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Dichloromethane is one solvent that is used widely in laboratory. It is so stable that it seldom reacts with other materials. There are only a few reports that involves dichloromehane as a reactant. Previous in our laboratory, we discovered a dichloromethane activation product. To study the details of the methylene insertion prouct, [(SCH2S)PS]2Zn form (Et4N)2 (PS3Zn)2, we used monodentate thiols in different condition as models to understand what condition thiols may react with dichloro methane. We found out thiols can react with dichloromethane under strong base. When there is aromatic ring in a thiol, that thiol will react with dichloromethane easily. Adding zinc salts showed that zinc ion is an inhibitor in thiolate/dichloromethane reactions. We synthesized Tris(3-trimethylsilyl-2-thiophenyl)phosphine [H3SiPS3] and SiPS3Zn complex to study the parallel effect of adding bulky silyl substitaents on PS3 ligand towards reaction with dichloromethane. Most conclusion are similar to that of monodentate thiols. There is one thing that differs from the results of monedentate thiols: the SiPS3Zn complex does react with dichloromethane.

The fabrication and characterization of boron-doped diamond microelectrodes for use in electrochemical detection coupled with capillary electrophoresis (CE-EC) is discussed. They exhibited low and stable background currents and sigmoidally shaped voltammetric curves for cysteine, cystine and Fe(CN)63-/4- . Evaluation of the CE-EC system and the electrode performance were accomplished using a 10 mM borate buffer, pH 8.8, run buffer, and a 70-cm-long fused-silica capillary (10-mm i.d.) with seven sulfur-containing amino acids (methionine, cysteine, cystine, homocysyeine, homocystine, glutathionine, glutathionine disulfide) as test analytes. Reproducible separation (elution time) and detection (peak current) of seven sulfur-containing amino acids were observed with response precisions of 5% or less.

Filter holders and continuous air monitors (CAMs) are used extensively in the nuclear industry. It is important to minimize leakage in these devices and in recognition of this consideration, a limit on leakage for sampling systems is specified in ANSI/HPS N13.1-1999; however the protocol given in the standard is really germane to measurement of significant leakage, e.g., several percent of the sampling flow rate. In the present study, a technique for quantifying leakage was developed and that approach was used to measure the sealing integrity of a CAM and two kinds of filter holders. The methodology involves use of sulfur hexafluoride as a tracer gas with the device being tested operated under dynamic flow conditions. The leak rates in these devices were determined in the pressure range from 2.49 kPa (10 In. H2O) vacuum to 2.49 kPa (10 In. H2O) pressure at a typical flow rate of 56.6 L/min (2 cfm). For the two filter holders, the leak rates were less than 0.007% of the nominal flow rate. The leak rate in the CAM was less than 0.2% of the nominal flow rate. These values are well within the limit prescribed in the ANSI standard, which is 5% of the nominal flow rate. Therefore the limit listed in the ANSI standard should be reconsidered as lower values can be achieved, and the methodology presented herein can be used to quantify lower leakage values in sample collectors and analyzers. A theoretical analysis was also done to determine the nature of flow through the leaks and the amount of flow contribution by the different possible mechanisms of flow through leaks.

[N,N??-bis-(mercaptoethyl)-1,5-diazacyclooctanato]NiII, Ni-1, is known to undergo metallation reactions with numerous metals. [N,N??-bis-(mercaptoethyl)-1,5-diazacycloheptanato]NiII, (bme-dach)Ni or Ni-1??, differs from Ni-1 by one less carbon in its diazacycle backbone ring producing subtle differences in N2S2Ni geometry. Metallation of Ni-1?? with PdCl2, Pd(NO3)2, and NiBr2 produced three structural forms: Ni2Pd basket, Ni4Pd2 C4-paddlewheel, and Ni3 slant chair. In attempts to provide a rationale for the heterogeneity in the active site of Acetyl coA Synthase, metal ion capture studies of Ni-1 in methanol found a qualitative ranking of metal ion preference: Zn2+ < Ni2+ < Cu+. Formation constants for metal ion capture of Ni-1?? in water were determined for Pb2+, Ni2+, Zn2+, Cu+, and Ag+. A quantitative estimate places copper some 15 orders of magnitude above nickel or zinc in binding affinity. Sulfur dioxide uptake by Ni-1?? is characterized by significant color change, improved adduct solubility, and reversible binding of two equivalents of SO2. These combined properties establish Ni-1?? as a suitable model for gas uptake at nickel thiolate sites and as a possibly useful chemical sensor for this poisonous gas. Comparisons of molecular structures,&#61472; &#957;(SO) stretching frequencies, and thermal gravimetric analyses are made to reported adducts including the diazacyclooctane derivative, Ni-1&#903;2SO2. Visual SO2 detection limits of Ni-1 and Ni-1?? are established at 25 ppm and 100 ppm, respectively. Structural studies of products resulting from reaction at the nucleophilic S-sites of (bme-dach)Ni and [(bme-dach)Zn]2 included acetyl chloride and sodium iodoacetate as electrophiles are shown. The acetyl group is a natural electrophile important to the citric acid cycle. Acetylation of (bme-dach)Ni produces a five coordinate, paramagnetic species. Iodoacetate is a cysteine modification agent known to inhibit enzymatic activity. The reaction of (bme-dach)Ni and sodium iodoacetate yields a blue, six coordinate nickel complex in a N2S2O2 donor environment. The bismercaptodiazacycloheptane ligand binds lead(II) forming an unprecedented structural form of N2S2M dimers, in which Pb2+ is largely bound to sulfur in a highly distorted trigonal geometry. Its unusual structure is described in comparison to other derivatives of the bme-daco ligand. The synthesis and structural characterization of square pyramidal (bme-dach)GaCl are also given and compared to the analogous (bme-daco)GaCl.

Thesis (doctoral)--Helsinki University of Technology, 2000. / Includes bibliographical references. Also available on the World Wide Web.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 139-140). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 139-140). Also available on the Internet.

Thesis (Ph. D.)--West Virginia University, 2002. / Title from document title page. Document formatted into pages; contains xxiii, 236 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 220-236).