Class of 2009 Abstract / OBJECTIVES: The primary objective of this experiment was to characterize the pH stability range of 20% Pluronic lecithin organogel (PLO). We intended to determine the viscosity at varying pHs. We prepared six samples of 20% PLO. METHODS: An initial rheological reading of each sample was recorded by a dynamic stress rheometer. Each sample was titrated drop-wise with citric acid or KOH in 0.5 pH increments. When the desired pH was obtained, a 0.5 mL sample was analyzed with a dynamic stress rheometer, RS-200, using Rheos software. RESULTS: Since PLO is a non-Newtonian substance, viscosity changed relative to shear stress and we were not able to examine a correlation of pH with viscosity. Instead we inputted the data into Microsoft Excel® and plotted a shear stress versus viscosity curve for each sample to identify trends. CONCLUSIONS: We were unable to achieve our primary objective of determining the viscosity characterization of 20% PLO at varying pHs due to the non-Newtonian nature of the material. Subjectively, we determined the viscosity of 20% PLO is not substantially affected by pH. Other factors such as temperature, excess liquid, and surfactant ability may influence viscosity and need to be examined in the future.

Sample preparation is the most error-prone step in chemical analysis. A great deal of efforts has been made to develop efficient techniques and protocols for sample preparation to accomplish important goals such as miniaturization and implementation of green analytical methodologies. Solid-phase microextraction (SPME) has successfully eliminated the use of hazardous organic solvents in extraction sampling, sample preparation, preconcentration and sample introduction to the analytical instrument in an effective manner. Ensuring thermal- and solvent-instability of traditional SPME extraction phases represented one of their main drawbacks. This was solved by the introduction of sol-gel SPME phases characterized by enhanced thermal-, solvent-, and stability over a wide pH range. Sol-gel SPME phases (sorbents) facilitated excellent preconcentration effects for a wide range of analytes. In this dissertation, hydrolytic and nonhydrolytic sol-gel routes were explored for the creation of zirconia-, titania-, and niobia-based novel hybrid organic-inorganic sorbents using sol-gel active polymeric ligands. These sorbents were prepared in the form of surface coatings for capillary microextraction and preconcentration of biologically important molecules such as catecholamine neurotransmitters and phosphopeptides. In comparison with other sorbents made only of inorganic transition metal oxides, the presented sol-gel sorbents facilitated efficient desorption of the extracted analytes by LC-MS compatible mobile phases. The sol-gel zirconia- and titania-based hybrid sorbents provided pH-stable (pH range: 0 - 14) and derivatization-free extraction media that effectively overcame the major drawbacks of traditional sorbents for the analysis of catecholamines (silica-based sorbents suffer from narrow operational pH window while polymer-based sorbents require additional sample derivatization steps). The modification of the terminal hydroxy groups in PPO with ZrCl4 or TiCl4 provided an enhanced sol-gel reactivity of the polymer modified-terminals. Such a modification procedure allowed for an efficient incorporation of the polymeric ligand into the evolving sol-gel network. The effectiveness of the PPO modification was also evaluated by a systematic thermogravimetric investigation exploring the loading of the ligand in sol-gel hybrid sorbents, which revealed an enhanced ligand-loading achieved via the nonhydrolytic sol-gel route used with modified-PPO. Sol-gel hybrid sorbents prepared by the nonhydrolytic sol-gel (NHSG) pathway provided excellent microextraction performance for catecholamines: low detection limits (5.6 – 9.6 pM), enhanced run-to-run reproducibility (RSD 0.6 – 5.1 %), excellent desorption efficiency (95.0 – 99.5 %) and high enrichment factors (EF) for epinephrine (EF ~ 1480) and for dopamine (EF ~ 2650) extracted from aqueous and synthetic urine samples at pH 10.5. Run-to-run and capillary-to-capillary reproducibility remained below 5 % when the peak area or the sorbent-mass was used as the reproducibility criterion. Niobia-based sol-gel sorbents prepared with and without organic ligand (polyethylenimine) were utilized as microextraction media for the enrichment of phosphorylated and nonphosphorylated tetrapeptide VYKA. Sol-gel niobia-based sorbents with covalently anchored polyethylenimine showed excellent selectivity toward the phosphopeptide compared to analogous titania-based sorbents. Specific extraction (SE) values were higher by 97.0 % when obtained by niobia-based sorbents. Excellent run-to-run peak area reproducibility (RSD < 5.1 %) and high EF of ~ 4000 were achieved. The sol-gel niobia-based coating facilitated excellent desorption efficiency (97.5 %), which suggests that the surface of the niobia sorbent possesses moderate-strength Lewis acid sites that avoided the need for special elution solvents that are conventionally used for the desorption of phosphorylated molecules from titania-based sorbents. The sol-gel pathway for the creation of microextraction phases is versatile and capable to provide unique control on the characteristics of the sorbents that are critically important for many sample preparation applications.

High-performance liquid chromatography (HPLC) is the most widely used analysis technique. However, its sensitivity is limited. Sample preconcentration methods, such as fiber-based solid-phase microextraction (SPME) and in-tube SPME (capillary microextraction) offer improved detection limits. It is, however, difficult to couple fiber SPME on-line with HPLC due to the need for complicated desorption devices. Such coupling is further complicated due to the limited solvent stability of the extracting phase both in the fiber and in-tube formats of SPME. In this research, surface-bonded sol-gel sorbents were developed to provide the solvent stability required for effective on-line hyphenation of capillary microextraction (CME) with HPLC. These sol-gel sorbents were prepared using (1) silica-based, (2) titania-based, and (3) germania-based sol-gel precursors. Sol-gel reactions were performed within fused silica capillaries to create a number of organic-inorganic hybrid sorbents in the form of surface-bonded coatings: (1) alkyl (methyl, octyl, octadecyl), (2) polydimethyldiphenylsiloxane, (3) titania poly(tetrahydrofuran), and (4) germania tri-block polymer. The sol-gel coated microextraction capillaries were capable of efficiently extracting a wide variety of analytes, including polycyclic aromatic hydrocarbons, ketones, aldehydes, aromatic compounds, amines, alcohols, and phenols with ng/L to pg/L detection limits. The sol-gel methyl coating demonstrated a counterintuitive ability to extract polar analytes. Sol-gel polydimethyldiphenylsiloxane coatings were found to be resistant to high temperature solvent exposure (150°C and 200°C), making them suitable for use in high-temperature liquid phase separations. To better understand how extraction takes place, effects of alkyl chain length and sol-gel precursor concentration were evaluated in the study on sol-gel alkyl coatings. The sol-gel titania poly(tetrahydrofuran) coating was also capable of extracting underivatized aromatic acids and polypeptides at pHs near their respective isolectric points. The sol-gel titania poly(tetrahydrofuran) coatings and the sol-gel germania tri-block polymer coatings demonstrated impressive resistance to extreme pH conditions, surviving prolonged exposure to 1.0 M HCl (pH approx. 0.0) and 1.0 M NaOH (pH approx. 14.0) with virtually no change in extraction behavior. Sol-gel germania tri-block polymer coatings were also stable under high temperature solvent conditions (200°C). In addition, for the first time, the analyte distribution constants between a sol-gel germania coating and the aqueous samples (Kcs) were determined.

The present diploma thesis is focused on the selected anti-aging substances in cosmetic products. The literature research provided us with the knowledge of essential skin characteristics and factors influencing the aging process. Furthermore, the thesis describes the basic physical forms of cosmetic products, the basic cosmetic materials and the current trends in the usage of anti-aging substances. The experimental part subsumes altogether four physical forms of cosmetic products – tonics, serums, masks and creams. In this work was testid a new anti-aging compound, developer by French company SOLABIA, which provided the company Miša a Harašta s.r.o. (M+H). It has tested four components: Fucogel, Camaderm Gly, Viniderm and Omega Ceramid. These anti-aging substances were addend to the four technology cosmetic form, which were prepared in our laboratory. Subsequently, the pH stability of the products was measured together with the rheological measuring and skin hydration measuring. All of the samples proved to be pH stable. The highest stability of viscosity and consistence was identified for masks and creams. It was found out that the added anti-aging substances have no impact on the stability of pH, viscosity and consistency. The skin hydration measuring proved that the anti-aging substances Vinidem and Camadem Gly have the greatest moisturising qualities.