Metal complex-substituted polysiloxanes as novel coatings for capillary electrophoresis and capillary electrochromatography

Two novel polysiloxane-based polymers, which contain metal complexes, have been prepared. To prepare the Co(TACN)3+(2) (TACN= 1,4,7-triazacyclononane) based polymers, an orthoamide derivative of TACN was added to bromobutane-substituted methylpolysiloxane and hydrolyzed with base. Co(II) was then coordinated to the TACN, followed by cobalt oxidation to make polymer A or followed by N-octyl TACN coordination and cobalt oxidation to make polymer B. In both materials, TACN forms thermodynamically and kinetically stable Co(TACN)3+(2) complexes in which the six coordination sites of the Co(III) are occupied by nitrogens from the TACN. The polymers were coated on fused-silica capillary columns and spherical silica particles, which were used for capillary electrophoresis and capillary electrochromatography, respectively. The open and packed columns showed strong and pH-independent reversed electroosmotic flow.     

Structure and properties of hydrophobically end-capped poly(ethylene oxide) solutions in the presence of monovalent and divalent cations

Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges.     

Ruthenium dihydride complexes: NMR studies of intramolecular isomerization and fluxionality including the detection of minor isomers by parahydrogen-induced polarization

NMR studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its spectral features. In contrast, when L = AsMe(2)Ph, the ccc and cct-L forms are present in similar quantities and, hence, must have similar free energies; for this complex, however, the cct-CO isomer is also detectable. These complexes undergo a number of dynamic processes. For L(2) = dppe, an interchange of the hydride positions within the ccc form is shown to be accompanied by synchronized CO exchange and interchange of the two phosphorus atoms. This process is believed to involve the formation of a trigonal bipyramidal transition state containing an eta(2)-H(2) ligand; in view of the fact that k(HH)/k(DD) is 1.04 and the synchronized rotation when L(2) = dppe, this transition state must contain little H-H bonding character. Pathways leading to isomer interconversion are suggested to involve related structures containing eta(2)-H(2) ligands. The inverse kinetic isotope effect, k(HH)/k(DD) = 0.5, observed for the reductive elimination of dihydrogen from Ru(CO)(2)(H)(2)dppe suggests that substantial H-H bond formation occurs before the H(2) is actually released from the complex. Evidence for a substantial steric influence on the entropy of activation explains why Ru(CO)(2)(H)(2)dppe undergoes the most rapid hydride exchange. Our studies also indicate that the species [Ru(CO)(2)L(2)], involved in the addition of H(2) to form Ru(CO)(2)(H)(2)L(2), must have singlet electron configurations.     

钼掺杂LaVO4上丙烷氧化脱氢

研究了钼掺杂LaVO4催化剂的丙烷氧化脱氢催化性能.加入钼对丙烷氧化脱氢反应有很好的助催化作用.当丙烷转化率恒定在10％和20％时，丙烯选择性在LaMo0.1V0.9O4.05上分别达到了56％和43％，而在LaVO4上仅为36％和22％，这归结为钼掺杂催化剂上有利于丙烯生成的可活动氧物种的增加和催化剂氧化还原性的改变.     

Dienamines as diels-alder dienes. An efficient synthesis of a key intermediate for drimane-related sesquiterpenes

An efficient synthesis of dienediester 3, a key intermediate for drimane-related sesquiterpenes, is described starting from enal 4.     

Impedance study of Ni–Co electro-deposition on Fe powder particles in fluidised bed systems

The electrochemical impedance method was applied during the electrochemical deposition of a binary Ni–Co coating on iron powder in a fluidised bed electrode system. The influence of the suspension density on the charge transfer in the course of the electro-deposition process was studied. At a potential of −900 mV (vs. Ag/AgCl/3 M KCl), when the binary Ni–Co layer was formed, the impedance data were characterised by two semicircles with the semicircle at high frequencies being larger in magnitude. A contribution of the diffusion process to the overall current was observed. The optimal suspension density for the charge transfer in the bed was 10×10⁻³–15×10⁻³ (i.e., 4–6 g of iron powder in 50 ml of electrolyte). The most probable mechanism of the charge transfer for the studied concentrations of powder particles is the convective mechanism. The iron particles dispersed in the electrolyte were considered to act as either a depolariser or an additional working electrode depending on the applied electrode potential and on the suspension density.     

Chemosensors for the marine toxin saxitoxin

Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed.     

Applicability of polymer theories to the thermodynamics of proteins at the air/water interface: example of β-lactoglobulin

Knowledge of the equation of state of adsorbed or deposited layers of proteins at the air/water interface is of fundamental interest in the understanding of the surface activity of these molecules. Using scaling laws of current polymer theories, it has been shown that the equation of state of the interfacial layer in the semi-dilute regime should relate the surface pressure to the surface concentration through a power law. The exponent of this power law should reflect the quality of the solvent and the conformation of the adsorbed polypeptide chain. In the case of β-lactoglobulin layers, in the range of surface concentrations that should correspond to the semi-dilute regime, the relationship between surface pressure and surface concentration is expressed as a power law. The exponent of this power law is strongly influenced by the nature of the aqueous substrate and by the net charge of the protein molecule. The use of scaling laws gives a coherent view of the expansion of the polypeptide chain in the interfacial layer and of the relationship between surface concentration and surface pressure in the semi-dilute regime. This result favours a strong similarity between β-lactoglobulin and a polymer chain in the interfacial layer. It is concluded that current theories of polymer adsorption could be applied to interfacial protein layers.     

Synthesis and characterization of highly ordered mesoporous thin films with -COOH terminated pore surfaces

Highly ordered mesoporous inorganic-organic hybrid thin films with covalently bonded carboxylic acid (-COOH) terminal groups on the pore surfaces were synthesized by evaporation induced self-assembly of tetraethoxysilane, organosilanes, and a nonionic surfactant followed by acid hydrolysis and characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, surface acoustic wave (SAW) based N2 sorption, and thermogravimetric analysis (TGA) techniques.     

Synthesis of 1,2-cis-Configurated Glycosylphosphonates

A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ).