The effect of inclusion inβ-cyclodextrin on the chemistry of peroxides: Reactions of radicals withβ-cyclodextrin

Studies by electron paramagnetic resonance (EPR), differential scanning calorimetry, thermogravimetric analysis, HPLC and NMR showed that radicals produced by thermolysis and photolysis of benzoyl peroxide,t-butyl peroxide and cumene hydroperoxide included in-cyclodextrin (-CD), undergo significant reaction with the-CD. The formation of-CD radicals was observed by EPR. Products formed by addition of radicals to-CD were also observed. Such host:guest radical reactions explain the reported stabilization of peroxides, found with-CD inclusion, as being primarily due to the interruption of chain reactions by trapping of the chain carriers. A small increase in activation barrier for cleavage of the included peroxide in-CD was also observed.     

Thiol- and thioether-based bifunctional chelates for the {M(CO)3}+ core (M = Tc, Re)

By analogy to the recently described single amino acid chelate (SAAC) technology for complexation of the {M(CO)3}+ core (M = Tc, Re), a series of tridentate ligands containing thiolate and thioether groups, as well as amino and pyridyl nitrogen donors, have been prepared: (NC5H4CH2)2NCH2CH2SEt (L1); (NC5H4CH2)2NCH2CH2SH (L2); NC5H4CH2N(CH2CH2SH)2 (L3); (NC5H4CH2)N(CH2CH2SH)(CH2CO2R) [R = H (L4); R = -C2H5 (L5). The {Re(CO)3}+ core complexes of L1-L5 were prepared by the reaction of [Re(CO)3(H2O)3]Br or [NEt4]2[Re(CO)3Br3] with the appropriate ligand in methanol and characterized by infrared spectroscopy, 1H and 13C NMR spectroscopy, mass spectrometry, and in the case of [Re(CO)3(L2)] (Re-2) and [Re(CO)3(L1)Re(CO)3Br2] (Re-1a) by X-ray crystallography. The structure of Re-2 consists of discrete neutral monomers with a fac-Re(CO)3 coordination unit and the remaining coordination sites occupied by the amine, pyridyl, and thiolate donors of L2, leaving a pendant pyridyl arm. In contrast, the structure of Re-1a consists of discrete binuclear units, constructed from a {Re(CO)3(L1)}+ subunit linked to a {Re(CO)3Br2}- group through the sulfur donor of the pendant thioether arm. The series of complexes establishes that thiolate donors are effective ligands for the {M(CO)3}+ core and that a qualitative ordering of the coordination preferences of the core may be proposed: pyridyl nitrogen approximately thiolate > carboxylate > thioether sulfur > thiophene sulfur. The ligands L1 and L2 react cleanly with [99mTc(CO)3(H2O)3]+ in H2O/DMSO to give [99mTc(CO)3(L1)]+ (99m)Tc-1) and [99mTc(CO)3(L2)] (99mTc-2), respectively, in ca. 90% yield after HPLC purification. The Tc analogues 99mTc-1 and 99mTc-2 were subjected to ligand challenges by incubating each in the presence of 1000-fold excesses of both cysteine and histidine. The radiochromatograms showed greater than 95% recovery of the complexes.     

Dipyridinium tetraisothiocyanatodioxotungstate(VI) and related compounds

Eight tetraisothiocyanatodioxotungstate(VI) salts with general formula, (BH)₂[WO₂(SCN)₄] (where B = pyridine, piperidine, quinoline, isoquinoline, 2-, 3-, and 4-picolines) are reported. These salts have been prepared by the reaction of sodium tungstate dihydrate with ammonium thiocyanate in the presence of HCl and isolated as pyridinium or related salts. The compounds have been characterized by elemental analysis, IR and electronic absorption spectra, conductance and magnetic susceptibility measurements, TGA/DTA, and molecular modelling studies The text was submitted by the authors in English.     

A basis for the type 〈n〉 hyperidentities of the medial variety of semigroups

Summary The medical varietyMV of semigroups is the variety defined by the medial identityxyzw = xzyw. This variety is known to satisfy the medial hyperidentitiesF(G(x ₁₁ ,, x _1n ),, G(x _n1 ,, x _nn )) = G(F(x ₁₁ ,, x _n1 ),, F(x _1n ,, x _nn )), forn 1. Taylor has observed in [2] thatMV also satisfies some other hyperidentities, which are not consequences of the medial ones. In [4] the author introduced a countably infinite family of binary hyperidentities called transposition hyperidentities, which are natural generalizations of then = 2 medial hyperidentity. It was shown that this family is irredundant, and that no finite basis is possible for theMV hyperidentities with one binary operation symbol.In this paper, we generalize the concept of a transposition hyperidentity, and extend it to cover arbitrary arityn 2. We show that theMV hyperidentities with onen-ary operation symbol have no finite basis, but do have a countably infinite basis consisting of these transposition hyperidentities.Research supported by NSERC of Canada.     

Investigation of capillary electrophoresis-laser induced fluorescence as a tool in the characterization of sewage effluent for fluorescent acids: determination of salicylic acid

The investigation of emerging contaminant issues is a proactive effort in environmental analysis. As a part of this effort, sewage effluent is of current analytical interest because of the presence of pharmaceuticals and their metabolites and personal care products. The environmental impact of these components is still under investigation but their constant perfusion into receiving waters and their potential effect on biota is of concern. This paper examines a tool for the characterization of sewage effluent using capillary electrophoresis-laser induced fluorescence (CE-LIF) with a frequency-doubled laser operated in the ultraviolet (UV). Fluorescent acidic analytes are targeted because they present special problems for techniques such as gas chromatography-mass spectrometry (GC-MS) but are readily accessible to CE-LIF. As an example of the application of this tool, salicylic acid is determined near the 100 ng/L (7 x 10(-10) M) level in sewage effluent. Salicylic acid is a metabolite of various analgesics. Relatively stable in the environment, it is a common contaminant of municipal sewage systems. Salicylic acid was recovered from freshly collected samples of the effluent by liquid-liquid extraction. Confirmation of identity was by electron ionization GC-MS after conversion of the salicylic acid to the methyl ester by means of trimethylsilyldiazomethane. CE-LIF in the UV has revealed more than 50 individual peaks in the extract and a background response that suggests a large and indeterminate number of additional compounds are present. These data together with complementary techniques provide information on the complexity and components in these effluent streams.     

Application of orthogonal collocation on finite elements for solving non-linear boundary value problems

A simple, convenient and easy approach to solve non-linear boundary value problems (BVP) using orthogonal collocation on finite elements (OCFE) is presented. The algorithm is the conjunction of finite element method (FEM) and orthogonal collocation method (OCM). The stability of the numerical results is checked by a novel algorithm which not only justifies the stability of the results but also checks the convergence of the method. The method is applied to the non-symmetric boundary value problems having Dirichlet’s and mixed Robbin’s boundary conditions.     

Bacterial characterization using protein profiling in a microchip separations platform

A rapid microanalytical protein-based approach to bacterial characterization is presented. Chip gel electrophoresis (CGE) coupled with LIF detection was used to analyze lysates from different bacterial cell lines to obtain signature profiles of the soluble protein composition. The study includes Escherichia coli, Bacillus subtilis, and Bacillus anthracis (Delta Sterne strain) vegetative cells as well as endospores formed from the latter two species as model organisms to demonstrate the method. A unified protein preparation protocol was developed for both cell types to streamline the benchtop process and aid future automation. Cells and spores were lysed and proteins solubilized using a combination of thermal and chemical lysis methods. Reducing agents, necessary to solubilize spore proteins, were eliminated using a small-scale rapid size-exclusion chromatography step to eliminate interference with down-stream protein labeling. This approach was found to be compatible with nonspore cells (i.e., vegetative cells) as well, not adversely impacting the protein signatures. Data are presented demonstrating distinct CGE protein signatures for our model organisms, suggesting the potential for discrimination of organisms on the basis of empirical protein patterns. The goal of this work is to develop a fast and field-portable method for characterizing bacteria via their proteomes.     

Simulative investigation for third order-IM terms in multi-tone RoF system

A multi-tone radio over fiber (RoF) system design for three RF signals has been investigated for different modulation techniques like direct and external modulation with EDFA and SOA amplification techniques. Frequency response has been studied including the effects of third order intermodulation terms. Frequency separation between the modulating tones has been varied to study its impact on received carrier power. The performance in terms of electrical RF power of three receiving channels at different frequency separations using different amplification techniques have been measured and compared. An improvement in the received RF power and IM suppression has been observed by using an external modulation based system with EDFA amplifier.     

Metastable ion studies: Ethyl(methoxy)(chloro)silanes

Metastable ion scanning was used to investigate the fragmentation patterns of ethyl(trimethoxy)silane, ethyl(dimethoxy)chlorosilane and ethyl(methoxy)dichlorosilane, their deuterated counterparts and ethyltrichlorosilane. For these compounds the molecule ion has a low abundance using 70 eV electron impact ionization. In all cases the base peak corresponds to the loss of neutral C₂H₅. When chemical ionization is employed with isobutane, usable peaks representative of the molecule ions are observed.