Sample preparation is a key step in chemical analysis, and includes isolation of target analytes, removal of interferences, preconcentration, and/or modification of target analytes (if needed). Sample preparation is also the most time-consuming and error-prone step in the whole analytical process. Traditional sample preparation techniques involve hazardous solvents. Considering the environmental and health safety, it is desirable to reduce or eliminate organic solvents in sample preparation. Solid phase microextraction (SPME) was introduced as a solvent free sample preparation technique. Capillary microextraction (CME) is one of the formats of SPME that can be easily coupled to high performance liquid chromatography (HPLC). In SPME and CME a solvent free sample preparation is accomplished by using a sorbent coating instead of hazardous organic solvents commonly used in conventional extraction techniques. This research is focused on the development and systematic examination of novel niobia-, titania- and silica-based organic-inorganic hybrid sol-gel sorbents for CME. Conventionally silica and titania based precursors were used in organi-inorganic hybrid sol-gel sorbents for CME, here novel niobia based precursor was used in creating organic-inorganic hybrid sol-gel sorbents. Poly tetrahydrofuran (polyTHF) as well as electrically neutral and charged organic ligands were used to prepare the sorbents for CME coupled to HPLC. Characterization of created sol-gel sorbents, evaluation of extraction performance, and enrichment of environmentally and biomedically important analytes including organophosphorus compounds were performed. CME performances of the created sorbents were characterized by specific extraction (SE) (a measure of extraction efficiency) and desorption efficiency (DE) (a measure of completeness desorption of extracted analytes). Scientific findings of this research has shown that sol-gel niobia-polyTHF sorbent provides 60 to 70 % higher SE values for different environmentally important analytes compared to analogously prepared silica-polyTHF sorbent. This superior extraction performance can be attributed to the presence of surface Lewis acid sites undergoing Lewis acid-base interactions with analytes representing Lewis bases. The prepared sorbents also have the ability to undergo van der Waals interactions due to the presence of polyTHF. Absence of Lewis acid sites on silica surface resulted in inferior extraction efficiency compared to niobia-polyTHF sorbents. Extraction efficiency of the created sol-gel based niobia-polyTHF was also explored in the enrichment of organophosphorus pesticides and compared with that of the state-of-the-art titania-based sorbent. Sol-gel niobia-polyTHF sorbent has provided 40 to 50 % higher SE values in the enrichment of organophosphorus pesticides compared to sol-gel titania-polyTHF sorbent which can be attributed to the presence of bronsted acid sites on niobia surface (but lacking on titania) along with Lewis acid sites. To explore relative contributions of electrostatic, Lewis acid-base and van der Waals interactions between sol-gel sorbents and analytes, two sol-gel sorbents, one containing a positively charged octadecyl ligand and the other a neutral octadecyl ligand were created. Positive charge was imparted by using N-octadecyldimethyl [3-(trimethoxysilyl) propyl] ammonium chloride (C18 (+ve)) as ligand bearing co-precursor. Similarly N-octadecyl trimethoxysilane was used to impart a neutral C18 ligand in sol-gel coating. Experimental results have shown that sol-gel Nb2O5-C18 (+ve) sorbent has superior extraction efficiency compared to sol-gel based Nb2O5-C18 and purely inorganic Nb2O5 sorbents in enrichment of organophosphorus compounds (nucleotides and organophosphorus pesticides). Electrostatic interactions between the positive charge of organic ligand (C18 (+ve)) and negative charge of phosphate group has contributed to the higher extraction performance of sol-gel based Nb2O5-C18 (+ve) sorbent. TiO2-C18 (+ve) sorbent was also created to compare with the novel sol-gel niobia based sorbents, since titania-based sorbents are considered as the state-of-the-art extraction material in the enrichment of organophosphorus compounds. Established research results has shown that sol-gel based Nb2O5-C18 (+ve) sorbent has provided 40 to 50 % higher specific extraction values for organophosphorus compounds compared to sol-gel based TiO2-C18 (+ve) sorbent. Desorption efficiency of sol-gel Nb2O5-C18 (+ve) and TiO2-C18 (+ve) sorbents were 96% vs 90%. This superior DE of sol-gel Nb2O5-C18 (+ve) sorbent can be attributed the higher Lewis acid strength of titania than nioiba. The developed sol-gel niobia based sorbents have also shown high pH stability compared to traditional sol-gel silica based sorbents. The created sol-gel sorbents were characterized by less than 5% run to run RSD values and also less than 5% capillary to capillary RSD values which indicated the high reproducibility of developed method. The developed sol-gel niobia sorbents are applicable to sample preparation in different fields including biomedical, environmental, forensic, defense etc.

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.

The aim of this research was to demonstrate the potential of the novel pre-concentration device, capillary microextraction of volatiles (CMV), for breath analysis. The CMV offers dynamic sampling of volatile organic compounds with its simple coupling to a GC inlet for GC/MS analysis, avoiding expensive thermal desorption instrumentation needed for sorbent tubes, as well as an increased surface area over a single SPME fiber. CMV collectively identified 119 compounds in the breath of 13 self-reported smokers and 7 nonsmokers. The presence and intensity of twelve compounds were used to classify all the nonsmokers 100% of the time using Principal Component Analysis to elucidate the groupings. In some cases, nicotine was not detected in smokers and they were confused with the nonsmokers. Nicotine was detected in the breath of 69% of smokers with an average mass of 143 ± 31 pg for cigarette smokers from the approximate 5 L sample of breath collected. The successful use of the CMV sampler and preconcentration of breath to distinguish between smokers and nonsmokers served as a proof of concept for future applications of the CMV for detection of marijuana smokers’ breath for impaired driver management.

The capillary microextraction of volatiles (CMV) device was equipped with a novel Peltier cooler to investigate cryofocused extraction of organic gunshot residue (OGSR) for the first time. Prior research demonstrated the CMV’s capabilities for detecting nitroglycerin, 2,4-dinitrotoluene, diphenylamine, and ethyl centralite on shooters’ hands via gas chromatography-mass spectrometry. Further method development increased the recoveries of these four target compounds with an optimal 20-minute equilibrium time at 80˚C followed by extracting 3 L at a 1 L/min flow rate. The Cryo-CMV was evaluated for detection of semi-volatile OGSR compounds. The unique challenges presented with sampling of semi-volatiles were overcome by sample heating, applying high (>1 L/min) sampling flow rates and heating the transfer line between the container and cooled CMV. Cryofocusing at -10˚C provided increased recoveries for smokeless powders and OGSR compounds and therefore demonstrates excellent potential for other forensic applications with analysis of VOCs from fire debris and illicit drugs.

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

For the first time, octahydroxyl methylresorcinarene with four hexyl groups on the lower rim was utilized in the in-situ preparation of a silica-based sol-gel organic-inorganic hybrid coating for sample preconcentration by capillary microextraction (CME). Tetraethoxysilane (TEOS) was chosen as a sol gel precursor to create a cross-linked sol-gel network via acid-catalyzed hydrolytic polycondensation reactions. Sol-gel chemistry helped in the in situ preparation of resorcinarene-containing extraction phase in the form of a surface coating. It also provided an effective means to chemically bind the coating to the inner surface of fused silica capillary via condensation of the hydroxyl groups in the sol-gel network with the silanol groups on the fused silica capillary inner surface. These chemically bonded sol-gel coatings demonstrated excellent thermal stability (up to 350 oC). The sol-gel resorcinarene coatings successfully extracted traces of polycyclic aromatic hydrocarbons (PAHs), ketones, phenols, amines, and alcohols from aqueous samples providing parts per trillion level detection limits (0.828 - 46.01 ng/L) in GC using a Flame Ionization Detector (FID). CME was performed by passing the aqueous samples through the resorcinarene coated microextraction capillary (10 cm). The extracted analytes where then thermally desorbed into the GC column connected to the exit end of the sol-gel microextraction capillary via a press-fit quartz connector. Peak area relative standard deviation (RSD %), a measure of the extraction performance reproducibility for the coated capillary, was found in the range of (1.1 % - 8.3 %). The sol-gel resorcinarene sorbent was characterized by FTIR spectrum which indicated the presence of hydroxyl groups in the coating even after the sol-gel reactions were completed which explains the affinity of the resorcinarene sol-gel coating toward polar analytes. Scanning Electron Microscopy (SEM) images of the coating reveraled the porous morphology and thickness of 3.5 - 4.0 µm for the coating. The sol-gel resorcinarene coated capillary provided excellent extraction performance for wide range of analytes.

Sample preparation is the most time-consuming and error-prone step in chemical analysis. Miniaturization and automation of the sample preparation equipment eliminating or reducing the use of hazardous organic solvents, online hyphenation of sample preparation with analytical instruments in a cost-effective way are important factors that need to be considered to design and implement innovative sample preparation techniques and strategies. Solid-phase microextraction (SPME) is a simple, environmentally benign technique well suited for hyphenation with analytical instruments. However, poor coating stability is a significant drawback of SPME employing conventionally prepared coatings. This shortcoming arises from the lack of chemical bonding between the sorbent coating and the substrate. Introduction of sol-gel coatings in SPME greatly improved thermal stability and solvent stability in SPME, by providing direct chemical bonding between substrate and the sol-gel coating. In traditional fiber format of SPME (where the sorbent coating is placed on the outer surface of an end-segment of the fiber) the coating remains vulnerable to mechanical damage. Capillary microextraction (CME), the capillary format of SPME (also known as in-tube SPME), allows to overcome this shortcoming by securing the sorbent coating on inner walls of the capillary. This dissertation focuses on the development and systematic investigation of novel silica- and germania-based perfluorinated and non-fluorinated sol-gel sorbents in the form of CME surface coatings: their preparation, material characterization, CME performance evaluation, preconcentration and recovery of various analytes including environmental pollutants. This research established that germania-based sol-gel sorbents are characterized by superior microextraction performance than analogous silica-based sorbents. This enhanced performance provided by germania-based sol-gel sorbents may be explained based on thermogravimetric analysis suggests that higher carbon loading on germania-based sol-gel sorbents. Germania-based phenyl- (Ph), phenethyl- (PhE), octyl- (C8), octadecyl- (C18) and cyclohexenylethyl- (ChE) ligand-containing sol-gel sorbents were prepared and various pollutants with aromatic rings (such as aromatic ketones, aldehydes and polycyclicaromatic hydrocarbons) were extracted and analyzed by CME-GC and CME-HPLC. It was observed that sol-gel sorbents containing aromatic ligands (PhE and Ph) provided superior microextraction performance for the analytes with aromatic ring(s) in their structure, than the sorbents with aliphatic ligands (C8 and C18). Investigation of sol-gel sorbents containing hydrophobic perfluorooctyl (PF-C8) and perfluorododecyl (PF-C12) ligands revealed that PF-C8 and PF-C12 sol-gel sorbents provided ~ 3 times higher microextraction efficiency (measure in terms of specific extraction, SE) than corresponding non-fluorinated counterparts, C8- and C12-, respectively. The synthesis and design of silica- and germania-based dual ligands sol-gel sorbents simultaneously providing superhydrophobicity and π-π interactions with analytes represent a significant accomplishment of this research. Such sorbents contained a PF-C12 and PhE ligands incorporated in sorbent chemical structure. In this case, perfluoro- group provided enhanced hydrophobic interaction and PhE group provided π-π interaction with the analytes. Combination of such interactions proved to be quite effective in the microextraction of alkylbenzenes and related compounds. Dual-ligand sol-gel sorbents with both equimolar and non-equimolar ligand concentrations were prepared. Experimentally it was established that sorbents with higher perfluorinated alkyl ligand concentrations had higher affinity for aliphatic hydrocarbons; however; when PhE concentration was higher, the dual-ligand sorbent showed enhanced affinity for aromatic compounds. The prepared sol-gel sorbents were characterized by less than 5% run-to-run RSD values, and also less than 5% capillary-to-capillary RSD values, which indicate that the sol-gel technique used in sorbent preparation was highly reproducible. The prepared sol-gel sorbents also showed that their performance does not deteriorate under aqueous saline matrix; therefore, it could be useful in the microextraction of pollutants from ocean water.