K+ and (KF) 2 K+
techniques for good analytical mea­ this position using the cationized ions, whereas KBr gave (KBr)K + and
surements. For example, mixtures molecular ion group [ ( M + N a ) + , Br+ ions; N a N 0 3 — ( N a N 0 3 ) „ N a +
containing glucose and glucose- 1-13C ( M + N a + 1 ) + ] after correction for the where η = 1, 2, 3; NaN 3 —(NaNs)Na+
as an internal standard were analyzed (M-l+Na)+ion(23). and CaCl 2 —CaCl+, Cat and CaCl 2 + (25).

288 A · ANALYTICAL CHEMISTRY, VOL. 51, NO. 2, FEBRUARY 1979


several classes, e.g., macrolides, poly­
enes, ansamycins, aminocyclitols, and
acyltetramic acids, have also been
studied (31). In all cases, members of
the molecular ion group [Mt or
( M + H ) + ] were present as base peaks.
This is an advantage since most of the
EI spectra of these compounds do not
yield this molecular weight informa­
100
tion.
+
80· [ ( M - 5 9 ) + H + N a ] Summary
659.5
60 The fundamental advantage of field
[M + H + Na] + + desorption mass spectrometry is the
40 689 "soft" ionization process for thermally
20 sensitive and relatively nonvolatile
671 compounds. For many organic com­
ι ι)ι |lt ^
-4-r pounds, the FD mass spectra pro­
650 700 800 850 duced show the molecular ion or mole­
cule-cation complex alone or as the
L peak of highest relative intensity. T h e
Figure 8. Field desorption mass spectrum of vitamin B 1 2 relative absence of fragmentation ex­
Indirect heating by laser-supported FD-MS (0-200 mW). Mass resolution 8000 (10% valley). Note dou­ cept under thermal surface conditions
bly charged ions m/e 689 and 659.6 (27) aids in the molecular weight determi­
nations but becomes a disadvantage
when structure determinations are at­
tempted.
The assessment of the F D / M S tech­
nique for rapid organic mixture analy­
sis is limited and subject to matrix in­
teractions. The presence or absence
of nearest neighbor interactions, e.g.,
protonations, cationization, etc., in the
mixture does alter the FD spectra of
the sought-for constituent. In spite of
these limitations, good quantitative
analyses have been conducted utiliz­
ing the stable isotope dilution tech­
nique.
The attainment of the FD mass
spectra of large intact molecules, such
as the antibiotics and vitamin Β ] 2 , has
been a challenge and landmark. It rep­
resents a significant advance in the
application of mass spectrometry to
high molecular weight constituents.
Figure 9. FD mass spectrum of the flavanone glycoside, hesperidin
Resolution >15 000 (10% valley), photographic detection. Note molecule-cation complexes at m/e Acknowledgment
633 and 649
Reprinted with permission from ret. 29. Copyright 1977 North-Holland Publishing Co. I thank Ben Lau (NCTR) and Dave
Brent (Burroughs-Wellcome Corp.)
Nonvolatile and thermally labile or­ tensity at m/e 1354 with additional for many interesting and valuable dis­
ganic molecules with molecular thermal/field induced fragments at cussions. I also express my apprecia­
weights up to 2100 daltons are promis­ lower amu's. The high-resolution mea­ tion to Tom Grafton (NCTR) for his
ing candidates for FD analysis. In re­ surement at 914.445 agrees with the accomplishing the scanning electron
cent years, much of the difficulty in ion of composition: C45H fi r,Nn06Co micrographs of the field emitters.
assigning structures to peptide antibi­ that results from a loss of the nucleo­
otics has been due to an inability to tide side chain. References
determine accurate molecular formu­ A number of research groups have (1) H.-K. Schulten, "Advances in Mass
las. Recently, FD studies have been applied the FD/MS technique to bio­ Spectrometry in Biochemistry and Medi­
conducted on several cationized ( 7 Li, logical and natural product analytical cine," Vol. 1, Chap. 25, Spectrum Publi­
23
Na, and :i9 K) triacetates of anti- problems. T h e peptides (through cations, Holliswood, N.Y., 1976.
amoebin I to ascertain its molecular (2) W. D. Lehmann and H.-R. Schulten,
nona-) have been studied for sequenc­ Anal. Chcm., 49, 1744 (1977).
ion (MW 1796). By utilizing the high- ing information as well as 50 other (3) S. Pfeifer, H. D. Reckey, and H.-R.
resolution peak-matching technique, compounds representing a wide vari­ Schulten, Fresenius Z. Anal. Chem., 284,
the molecular formula: C88H38N17- ety of phospholipids and related bio­ 193 (1977).
0 2 nNa - 1818.9596 was confirmed chemical materials (28, 29). The natu­ (4) H. D. Beckey, S. Bloching, M. D. Mi-
(26). The FD spectra of vitamin B 1 2 , gahed, E. Ochterbëck, and H.-R. Schul-
ral product, hesperidin, is an example ten, Int. J. Mass Spectrom. Ion Phys.,
a complex macrocyclic ring system, of several surface FD mechanisms op­ 8, 169(1971).
has recently been completed (27). The erating simultaneously, which is indi­ (5) H. D. Beckey and H.-R. Schulten,
structure and FD spectrum are shown cated by the presence of both M t and Angew. Chem. (Int. Ed.), 14,403 (1975).
(6) H. D. Beckey, Κ. Levsen, F. W. Rôll-
in Figure 8. As indicated, the molecu­ ( M + N a ) + ions as seen in Figure 9 gen, and H.-R. Schulten, Surf. Sri., 70,
lar ion is present with high relative in­ (30). Various antibiotics representing 325-62(1978).

290 A · ANALYTICAL CHEMISTRY, VOL. 51, NO. 2, FEBRUARY 1979


(7) Third Annual Field Desorption Mass
Spectrometry Workshop, Burroughs-

Varian
Wellcome Corp., Research Triangle
Park, N.C., Feb. 2-3, 1976.
(8) H. D. Beckey, "Principles of Field Ion­
ization and Field Desorption Mass Spec­

announces
trometry," Pergamon. London, England.
1977.
(9) E. W. Miiller, Ζ. Phys., 131, 136 (1951).
(10) M. G. Inghram and Κ. J. Gomer, J.
Chem. Phys., 22, 1279 (1954).
(11) F. Speier, H. J. Heinen, and H. D.
Beckey, Messtechnik, 80 (6), 147 (1972).
(12) H. D. Beckey, A. Heindrichs, E. Hilt,
M. D. Migahed, H.-R. Schulten, and H.
training
U. Winkler, ibid., 78 (9), 196 (1971).
(13) D. M. Taylor, F. W. Rollgen, and H.
D. Beckey, Surf. Sci., 40, 264 (1973).
(14) B. Ajeian, H. D. Beckey, A. Maas, and
courses
Little things
U. Nitschke, Appl. Phys., 6, 111 (1975).
(15) E. Miiller and S. V. Krishnaswamy,
Surf. Sci., 36, 29-47 (1973).
(16) H. D. Beckey, "Field Ionization Mass
in gas
mean a lot
Spectrometry," pp 3, 207-10, 228-38,
Pergamon Press, Elmsford, N.Y., 1971.
(17) C. B. Duke, "Tunneling in Solids," pp
39-45, Academic Press, New York, N.Y.,
chroma­
in HPLC
1969.
(18) F. W. Rollgen and H. D. Beckey, Z.
Naturforsch., 29a, 230-38 (1974).
(19) G. W. Wood, E. J. Oldenburg, P. Y.
Lau, and D. L. Wade, Can. J. Chem., 56,
tography
Inlet filters. Rheodyne inlet filters can
be connected between the sample in­
1372-7 (1978).
(20) F. W. Rollgen and H.-R. Schulten,
Schedule for
jection valve and the column to protect
the column from plugging. The 2 micron
Org. Mass Spectrom., 10, 660 (1975).
(21) W. D. Lehmann and H.-R. Schulten, February, March
filter element prevents plugging
caused by particles in the samples or
Angew. Chem. {Int. Ed.), 16, 184 (1977).
(22) W. D. Lehmann, H. D. Beckey, and and April 1979:
H.-R. Schulten, Anal. Chem., 48, 1572
by injection valve wear particles. (1976). Basic Gas Chromatography
Pressure rating of the filter assembly is (23) W. D. Lehmann and H.-R. Schulten, Feb. 21-23, Florham Park. NJ
7000 psi (500 bar). Only type 316 stain­ Biomed. Mass Spectrom., 5, 208 (1978). March 7-9, Houston,TX
less steel and PTFE contact the stream. (24) H.-R. Schulten, R. Ziskoven, and W. April 10-12, Chicago, IL
U.S. prices are $45 for the Model D. Lehmann, Z. Naturforsch., 33c, 178 Lecture & Lab, 3 days, $225
7302 Column Inlet Filter and $20 for a (1978). Lecture only, 2 days, $155
package of 5 2μ(η filter elements (25) H.-R. Schulten and F. W. Rollgen,
Angew. Chem. (Int. Ed.), 14, 561 (1975).
and gaskets. (26) Κ. L. Rinehart, J. C. Cook, .Jr., H. Gas Analysis by
Pressure Relief Valve. Rheodynes Meng, K. L. Olsen, and R. C. Pandev, Gas Chromatography
Model 7037 Pressure Relief Valve Nature, 269,832 (1977).
(27) H.-R. Schulten and H. M. Schiebel, March 12-13, Houston,TX
protects your equipment against damage Naturwissenschaften, 65, 223 (1978). Lecture & Lab, 2 days, $225
from over-pressure. You can set it (28) J. Asante-Poku, G. W. Wood, and D.
anywhere in the range of 2000 to E. Schmidt, Jr., Biomed. Mass Spec­ Automatic Gas
7000 psi (140 to 500 bar). U.S. price trom., 2, 121 (1975). Chromatography*
is only $270. So, when you consider the (29) G. W. Wood, P. Y. Lau, G. Morrow,
fact that you can blow a pressu re gauge G.N.S. Rao, D. E. Schmidt, Jr., and J. March 14-16, Houston.TX
in less than 1 second, it's a real bargain. Tuebner, Chem. Phys. Lipids, 18, 316 April 18-20. Chicago. IL
(1977). Lecture & Lab, 3 days, $200
Teflon Rotary Valves. Type 50 Rheodyne (30) H.-R. Schulten and D. E. (James,
Valves are real workhorse accessories Biomed. Mass Spectrom., 1, 120 (1974). Glass Capillary
for your LC equipment. (31) K. L. Rinehart, Jr., and J. C. Cook,
Use them for sample injection, column Jr., J . Antibiot., 27, 1 (1974). Gas Chromatography
switching, recycling, reagent switching, Feb. 13-14, Denver, CO
fraction collection, stream sampling March 1-2, Florham Park, NJ
and quantitive reagent injection. Avail­ Lecture & Lab, 2 days, $225
able in four different versions, these Maintenance of the
valves are chemically inert with zero
dead volume, operate at 300 psi. They Gas Chromatography
are offered in 0.8 or 1.5 mm bore and in Feb. 26-27, Florham Park, NJ
either manual or automatic versions. April 16-17, Chicago. IL
U.S. price of 0.8 mm bore 3 and 4-way Lecture & Lab, 2 days, $225
valves is $80. The 6-position and To enroll in Chicago. Denver and
sample injection valves are priced at $95. Houston courses, please contact the
Cost of 1.5 mm bore valves is $2 more. Varian Instrument Division Training
Write for more data. For full information, Department, 2700 Mitchell Drive.
please address Rheodyne, Inc., 2809 Walnut Creek, CA 94598; Telephone
Tenth Street, Berkeley, CA94710. Phone (415) 939-2400. ext. 225. Enroll in Flor­
(415)548-5374. ham Park courses at Varian Instru­
ment Division Training Department,
Warren D. Reynolds is chief, Bioana- 25 Hanover Road,
lytical Methods Branch, NCTR. His Florham Park, NJ 07932;
interests include high-pressure liquid Telephone (201) 822-3700.

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ANALYTICAL CHEMISTRY, VOL. 5 1 , NO. 2, FEBRUARY 1979 · 293 A

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