Journal of Chromatographic Science 2013;51:704 715
doi:10.1093/chromsci/bmt040 Advance Access publication April 16, 2013
Preparative Gas Chromatography and Its Applications
Hua-Li Zuo1, Feng-Qing Yang1*, Wei-Hua Huang2 and Zhi-Ning Xia1
1
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China, and 2Institute of Clinical
Pharmacology, Hunan Key Laboratory of Pharmacogenetics, Central South University, Changsha 410078, China
*Author to whom correspondence should be addressed. Email: fengqingyang@cqu.edu.cn
Received 1 October 2012; revised 10 March 2013
Although hundreds of papers related to preparative gas chromatog-
raphy ( pGC) have been published since the late 1950s, the success
of the GC technique has largely been associated with analytical
instead of preparative purposes. Actually, pGC is an ideal alternative
technique for the preparation of pure substances, especially volatile
compounds. This paper reviews the papers (written in English) asso-
ciated with pGC published over the period from the 1950s to the
2010s. For large scale preparation, large sample injection and vapor-
ization, a high loading capacity column, a gas splitter at the end of
the column and a special collecting device are fundamentally import-
ant for a pGC system. The primary components of pGC system, in-
cluding injector, column, splitter, detector and collection traps, are
briefly introduced. Furthermore, the applications of pGC in the separ-
ation and purification of volatile compounds from natural essential
oils, in addition to the purification of isotopes, isomers and enantio-
mers are summarized.
Introduction
Gas chromatography (GC), invented by Martin and Synge in
1941 (1), was rst applied for the separation of a series of fatty
acids in 1951 (2). After this, the GC technique developed rapidly
and was the rst analytical instrument to be controlled by a com-
puter. The term preparative GC ( pGC) usually describes the use
of large-diameter columns to purify relatively large quantities of
materials by using a sample collection system at the column
outlet (3). Currently, GC is one of the most important and wide-
spread techniques in the eld of analytical chemistry. However,
the success of the GC technique is largely associated with chem-
ical analysis instead of pGC (4). Although Varex Corporation
commercialized a preparative scale GC (Model PSGC-10/40) late
in the last century, only a preparative fraction collector for GC
(Gerstel PFC, Gerstel GmbH & Co.) is still available on the
market today.
Actually, pGC is an important and practical alternative to
other preparative techniques such as preparative high-
performance liquid chromatography ( pre-HPLC), especially for
volatile compounds. There have been many applications of pGC
in the elds of synthetic chemistry (5 14); the ne chemical in-
dustry (15); the preparation of avors and fragrances, or odor-
iferous constituents (16 19), which are primarily used in
cosmetic industry sectors (20); environmental chemistry (21
24); pharmaceuticals (25); biology (26, 27); toxicology (28); and
compound-specic radio carbon analysis (CSRA) (21, 22).
According to the SciFinder database (Figure 1), papers related
to pGC have been published continuously since the late 1950s,
and more than 200 papers were published during the 1960s.
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Review Article
Although the publications related to pGC decreased during the
late 20th century, pGC has regained attention by researchers
during the past decade. It is believed that the characteristics and
advantages of pGC will gain more attention, and it is expected
that pGC will be a complementary technique for pre-HPLC in
the future. Several good books or book chapters have dealt with
pGC (29 31). In this paper, based on the articles (written in
English) associated with pGC published over the period of
1950s to 2010s, the components of the pGC system and the
applications of pGC were reviewed to provide scientic informa-
tion for further studies.
pGC system
The pGC system consists of a carrier gas system (including the
carrier tank, its path and a pressure controller), an injection
system (including injection port and vaporizer), a separation
column, splitter and detector and a trap used to collect the efu-
ents, which was not included in the analytical equipment. Today,
most of the pGC systems reported in the literature for prepara-
tive purposes have been modied from the analytical systems.
Sampling
Usually, the injection of the sample is accomplished manually by
a syringe (20), which is a laborious and time-consuming process.
An automated sampler controlled with a microprocessor has
been used, whereas the splitless injection mode is most com-
monly used for preparative capillary GC ( pcGC) (32, 33).
Furthermore, the cool injection system (CIS), which restricts
both thermal degradation and chromatographic discrimination
of the analyte to some extent, has also been frequently applied
in pGC and in analytical GC (33 35). In addition, a CIS contains
a mass ow controlled switching device combined with a dual
column system pcGC, designed by Rijks and Rijks, which did
well in the separation of complex samples, especially those of
low concentrations (36). A newly invented injection method for
pGC named a gas booster sample injection device was combined
with a large volume sample dosing ring and a pneumatic six-way
valve to control the sample introduction, and it also adopted
high-temperature desorption combined with diaphragm booster.
As a result, this unit efciently transferred large amounts of the
analyte to the sample loop (37, 38).
The loading quantity is considered to be one of the key factors
that affect the separation efciency for pGC. Therefore, special
attention should be paid to sample overloading, because this can
result in poor separation of the compounds or broader peaks
that decrease the resolution. However, this does not mean that a
 Figure 1. Publications related to pGC according to the SciFinder database.
large sample introduction is absolutely not allowed. For
example, if the amount of monomer obtained from multiple
small injections was less than a single larger injection, slight
overloading might be acceptable. Although this also suffers from
the loss of resolution, it is compensated by consuming much less
time. To improve the injection amount, an expanded vaporizer is
one of the most frequently used approaches. For example, for
the separation of volatile components from Curcuma rhizome,
an 8 cm  6.60 mm vaporizer was used (39). Furthermore,
Staerk et al. (40) modied the injector with an expansion vessel
constructed from a 1 m  0.53 mm i.d. stainless steel tube and
connected to the system by a six-way valve. However, the large
amount of injection may lead the volatile components with
higher boiling points condensed in the system, which may cause
a series of problems, including the blockage of conduits and
joints, uctuations in pressure and recontamination of the puri-
ed compounds. To solve this problem, Maroulis et al. (41)
designed a container at the injection site to supply liquid solvent
to wash away the deposit efuent after the last separation was
nished (or before the following preparation started). In add-
ition, vaporization of the sample before injection can prevent
the high pressure caused by instant gasication and avoid the
pollution of the injection port by the non-volatile compounds,
and thus the injection amount may be improved (15).
Column
Gas-liquid chromatography (GLC) is primarily used for the prep-
aration of low-boiling halides (42) or for the study of the struc-
ture or conguration of compounds (4347). The preparation
quantities of GLC may go from nanogram to microgram (48).
Although gas-solid chromatography (GSC) allows the harvest of
much larger quantities of the target compounds, it has primarily
been applied for more types of different chemical compounds
(39, 49) or for individual pharmacology/toxicology research.
Capillary columns, belonging to GLC, have predominantly been
used in GC (including pGC). However, the yielded compounds
may be contaminated by the vaporized stationary phase when a
high separation temperature is applied (42). Therefore, the sta-
tionary phase used in a pGC column must be physically and ther-
mally stable, and chemically inert, to avoid taking part in
chemical reaction during the preparation process (50). On the
other hand, for infrared (IR) or nuclear magnetic resonance
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Figure 2. FID chromatogram of technical p-nonylphenol on an HP-5 MS column
(30 m  0.32 mm i.d., 0.5 mm) and selected fractionation time windows. Eleven
fractions containing 77552 mg of isomers were collected after 600 single injections
(32). Adapted from Fig. 2 in Meinert, C., Moeder, M., Brack, W.; Fractionation of technical
p-nonylphenol with preparative capillary gas chromatography; Chemosphere, 2007, Vol.
70, p217; Copyright # 2007 Elsevier Ltd., with permission from Elsevier.
(NMR) analyses, the response of the stationary phase may mix
with the compounds of interest. Therefore, the IR and NMR
absorptions of 17 liquid stationary phases (including carboxylic
esters, ethers and silicones) commonly used in pGC have been
reported (51).
To enhance production, much effort has been devoted to in-
creasing the loading capacity of a column by extending its diam-
eter (52). However, increasing the column diameter can lead to
extreme losses in column efciency and separation resolution
(3, 53). The efciency of preparative columns with a relatively
large diameter (up to 40 mm) is approximately half that of
normal analytical packed columns (2 4 mm) (54). There is no
doubt that the larger the column diameter, the slower the heat
delivery rate from the outside to the center of the column (55).
Therefore, the larger diameter columns can lead to inhomogen-
eous heating when the oven temperature is programmed to rise,
which results in a retention time drift from time to time. It has
also been observed that the maximum ow rate and concentra-
tion of a component occur in the center of a column (56). The
efciency of large diameter columns can be improved by increas-
ing the length of the column or increasing the percentage of the
stationary liquid, or by operating at lower or isocratic tempera-
ture. However, accompanied by a considerable increase in
elution time, peak broadening may occur for compounds with a
high boiling point (bp) (57). Bayer et al. (58) described a theory
to explain why column efciency was lost with greater diameter.
By investigating the reproducibility of column packing, they indi-
cated that if the columns with 5 to 10 cm diameters were
packed under a longer time with consistent rocking, they may as
efcient as columns with 1 cm diameter. Reiser (59) suggested
an idea through an experiment that internal radial nned
columns provided higher efciency and resolution than regular
columns with the same diameter. On the other hand, Weinreich
(57) proposed a column with a 3-in.-thick diameter that was
heated inside instead of outside, which appropriately eliminated
the serious temperature gradient caused by conventional
columns. A method by using analytical columns in parallel with a
pGC column may either save time or avoid a decrease in
Preparative Gas Chromatography and Its Applications 705
 706 Zuo et al.

Table I
Applications of pGC in the Separation of Volatile Compounds from Natural Essential Oils*

Sample Target compounds Injection Column Carrier Detector Reference

gas
Methanol extract of Curcuma rhizome b-Elemene, curzerene, curzerenone, curcumenol and curcumenone Manual injection Packed column with 10% OV-101 Nitrogen FID 39
Peppermint oil Menthol and menthone Automated DB-5 Hydrogen FID 145
splitless injection
Volatile components of maize Fractions attractive to Cotesia marginiventris females On-column HP-1MS (1); HP-Innowax (2) Helium FID 108
injection
Volatile components extracted from coriander (E)-2-Undecenol, 2-phenylethanol, (E,E)-2,4-undecadienal and an unknown compound Automated Supelco-WAX Helium FID 106
splitless injection
Essential oil from Acorus tatarinowii cis- and trans-Asarone Manual injection Packed column with 10% OV-101 Nitrogen FID 49
Essential oil of Radula perrottetii Viscida-3,9,14-triene, viscida-3,11(18),14-triene, bisabola-2,6,11-triene, Manual injection Packed column with CPSil-5-CB (1); CPSil-19-CB (2) NA NA 146
bisabola-1,3,5,7(14),11-pentaene, bisabola-1,3,5,7,11-pentaene,
6,7-epoxybisabola-2,11-diene, 1-methoxy-4-(2-methylpropenyl)benzene,
bisabola-1,3,5,7(14),10-pentaene, ar-tenuifolene, a-helmiscapene and bhelmiscapene
Essential oil of Plagiochila asplenioides Aromadendra-1(10),3-diene, ent-4-epi-maaliol, bisabola-1,3,5,7(14)-tetraene, Manual injection Packed column with SE-30 on Chromosorb W-HP (1); Helium FID 147
bisabola-1,3,5,7-tetraene, muurolan-4,7-peroxide and plagiochilines W and X OV-1701 on Chromosorb G-HP (2); SE-52 on
Chromosorb W-HP (3)
Essential oil of Otostegia integrifolia ()-1-Methyl-4-(5,9-dimethyl-1-methylene-deca-4,8-dienyl)-cyclohexene Manual injection Packed column with SE-30 on Chromosorb W-HP (1); NA FID 100
SE-52 on Chromosorb W-HP (2)
Essential oil of Meum athamanticum a-/b-Barbatene, isobazzanene and isobarbaten Manual injection Packed column with OV-1701 on Chromosorb W-HP Helium FID 120
(1); SE-52 on Chromosorb G-HP (2)
Essential oil of Osyris tenuifolia, Tritomaria Sesquiterpenes, tenuifolene, artenuifolene, 2,(7Z,10Z)-bisabolatrien-13-ol and Manual injection Packed column with SE-30 on Chromosorb W-HP (1); Helium FID 112, 107,
polita, Bazzania japonica and Marsupella lanceoloxide OV-1701 on Chromosorb G-HP (2); SE-52 on 101, 102
emarginata Chromosorb W-HP (3)
Mixture of peppermint, spearmint and lavender Geraniol, carvone, linalyl acetate and pulegone Automated 1D: DB-5 column; 2D: DB-Wax Hydrogen FID 60
essential oils splitless injection
Essential oils of mosses of the genera Mnium, 10,11-Dihydro-a-cuparenone, 10-epi-muurola-4,11-diene, ()-muurola-4,11-diene, Manual injection Packed column with SE30 on Chromosorb G-HP (1); Helium FID 103
Plagiomnium, Homalia, Plagiothecium and ()-muurola-4,11-diene, ()-daucene, dauca-3,8-diene, and SE-30 on Chromosorb W-HP (2)
Taxiphyllum ()-3,4,5-trimethyl-5-pentyl-5H-furan-2-one
Essential oil of Lophocolea heterophylla Furanoeudesmane alcohol, furanoeudesma-4(15),7,11-trien-5a-ol Manual injection Packed column with PS-086 on Chromosorb W-HP Helium FID 114
Peppermint essential oil 1,4-Dimethoxybenzene Automated 1D: DB-5 column; 2D: DB-Wax Hydrogen FID 61
splitless injection

*Note: NA indicates not available.

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 efciency (20), but it might be difcult to control the compo-
nents simultaneously eluting from each column. Currently, the
novel preparative multidimensional gas chromatography
( prep-MDGC) combined with heart-cut device has demon-
strated a more efcient separation, particularly for complex
samples (5, 17, 22, 6063), and a three-channel electronic pres-
sure control module (EPC) has been used to provide sufcient
pressure for the Deans switch (DS) to achieve a high separation
resolution even when relatively large amounts of sample are
injected (63). pcGCs equipped with cutting and back-ushing
devices described by Schomburg et al. (54, 64) have been used
for discarding the non-volatile material and separating the
selected part in high resolution, and the pGC system composed
with a set of recirculated columns designed by Golay et al. (65)
can be considered to be the foundations on which prep-MDGC
is laid. In addition, the use of prep-MDGC equipped with differ-
ent columns makes it possible to obtain the target compounds in
complex matrices by different stationary phases (66).
Splitter and detector
When the splitter is installed in the front of the column, split in-
jection can be adopted. To ensure a certain volume of sample,
splitless injection is commonly employed in pGC (32, 33, 61).
The splitter installed behind the column allows the simultaneous
detection and collection of the efuent. For destructive detec-
tors such as the most widely used ame ionization detector
(FID), the splitter separates the gas ow and diverts a small part
to the detector and the rest of the ow to the traps.
Furthermore, because the splitter ratios may have great effects
on the detection and collection of the efuent and on the total
efciency of the pGC system (4), the splitter ratios need to be
investigated in some cases (67). Roeraade and Enzell designed a
pneumatically controlled splitter, which can achieve a split ratio
between 0 and 100%, depending on two independently con-
trolled regulating systems for instantaneous change (68).
With the use of a thermal conductivity detector (TCD), a non-
destructive detector, it is not necessary to set the splitter after
the column. However, the sensitivity of the detection can be
inuenced by the response time of the TCD. Modell (69)
invented a backed-bed TCD with a short response time, which is
less inuenced by the ow rate of the carrier gas than conven-
tional detectors. Maroulis et al. (41) designed a conduit with
copper jackets that was coupled to sources of thermal energy
and joined within the TCD to prevent undesired condensation
within the conduits.
In the last two decades, hyphenation of GC with mass spec-
trometry (MS) and NMR, which are efcient methods used for
structural determination, has gained increasing interest.
Although GC MS has widely been used, the MS detector is
rarely applied in pGC. Nevertheless, Mandalakis and Gustafsson
(34) combined a pcGC system and accelerated MS (AMS) to
measure the 14C contents of polycyclic aromatic hydrocarbons
(PAHs).
Carrier gas
The choice of carrier gas is important because it affects the sep-
aration efciency in addition to the sizes and shapes of detector
signals (70, 71). The inuence of carrier gas on the separation
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Figure 3. FID chromatogram for Ezhu extract on a stainless steel column packed with
10% OV-101 (3 m  6 mm i.d.) and selected fractionation time windows. Five fractions
containing 5.1 46.2 mg of b-elemene (F1), curzerene (F2), curzerenone (F3),
curcumenol (F4) and curcumenone (F5) were collected after 83 single injections
(20 mL) (39). Adapted from Figure 2 in Yang, F.Q., Wang, H.K., Chen, H., Chen, J.D.,
Xia, Z.N. Fractionation of volatile constituents from Curcuma rhizome by preparative gas
chromatography; Journal of Automated Methods and Management in Chemistry, 2011,
Vol. 2011, p3; Copyright # 2011 F. Q. Yang et al., with permission from the authors.
process has been discussed in detail by Verzele (72). Although
various carrier gases have been used in analytical GC (71), pGC
only adopts the three most commonly used gases, including
hydrogen, nitrogen and helium. Nitrogen is a more suitable
carrier gas for pGC than hydrogen and helium, because of the
high price of helium and the potential danger of hydrogen. In
addition, the ow rate of carrier gas also affects the sensitivity of
TCD (69) and the trapping efciency (73), and an overly high
ow rate may ush away the liquid stationary phase (50, 51).
Trap (fraction collector)
The collection of the fractions eluted from pGC is as important as
the separating process (74). The efciency of a trap used to collect
the target efuent may simply be expected to be as high as pos-
sible. However, affected by various factors, recovery values of the
selected eluates may be low and uctuating. Poor trapping ef-
ciency is sometimes caused by the formation of aerosol (7577),
especially for those components with poor volatility. It has been
demonstrated that the recovery values were proportional to the
volatility of target compounds, and the temperature of the col-
lecting device also intensely affected the efciency (73). It is im-
perative that the temperature of the connecting channel
between the collecting device and the GC system be maintained
above the bp of the constituents to prevent undesired condensa-
tion (20). Many conventional methods for the collection of
samples from pGC are available, including thermal gradient traps
(7880), electrostatic precipitation (8183), Volman collector
(84) with cartridge or aluminum rod heater and fritted lter traps
(77), which all provide efcient recovery values of aerosol
forming compounds. Furthermore, the trapping method of efu-
ent in a glass coil immersed in liquid nitrogen with a vacuum
manifold device can also effectively avoid the aerosol formation
and sample losses (85). In addition, a trap using potassium
bromide (KBr) powder as an inert support to adsorb the sample
can simplify the following IR identication step (86).
Actually, cold traps, on which many modied traps are based,
are most frequently used in pGC (77, 87). The temperatures for
the cool traps are closely related to the bp of the target com-
pounds. For compounds with high bp, room temperature
Preparative Gas Chromatography and Its Applications 707
 Figure 4. FID chromatogram for asarone isomers on a stainless steel column packed with 10% OV-101 (3 m  6 mm i.d.) and selected fractionation time windows (A); capillary
GC FID chromatogram of the collected fractions (B); MS spectra of the collected fractions (C); 178 mg and 82 mg, respectively, of cis-asarone (F1) and trans-asarone (F2) were
collected after 90 single injections (5 mL) (49). Adapted from Figures 1 and 2 in Zuo, H.L., Yang, F.Q., Zhang, X.M., Xia, Z.N. Separation of cis- and trans-asarone from Acorus
tatarinowii by preparative gas chromatography; Journal of Analytical Methods in Chemistry, 2012, vol. 2012, p2; Copyright # 2012 H. L. Zuo et al., with permission from the
authors.

circumstances can serve as adequate cooling conditions; for
compounds with moderately low bp, solid CO2 in a Dewar ask
is preferred (88); for compounds with extremely low bp, liquid
nitrogen should be employed (34, 89, 90). A pear-shaped ask
(91) or a trap consisting of a gas dispersion tube (bubbler) with
a fritted cylinder (92) may improve the recovery to some degree.
Furthermore, for collecting compounds with high molecular
weight such as methyl esters of the polygenic acids and fatty
acid methyl esters, which more easily lose collecting efciency,
a particular trap was established, consisting of a series of bottles
tted with sintered glass distributors and containing acetone
connected in series with the outlet (93). In addition, Roeraade
and Enzell designed a six-port ow distributor made of
platinum-iridium at the end of the column. The multi-channel
distributor connected to the traps consisted of coiled glass capil-
lary tubing, the inner walls of which were wetted with suitable
solvent and cooled in liquid nitrogen; this ensured maximum
trapping efciency, even for very small amounts of material (68).
In recent years, some new styles of collectors have been in-
troduced. Liu et al. designed an efcient trap that consists of
an enrichment unit with a temperature controller, a second dia-
phragm pump (differing from that in the sampling system), a gas

708 Zuo et al.

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 component collection tube and a cold well (94). The inlet of the
enrichment unit is connected to the outlet of the chromato-
graphic detector via a valve. Hu et al. tried to make a preparative
fraction collector with improved reliability and automation by
using a microprocessor controller and a corrosion resistance
magnetic valve (95). Moreover, traps based on megabore capil-
lary columns, named open tubular traps (OTTs), have also been
used in pGC (96, 97).
Currently, the commercially available fraction collector for GC
(Gerstel PFC), equipped with six sample traps and one waste
trap, collects individual fractions after GC separation. The PFC
system is controlled by a microprocessor, which automates the
collection process. Although the PFC has been used in several
studies (23, 98, 99), the technical limitation to only six collect-
able fractions using one PFC still hinders its applications. One
study combined two PFCs via a special zero-dead volume efu-
ent splitter, which enhanced the number from six to 12 collect-
able fractions within one GC running cycle (32). This method
provided the fractionation of nonylphenol isomers into 11 frac-
tions containing 77 552 mg of isomers collected after 600
single injections (Figure 2). This yield is sufcient to allow subse-
quent bio-testing in the E-screen assay. Therefore, a PFC system
developed with more sample traps can effectively enhance its
applications, especially for those samples with multiple compo-
nents.
Applications of pGC
pGC is widely used in various elds, either to obtain an individ-
ual compound for structural identication or to produce a
certain amount of pure compound for application in industrial
large-scale preparation. In laboratories, pGC has been a practical
tool to prepare small quantities of high purity materials.
Volatile components from natural essential oil
Essential oils are some of the most valuable natural products
with multiple pharmacological activities. pGC is frequently used
to collect desired fractions of the efuent from many other
naturally present matrix components, and has been regarded as
an ideal approach to separate volatile components from natural
materials. The applications of pGC for separating volatile compo-
nents from natural essential oil are summarized in Table I.
The volatile compounds of essential oils from natural sources
have primarily been extracted by hydro-distillation (100 104),
reux heating with less polar organic reagent (104) or a water
alcohol system (105). Because a moist sample can damage the
column, it is better to remove the water that is infused during
the extraction process, e.g., by drying over anhydrous sodium
sulfate (106, 107). On the other hand, the sample subjected to a
GC system must rst be thermally stable enough to avoid
thermal degradation (20), and of course, the sample should be
vaporizable because the non-volatile compounds can pollute the
GC system. Furthermore, the pGC system adopts larger diameter
columns and larger loading sample size, which will undoubtedly
result in a large decrease in the plate number and separation
resolution. Thus, proper pretreatment of the sample is needed
to produce the desired purity of products. The pGC preparation
procedure can be simplied by combining with other techni-
ques such as separation and removal of the unconcerned com-
ponents by silica gel chromatography (8, 49) or collection of the
striping components adsorbed by the silica medium (108, 109),
extraction of the target components by using a certain polar
reagent or collection of the distilled product under a certain
temperature range (110). On the other hand, several non-volatile
or semi-volatile compounds can contaminate the injection port
and the column head if the crude oil is directly injected into
GC system. Therefore, removing the non-volatile components
by silica gel chromatography can extend the lifetime of the
system (39).
Low volatility compounds such as terpenes, sesquiterpenes
and sesquiterpenoids, which are ubiquitous in essential oil, are
usually isolated by pGC (39, 101, 102, 107, 111, 112). Staritas
et al. (103) obtained four terpenes, 15 sesquiterpenoids, two
diterpenoids and the aliphatic metabolites from the hydrodistil-
lation product of mosses by pGC. b-Elemene, curzerene,
curzerenone, curcumenol and curcumenone (with yields of
5.1 46.2 mg after 83 single injections of 20 mL) were separated

Table II
Applications of pGC in the Separation of Isotopes, Isomers and Enantiomers*

Sample Target compounds Injection Column Carrier Detector Reference

gas
Mushroom odor 1-Octenyl-3-acetate Manual injection Packed column with modified b-CD on Chromosorb Hydrogen TCD 128
P-NAW
Mixture of enflurane and isoflurane Enflurane and isoflurane Manual injection Packed column with SE-54 on Chromosorb Helium FID 129
P-AW-DMCS
Racemic 2-chloropropionate Enantiomers of methyl Six-way valve Packed column with b-CD on Chromosorb A Hydrogen FID 40
2-chloropropionate injection
Natural gas Isotope of nitrogen Direct infusion NA Helium TCD 148
Racemic isoflurane Enantiomers of isoflurane Manual injection Packed column with b-CD on Chromosorb W-AW Hydrogen TCD 125
Fluoroether anesthetics Desflurane, enflurane and isoflurane Manual injection g-CD coated capillary column Hydrogen FID 149
Hydrogen isotope mixture Tritium and deuterium Pressurized Packed column with Pd deposited on porous a-Al2O3 Helium TCD 124
injection
Racemic perhydrotriphenylene All trans-perhydrotriphenylene Manual injection Packed column with TBDMS-b-CD and SE-54 on Nitrogen TCD 150
Chromosorb P-AW-DMCS FID
Racemic 1-chloro-2,2-dimethylaziridine ()-1-Chloro-2,2_dimethylaziridine Manual injection Packed column with OV-101 impregnated on Nitrogen NA 151
Chromosorb W-AW-DMCS
1,1,1-Trichloro-2,2-bis(p-chlorophenyl) Chlorine isotope Cooled injection BPX-5 Helium FID 33
ethane system

*Note: NA indicates not available.

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 710 Zuo et al.

Table III
Miscellaneous Applications of pGC*

Sample Target compounds Injection Column Carrier Detector Reference

gas
Sweet potatoes Ipomeamarone Manual injection Packed column with SE-30 on GC PGC Hydrogen TCD 152
Products arising from reaction of phenylacetylene with 2-Para-aryl-substituted 1,3,5-triphenylbenzene Automated splitless DB-5 Hydrogen FID 5
para-substituted aryl-iodides injection
Chemical reaction product a-Nerol and a-geraniol Manual injection Packed column with Carbowax 20M adsorbed on silane-treated Helium NA 153
Celite
Crude Si(CH3)4 containing n-butane, 2-methylpentane, Tetramethylsilane Manual injection Packed column with SE 30 on Chromosorb A Helium FID 154
3-methylpentane and tetrahydrofuran
Distillate of pineapple juice 2,5-Dimethyl-4-hydroxy-3(2H)-furanone On-column injection Packed column with G.E. SF96 on firebrick (1); Carbowax 20M Helium NA 109
on Chromosorb W (2)
Mixture of juvenile hormones Juvenile hormone III Manual injection Packed column with OV-1 Helium FID 155, 156
Polybrominated biphenyl contegers Active fraction of polybromlnated biphenyl mixture Manual injection Packed column with OV-1 (1) or OV-17 (2) on Chromosorb Nitrogen FID 26
W-AW-DMCS
Extracts of gum haggar and gum myrrh d-Elemene and b-bourbonene On-column injection HP-1 Hydrogen FID 87
Mixture of metal TPM complexes Metal TPM complexes Automated liquid Packed column with Apiezon L on Universal B Nitrogen FID 141
injection
Triglyceride mixtures Triglyceride Manual injection Packed column with JXR (1) or SE-30 (2) on Chromosorb W Hydrogen FID 135
Raw water sources for drinking water production Off-flavor compounds in water Manual injection DB-l Helium FID 157
Commercial styrene Styrene monomer Manual injection Packed column with SE-30 Chromsorb W Nitrogen FID 140
Atmospheric aerosol Naphthalene, phenanthrene, fluoranthene, pyrene, Cooled injection Capillary column coated with a cross-bonded methyl silicone Helium FID 21
chrysene and benzo[a]pyrene system
Mixture of PAHs Fluorene, retene, chrysene, pyrene, fluoranthene and Cooled injection Supelco SPB-5 capillary column Helium MSD 34
perylene system
Portuguese wines from the Douro region 2,6,6-Trimethylcyclohex-2-ene-1,4-dione and diacetyl Manual injection Packed column with Carbowax 20 M on Chromasorb W Nitrogen FID 158
Crude sex hormone extract of Pseudococcus cryptus 3-Isopropenyl-2,2-dimethylcyclobutylmethyl Manual injection FFAP column Helium TCD 159
3-methyl-3-butenoate
Green river formation oil shale Steranes and triterpanes, e.g., 5a-cholestane and Six-way valve Packed column with OV-1 on Supelcoport Helium FID 160
5a-ergostane injection
Methylene chloride extracts of roasted peanuts Low molecular weight pyrazines and a pyrrole Manual injection Packed column with Carbowax 20M on Gas-Chrom Q (1); Helium Four-filament hot-wire 18
SE-52 on Gas-Chrom Q (2) detector
Cod liver oils Methyl esters of polyunsaturated acids On-column injection Packed column with Apiezon L on Chromosorb G Nitrogen FID 67
2,4-Diketone fraction from hydrolysates of various 2,4-Heptadecanedione, 2,4-nonadecanedione, Manual injection Packed column with UCW 98 on Diatoport 5 Helium FID 161
mammalian tissues 2,4-heneicosanedione, 2,4-docosanedione and
D12-2,4-heneicosenedione
Petroleum distillates 2-Methyl-6,7-dihydro-1,5-pyrindine Flash vaporization Packed column with Reoplex 400 on Johns-Manville C-22 Nitrogen TCD 162
injection firebrick
Cognac Volatile components in wine Manual injection Packed column with LAC-1-R-296 on Chromosorb W (1); NA TCD 163
capillary column coated with polypropylene glycol (2)
Calvados and cognac Fractions of groups of compounds Manual injection Packed column with SE-30 on Chromosorb PWA Hydrogen TCD 16
Tissue hydrolysates Amino acids On-column injection Packed column with EGA on Chromosorb W-AW Argon FID 164

*Note: NA indicates not available; MSD indicates mass selective detector.

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 from the methanol extracts of Curcuma rhizome pretreated by
silica gel chromatography (Figure 3) (39). The cis- and trans-
asarone isomers (with yields of 178 and 82 mg, respectively,
after 90 single injections of 5 mL) were separated by pGC from
their mixture, which was fractionated from the essential oil of
Acorus tatarinowii by silica gel chromatography (Figure 4) (49).
b-Sinensal was separated from California cold-pressed orange oil
by a combination of vacuum distillation, silica gel chromatog-
raphy and pGC (113). Rodin et al. (109) used pGC to separate
volatile avor and aroma components from pineapple.
Furanoeudesmane alcohol was isolated from the essential oil of
the liverwort Lophocolea heterophylla (114).
Separation of isotopes, isomers and enantiomers
Dating back to the 1960s, pGC has intensively been used in aca-
demia to purify the compounds arising from chemical reactions
for further structural elucidation (5, 115 117). More important-
ly, pGC has successfully been applied for the separation
of stereoisomer reaction products of synthesis or hydrolysis
(43 46, 118), which represented great contributions to the re-
search of mechanisms for chemical reactions. Furthermore, pGC
also allowed the separation of diastereoisomers (119) and wide-
spread isomers in natural essential oils (49, 120). On the other
hand, although cryogenic distillation has been known and used
for the separation of the hydrogen isotopes tritium and deuter-
ium, pGC is more suitable and particularly applicable for the iso-
lation of hydrogen isotopes on a large scale (121, 122).
Furthermore, the pGC system at Joint European Torus (JET),
which is a type of displacement chromatography that uses palla-
dium (Pd) as working material because of its large isotope
effects on hydrogen absorption and hydride formation (123),
can produce deuterium and tritium of high purity at low tem-
perature with good production efciency (124).
Various cyclodextrin-based stationary phases have been used
in GC for approximately 20 years (125, 126). Derivatived cyclo-
dextrins (CDs) as chiral selectors can be used as reliable station-
ary phases for the pcGC separation of enantiomers of different
structural characteristics (127130); this separation mechanism
has been thoroughly illustrated (131). Considering the large ex-
perimental effort needed for the optimization of those
preparative-scale separations (126), Staerk et al. (132) devel-
oped a model of elution band proles in the pGC separation of
enantiomers based on the equilibrium-dispersive model of non-
linear GC, which may be used to speed the optimization process
by computer modeling.
The applications of pGC for isotopes, isomers and enantio-
mers are summarized in Table II.
Miscellaneous
The separation of a few milligrams of pure substance from a
mixture of biological origins is often important for the studies of
steroids, alkaloids and many other compounds. A pGC method
was developed for the separation of steroids and alkaloids at
milligram-scale by using relatively thin-lm column packing
(133). Furthermore, certain quantities of low concentration fatty
acids have successfully been prepared by pGC (134). The frac-
tionation of high molecular weight triglycerides by GLC and
thin-layer chromatography (TLC) on silica gel impregnated with
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silver nitrate has resulted in considerable progress and is widely
used in the structural elucidation of natural fats and oils (135
139). On the other hand, cannabidiol, tetrahydrocannabinol and
cannabinol, which are three primary cannabinoids, have been
isolated by pGC from the enriched extract of cannabis (104). As
a purication technique, pGC has been used for the purication
of a styrene monomer from its commercial products (140). In
addition, it has been shown that wire mesh packing as carrier of
the stationary phase is effective for separating the binary azeo-
trope of 1-propanolwater (15). pGC was also used to purify
metals as their volatile derivatives (141) and as a purication pro-
cedure in toxicology. It can obtain large enough amounts of
toxic agents with sufcient purity from tissue for further identi-
cation (142). Miscellaneous applications of pGC are summar-
ized in Table III.
Conclusions
Although pGC has widely been used, it is still not comparable to
pre-HPLC, which has constantly been used in the pharmaceut-
ical industry for the isolation and purication of biological
active substances. For pGC, several aspects should be inten-
sively improved. First, the scaled-up pGC column requires
large volumes of carrier gas to provide a certain pressure, and
it is difcult to reutilize the mobile phase. Second, the sample
must be fully vaporized onto the column to ensure radial dis-
tribution of the sample across the column. Third, because the
target compounds are eluted in a very dilute form from the
column, they must be extracted or condensed from the gas
stream, which makes it difcult to achieve high efciency.
Finally, although a large GC column provides a high productiv-
ity, it is difcult to achieve the goal of automatic production
control; the capillary column is unsuitable for industrial appli-
cations.
Nevertheless, pGC is successful in many rather special applica-
tions. For example, pcGC, combined with a computer-based
structural generation tool used for mutagenicity prediction, has
been applied within effect-directed analysis (EDA) to reduce
sample complexity and to identify candidate mutagens in the
samples (23). Since Eglinton et al. (143) rst reported the isola-
tion of monomer compounds by pcGC and subsequent radiocar-
bon (14C) isotope analysis by ofine AMS, the combined use of
these techniques has provided a powerful analytical tool to
achieve CSRA (144). Although the preparation process of CSRA
can be accomplished by either HPLC or pcGC, the clear and
highly resolved analytical separations of the capillary columns
has made pcGC more attractive for natural abundance
CSRAs (22).
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (21275169, 81202886 and 21175159), the
International Cooperation Project of Ministry of Science
and Technology (2010DFA32680) and the Natural Science
Foundation Project of CQ CSTC (2010BB5070). We are grateful
to Dr. Liya Ge from Nanyang Technological University for her
help in checking the written English of the manuscript.
Preparative Gas Chromatography and Its Applications 711
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