Chemistry Commons^™

Thermal Studies Of Complex Formations Of First Row Transition Metals With Phenolic Compounds In Aqueous Solution, Nabil Adnan Amro

Masters Theses

The coordination chemistry of protocatechuic acid and catechols with the first row of transition metals was studied as a model for the more complicated natural humic substance.

The reaction between Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and the phenols, catechol and protocatechuic acid in aqueous solution was studied by the spectrophotometric method. The composition of the complexes formed was determined by continuous variation, iso-molar series and molar ratio methods. The presence of complexes with metal:ligand ratio of 1:1, 1:2 and 1:3 was established in the pH range 3 to …

Induced Acceleration Of Phosphine Exchange In Metal Carbonyls By Pendant Groups Of Coordinated Polyphosphines, Ping Ye

Masters Theses

The kinetics and thermodynamics of isomerization of (OC)₅CrPPh₂CH₂CH(PPh₂)₂ to its linkage isomer, (OC)₅CrPPh₂CH(PPh₂)CH₂PPh₂, in chloroform-d have been studied with ³¹P{¹H} NMR.

(OC)₅Cr[η¹-PPh₂CH₂CH(PPh₂)₂] ⇄ (OC)5Cr[η¹-PPh₂CH(PPh₂)CH₂PPh₂]

The equilibrium constants for the reaction are 3.60, 2.61, 2.04, and 1.67 at 10 °C, 25 °C, 40 °C, and 53 °C, respectively. The forward reaction becomes more favorable as the temperature …

An Expeditious Synthesis Of Β,Γ-Unsaturated Δ-Lactones: Useful Pharmacological Synthetic Intermediates, Li Xiong

Masters Theses

Two-carbon ring expansions of vinyl β-lactones, were carried out by Lewis acids (BF₃-Et₂O or Et₂AlCl) via an ionization/cation rearrangement. β,γ-unsaturated δ-lactones were produced as efficient protocols for the synthesis of bioactive substances.

Vinyl β-lactones were prepared via ring closure of corresponding unsaturated β-hydroxy acids. Differently structured substrates were examined to study the influence of the substituents on the rearrangement. Other factors, such as temperature, solvent and catalyst were also studied in search of suitable reaction conditions.

This method is moderately successful in providing fused-ring δ-lactones, but higher yields (so far total yield of 24.8%) …

Identification Of Organosulfur Compounds In Illinois Coal, Mandy N. Amin

Masters Theses

The goal of this research was to identify representative organosulfur compounds in Illinois coal which are removed by a mild, chemical desulfurization procedure. Pyridine was used to extract three raw Illinois coals. Coal with a significant amount of elemental sulfur was treated with 1:1 HCl/HF followed by lithium aluminum hydride before pyridine extraction. Pyridine soluble extracts were extracted with tetrahydrofuran. Nickel boride desulfurization was performed on the soluble extracts of the three coals. The before and after desulfurized THF soluble extracts were fractionated and purified by liquid chromatography and the eluents were anlyzed by gas chromatography/mass spectrometry to characterize the …

Constancy Of Bond Dissociation Energy Ratios For Ab₂/Ab Systems, Danyu Xu

Masters Theses

G2 and G2(MP2) theories have been used to study the bond dissociation energies D⁰_m of a series of AB₂, AB₂⁺, AB₂^-, AB, AB⁺ and AB^- systems. A total of fifty-four molecules and ions have been examined, for which B = O, S or Se and A = C, S, Ge, N⁺, P⁺, As⁺, B^-, Al^- or Ga^-. Each triatomic system has sixteen valence electrons and each diatomic system has ten valence electrons. Both triplet and singlet spin …

A Chemical Extraction Study Of Lead Contaminated Soil From Granite City, Il, Yan Zhang

Masters Theses

Granite City, IL, surface soil ( 0-10 cm ) contaminated with lead was studied by both single- and a four-step sequential chemical extraction procedures designed to establish the partitioning, mobility and availability of lead in soil. The five fractions corresponding to the selected extractants were exchangeable, carbonates-bound, Fe-Mn oxides bound, organic matter and residual. Lead contamination of the soil was determined as a function of particle size and soil depth.

The contaminated sample had the highest lead content of 573.1 mg/kg at the 4 cm soil depth level, and on average was about 8.8 times that of background soil. Most …

Azo Dyes Based On 1,10-Phenanthroline, Minchong Mao

Masters Theses

A series of new phenanthroline based azo-dye ligands, produced by diazotizing 5-amino-1,10-phenanthroline (5-NH₂-phen) and then coupling this intermediate to a variety of coupling components, has been synthesized and characterized. The coupling components used were β-naphthol, phenol, and 2,6-dimethylphenol, and the three dye ligands were named phen-azo-β-naphthol, phen-azo-p-phenol, and phen-azo-2,6-dimethylphenol, respectively. ¹H-NMR and IR spectra showed that the dyes exist primarily in the azo form in DMSO solution and as solids. UV-Vis spectra (in MeOH) showed intense (ε ≅ 10⁴ M^-1cm^-1) absorptions ranging from 380 nm to 500 nm for these ligands.

The …

Side Chain Effect On Micellarly Catalyzed Hydrolysis Of Hydroxamic Acids In Perfluorooctanoic Acid Environment, A.C. Menik Fernando

Masters Theses

The side chain effect on micellar catalysis of hydroxamic acids with perfluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution has been demonstrated in this thesis.

The rate constant-surfactant concentration profiles were used to estimate the critical micelle concentration and the second order rate constant for hydrolysis in the aqueous bulk phase.

The pseudo-phase ion exchange model satisfactorily explains the surfactant effect. The second order rate constants in the aqueous bulk phase show a direct relationship with steric substituent constants. The major influence of the change in micellar catalysis is the location in the micelle where the substrate …

The Effect Of Chromium Compounds On The Mutagenic Rate Of Benzo[A]Pyrenediolepoxide In Human Fibroblasts, Yordanos Tesfai

Masters Theses

Cancer researchers are interested in identifying the environmental causes and synergistic influences of different chemical carcinogens in order to decrease the risk of cancer. There are numerous studies which have investigated the effect of individual carcinogens but relatively few in which a well defined mixture of chemicals have been used. The present study was performed to examine the effect of chromium compounds on benzo[a]pyrene diolepoxide (BPDE) induced cytotoxicity and mutagenicity in human fibroblasts. Cytotoxicity was measured by the ability to fonn colonies while selection of 6-thioguanine resistant mutants were used to study mutagenesis in human fibroblasts.

Our results indicate that …

Rapid Method For Determination Of Iodine Numbers Of Vegetable Oils, Ondrej Hendl

Masters Theses

There is a great deal of interest by the public about the total unsaturation of fats and oils used in commercial products as an indication of nutritional value. Dealers in fats and oils are extremely interested in characterizing these products. The unsaturation is a guide to the expected stability of food additives, such as edible oils and foods in which they are used. Unsaturation is typically evaluated as an iodine number (IN), calculated for these additives based on their consumption of iodine through addition across the carbon-carbon double bonds. The classical titration method can typically take 45 minutes.

The investigation …

A Hplc Method To Assay Mycotoxins - Fumonisin, Ochratoxin And Zearalenone, Nalini Sadagopan

Masters Theses

A HPLC method to quantitate the mycotoxins Fumonisin B1 (FB1), Ochratoxin A(OA), and Zearalenone (ZON) was developed and validated. Mycotoxins are secondary metabolites of fungi like Fusarium, Asperigillus and Penicillium that contaminate crops. They have a wide array of chemical structures which facilitate their analytical detection.

The analytical method consists of reverse phase chromatography and fluorescence detection. Sample cleanup was performed using SAX and C18 cartridges prior to analysis on the HPLC.

The method developed for FB1 is unique in that it is more sensitive, accurate, and reproducible than the existing methods. Automation is one of the salient features that …

Reactions Of Chlorine And Some Of Its Oxygen Derivatives With Phenol, Lizhuo Zhang

Masters Theses

Chlorine is widely used in industry. It is also the most commonly used disinfectant in water treatment plants. Since the amount of chlorine used is increasing each year, environmental and health concerns arise due to its reactivity with various of organic compounds. Many chlorinated organic compounds are toxic and as a result other non-chlorinating compounds, such as chlorine dioxide, might be potential substitutes in the future, especially in water treatment plants.

Previous studies have indicated that chlorinated organic compounds are not formed when chlorine dioxide is used as a disinfectant. Furthermore no reaction occurs between chlorite and phenol in the …

An Investigation On Nonenzymatic Autoxidation Of Phenolic Compounds In Natural Waters, Lei Jiang

Masters Theses

The nonenzymatic autoxidation of the phenolic compounds chlorogenic acid in aqueous solution was studied. The study demonstrated that the oxidation rate of chlorogenic acid was strongly dependent on pH. The higher the pH, the faster the rate of oxidation. The involvement of phenolate ions and radicals in oxidation reactions are two possible reasons for the pH dependency. The presence of a trace amounts of reducible transition metal ions, such as copper(II), dramatically increases the oxidation rate of chlorogenic acid. Light also increases the oxidation rate of chlorogenic acid. However, the photochemical reaction was a much slower process.

The TLC and …

Segmental Motion Of Surface-Bound Swollen Poly(Methyl Acrylate)-D, Minghua Liang

Masters Theses

"Poly (methyl acrylate)-d_a (PMA-d_a) was prepared and adsorbed on silica then swollen with toluene and carbon tetrachloride. Comparisons of deuterium NMR spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, for the adsorbed polymer at different temperatures were made to obtain information about the backbone motion of the surface-bound polymer. The results suggest that the local fast motions may be similar to those in the corresponding solution, but the longer-range molecular motions were more restricted than those in solution. The log-normal distribution yielded mean correlation times which were 4-10 times slower for the …

Synthesis And Characterization Of Bifunctional Silica Gel Surfaces, Alufelwi Maxwell Tshavhungwe

Masters Theses

Bifunctional silica surfaces consisting of various combinations of the following organofunctional silanes were synthesized and characterized using diffuse reflectance infrared spectroscopy: hexamethyldisilazane, octyldimethylmethoxysilane, phenyldimethylethoxysilane, (3-aminopropyl) -dimethylmethoxysilane, ( 2 - cyanoethyl)triethoxysilane, and trimethylmethoxysilane.

The relative amounts of organosilanes loaded on a silica surface were obtained from band area ratios of IR bands. Ratios of organosilanes bonded to the same silica surface were calculated from normalized band areas of the isolated silanol peak. In reactions in which surface coverage was incomplete, the relative amount of inaccessible silanols was determined from the band area ratio of the silanol peak. Comparisons of organosilane loading …

Mechanistic Studies On Malate Dehydrogenase From Escherichia Coli, S. Kirk Wright

Masters Theses

Kinetic studies and chemical modification studies were performed on malate dehydrogenase from Escherichia coli (eMDH). Chemical modification studies using diethylpyrocarbonate and iodoacetic acid, along with log V/K profiles indicate that one ionizing group with a pK_a between 7.9 and 8.5 acts as a general acid/base in the catalytic mechanism. Log V profiles suggest that malate binds to the correctly protonated form of the enzyme. These results imply that a histidine residue is required for catalysis.

A primary deuterium kinetic isotope effect of 1.43 (±0.14) was observed on V/K using malate-2-d, while no isotope effect was measured on V_{max …}

Effects Of Insulin And Insulin Mimetics On Antioxidant Enzyme Levels: In Vivo And In Vitro, Shikha Varma

Masters Theses

Tissue antioxidation status is considered to be an important factor for elucidating the etiology of diabetes and its physiological complications. This study was aimed to determine the in vivo antioxidant enzyme levels in the altered antioxidant status of diabetic rat liver with the treatment of two potent insulin mimetics, vanadium and selenate. The direct effects of vanadate, selenate, and zinc (another insulin mimetic) on the antioxidant enzyme levels in primary rat hepatocytes in culture was also determined. Levels of superoxide dismutase (SOD), catalase (CAT) and gluthahione peroxidase (GPX) were determined in both model systems.

In the vivo model, insulin treatment …

Regulation Of The Expression Of Lipogenic Enzymes By Insulin-Mimetics, Juiyu Wu

Masters Theses

Many researchers have shown that selenate (SeO₄^2-) and vanadate (VO₄^2-) have insulin-mimetic effects in certain biological processes. These mimetic effects include increasing glucose transport, regulating glycolytic enzymes, normalizing plasma glucose levels and activities of insulin regulated enzymes in diabetic rats. To clarify the functions and roles of these insulin-mimetics in different insulin-regulated metabolic pathways, the expression of the genes for glucose-6-phosphate dehydrogenase (G6PDH) and fatty acid synthase (FAS) were investigated. G6PDH is a key enzyme in the pentose phosphate pathway and is also involved in lipogenic metabolism by providing 55-70% of the NADPH utilization …

Structural Effects On Micellar Catalyzed Hydrolysis Of Hydroxamic Acids With Perfluorooctanoic Acid As Surfactant, Xing Zhang

Masters Theses

This thesis demonstrated the structural effects on micellar catalyzed hydrolysis of hydroxamic acids with prefluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution.

For different hydroxamic acids, the observed pseudo-first order rate constant-surfactant concentration profiles were obtained and were used in the determination of critical micellar concentrations (cmc).

The micellar catalytic effect was satisfactorily explained by the pseudo-phase ion exchange (PPIE) model. The PPIE model was successfully applied in the determination of the reaction rate constants both in the water phase and in micellar pseudo-phase.

Further investigation into more appropriate hydroxamic acids is suggested in order to obtain …

The Synthesis And Characterization Of Novel 5,6-Disubstituted 1,10-Phenanthrolines, Liansheng Zeng

Masters Theses

Two new ligands, 5-amino-6-nitro-1,10-phenanthroline (5-NH₂-6-NO₂-phen), produced by amination of 5-NO₂-1,10-phenanthroline, and 5,6-diamino-1,10-phenanthroline (5,6-(NH₂) ₂-phen) ,produced by reduction of 5-NH₂-6-NO₂-phen, have been synthesized and characterized. The ligand 5-NH₂-6-NO₂-phen has been coordinated to a Ru(II) metal center to produce the Ru(II)-polypyridine complex [ (bpy) ₂Ru (5-NH₂-6-NO₂-phen)] (PF₆ ) ₂ (bpy= 2, 2' -bipyridine) . This complex has been characterized by IR, UV-Vis, ¹H-NMR, and cyclic voltammetry (CV) .

Novel Compounds (Including Transition-Metal Complexes) Based On 1,10-Phenanthroline-5,6-Dione, Hui Zhou

Masters Theses

This thesis describes the synthesis of the transition metal complex [(bpy) ₂Os^II (pptd)] (PF₆)₂^·2H₂O, an analog of [(bpy) ₂Ru^II (pptd)] (PF₆)₂^·2H₂O. Spectroscopic and electrochemical data on this complex are reported here. It was found that the electronic communication between the metal center and the pteridinedione portion of pptd did not appear to be enhanced in the Os(II) complex relative to its Ru(II) analog. The increased ability of Os(II) to undergo backbonding appeared to affect only the 1,10-phenanthroline portion of pptd.

A useful …

The Synthesis Of N-Chlorosulfonyl Β-Lactams And Their Rearrangements, Lihua Zhang

Masters Theses

The synthesis of several N-chlorosulfonyl-β-lactams and their rearrangements have been carried out via CSI (chlorosulfonylisocyanate) reaction. The mechanism of β-lactam synthesis as well as its rearrangements were also studied. The characterization of β-lactams was performed with IR, ¹H and ¹³C NMR, and HRMS. β-lactams 2-chlorosulfonyl-1-methyl-2-azabicyclo[4.2.0]octan-3-one (71), 1-chlorosulfonyl-4-methyl-4- (phenylmethyl)azetidin-2-one (74) and 1-chlorosulfonyl-4,4- (diphenylmethyl)azetidin-2-one (75) were synthesized for the first time. β-lactam 4-chlorosulfonyl-3, 9, 9-trimethyl-4-azatricyclo [6.1.0.0^3,6] nonan-5-one (73) was obtained as crystalline solid instead of liquid.

Different effects, such as temperature, solvents and catalysts, on the rearrangement of the …

Equilibrium And Kinetic Studies Of Isomerization Of (Oc)5m[Η1-Pph2ch2ch(Pph2)2] And (Oc)5m[Η1-Pph2ch(Pph2)Ch2pph2] (M=Cr, Mo, W), Weiying Lin

Masters Theses

It has been found that (OC)₅M[η¹-PPh₂CH₂CH(PPh₂)₂] and (OC)₅M[η¹-PPh₂CH(PPh₂)CH₂PPh₂] (M=Cr, Mo, W) exist in equilibrium in solution. This linkage isomerization is the first experimental evidence for the exchange of terminal and coordinated phosphorus groups in pentacarbonyl complexes of group 6 metals.

(OC)₅M[η¹-PPh₂CH₂CH(PPh₂)₂] ⇌ (OC)₅M[η¹-PPh₂CH(PPh₂)CH₂PPh₂]

(M = Cr, Mo, W)

In this work, equilibrium …

Isomerization And Chelation Studies Of Dangling Phosphine Complexes Of Group 6, Zhongjiang Jia

Masters Theses

Vinyl addition reactions, catalyzed by 2,2'-azobis(isobutyronitrile) (AIBN), have been used to prepare six pentacarbonyl complexes of group 6, each of which contains a dangling Ph₂PCH₂CH₂P(p-tol)₂ ligand.

Each of the six complexes undergoes slow isomerizationand chelation at 55 °C in perdeuterated toluene:

The reactions were monitored by ³¹P{¹H} NMR spectroscopy. The isomerization reactions are reversible in solution, while the chelated products form irreversibly with the loss of carbon monoxide. The rate constants, K₁ and K_-1, have been determined for the three pairs of linkage isomers. Equilibrium …

The Synthesis And Characterization Of [Ruii (Bpy) 2 (Biphen) ] (Pf6)2 And [ (Bpy) 2ruii (Biphen) Ruii (Bpy) 2] (Pf6)4, Mei-Yueh Chang

Masters Theses

A new bidentate polypyridine bridging ligand (biphen), produced by the condensation of 1,10-phenanthroline-5,6-dione with 5,6-diamino-phenanthroline has been synthesized and characterized. In addition the monometallic complex [(bpy)₂Ru^II(biphen)](PF₆)₂ and the bimetallic complex [(bpy)₂Ru^II(biphen)Ru^II(bpy)₂](PF₆)₄ have been prepared. The complexes were characterized by elemental analysis, by ¹H-NMR spectroscopy and by cyclic voltsmmetry(CV).

The results of these analyses seem to indicate that biphen acts like two independent units when attached to a - Ru^II(bpy)₂ fragment. a bipyridine portion and a phenazine portion. Moreover, …

The Reaction Of Caffeic Acid And Copper (Ii) In Natural Water, Ling Xiaozheng Xu

Masters Theses

The interaction of the lignin precursor compound caffeic acid with copper(lI) in aqueous solution was studied. In the presence of a reducible transition metal, such as copper, caffeic acid undergoes oxidation. Oxygen was shown to play an important role in the reaction. The UV-visible data demonstrated that the conjugated double bond in the propenoic acid side chain of caffeic acid slowly disappeared during the reaction. The molecular weight experiments indicated that the product was a dimer. FTIR spectrum agreed with two possible dimer structures involving the side chain of caffeic acid. In addition, the reaction was shown to be reversible. …

Photoionization With Excitation Of The 4s And 4p Subshells In Krypton, Ahmad Farhat

Masters Theses

High-resolution photoelectron spectra of the nd, Rydberg satellites in krypton have been measured for the first time for six different angles and for photon energies between 68.5 and 250 eV. The relative intensities of these satellites with respect to the 4s and 4p main lines are in very good accord with the most recent measurements of Krause et al. (1992) at 68.5 eV. They also confirm that the theoretical predictions for the relative intensity of these satellites are too high. We determine the ratios for nd satellites with respect to the 4s and 4p main lines, and extract the angular …

Application Of A Modified Analytical Derivatization Method To The Determination Of Microbial Metabolites In Aquifer Systems, Jie Lu

Masters Theses

The geochemical evolution of Low Molecular Weight Fatty Acids (LMWFA's) in various ground water samples and aquifer solid samples from both contaminated and uncontaminated sites has been studied. An improved analytical method has been established for both qualitative and quantitative determination of LMWFA's. The low molecular weight (LMW) organic acids are metabolic intermediates of the oxidative biodegradation of hydrocarbon contaminants. The hydrocarbons are believed to be the electron donors in these redox reactions. Formic and acetic acids were found to be the major LMWFA's in these ground water samples and aquifer solid samples. Their concentrations increase as the redox condition …

Quantitative Analysis Of Steroids By 13C Nmr Spectroscopy, Pei Wang

Masters Theses

Steroids are usually analyzed quantitatively by using HPLC with ultraviolet detection and are confirmed by FTIR, GC-MS. Quantitative ¹³C NMR method provide an alternative means to analyze steroids. Chromatographic separation and subsequent identification by match with a spectroscopic data base spectrum is not required for quantitative analysis of mixture components. Instead, equivalent information is obtained by creating subspectra from resonances with equivalent peak areas within a quantitative NMR spectrum. Techniques for eliminating Nuclear Overhauser Enhancement (NOE) effect is described.

Approaches To And Synthesis Of Chalcone Amides, Gregory S. Marczak

Masters Theses

A series of "chalcone" amides have been prepared. These amides are unique in the position of the substituted hydroxy and methoxy functional groups. Early approaches to the synthesis of the amides proved difficult when preparing intermediates from the phenolic substituents. These phenols were then protected to lead to easier formation of the intermediates, and then deprotected to yield the corresponding chalcone amides. The approaches to the preparation of these compounds is presented, along with the physical data used to characterize the chalcone amides.