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51.
A novel 3D polymeric heteropolynuclear sodium(I) lead(II) complex containing different ligands, [NaPb(ClO4)(en)(NO2)2] was synthesized and characterized by elemental analysis and IR, and 1H‐, 13C‐, and 207Pb‐NMR spectroscopy. The single‐crystal X‐ray data of [NaPb(ClO4)(en)(NO2)2]n established that the complex is a three‐dimensional polymer, [(en)Pb(μ3‐ONO)2Na(μ3‐ONO)2Na(μ‐O2ClO2)Na]n. The Pb and Na atoms have four‐ and eight‐coordinate geometry, respectively. The lone pair of electrons at the PbII atom is ‘stereochemically active’.  相似文献   
52.
One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently, enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed as a model substrate, and SO2-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis of the carbohydrate moieties.  相似文献   
53.
Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and 1H NMR spectroscopy.  相似文献   
54.
New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no Tg. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution 13C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state 13C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state 13C chemical shifts of 34 and 33 ppm, respectively, for the central CH2 units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc.  相似文献   
55.
Two new coordination polymers of PbII complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)2(μ‐ebp)1.5]n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, 1H‐ and 13C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb2+ ions are doubly bridged by both the ebp and the SCN ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb2+ ion in 1 is a distorted monocapped trigonal prism, in which the Pb2+ ions have a less‐common holodirected geometry. In 2 , the Pb2+ ions are bridged by AcO ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb2+ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb2+ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb2+ ion is possibly occupied by a configurationally active lone pair of electrons.  相似文献   
56.
Summary Mono, bis and tris complexes of rhodium(III) with phenyl-2-picolylketone-2-pyridyl hydrazone (PPKPyH) have been characterized. In every case, the imino-proton of PPKPyH shows marked acidity associated with the coordination to rhodium(III). Electronic spectra show that all complexes are octahedral. The B-values suggest a strong covalency in the metal-ligand -bond and the Dq-values indicate a medium-strong ligand field. The magnetic susceptibility indicates that PPKPyH forms low-spin complexes with rhodium(III).1H n.m.r. spectra show that the tris(ligand) complexes arecis isomers. I.r. spectra show that the ligand is neutral or monobasic tridentate or bidentate. Far i.r. studies show that [Rh(PPKPyH)X3] · 2 H2O (X = Cl, Br or I) aremer isomers. The effect of pH variation on the rection products is also discussed.  相似文献   
57.
Ensafi AA  Khayamian T  Atabati M 《Talanta》2003,59(4):727-733
A sensitive cathodic stripping voltammetric method is developed for determination of lead(II), with adsorptive collection of complexes with Pyrogallol red (PGR) on to a hanging mercury drop electrode. After accumulation of the complex at −0.80 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from −0.20 to −0.50 V with differential pulse method. Then the reduction peak current for the lead(II)-PGR complex is measured at −0.39 V. The influence of reagent and instrumental variables was completely studied by factorial design analysis. The optimum analytical conditions for the determination of lead(II) were established. Under optimum conditions, lead(II) determined in the range of 0.1-30.0 ng ml−1 with a limit of detection of 0.06 ng ml−1. The method is successfully applied to determination of lead(II) in water sample.  相似文献   
58.
High performance liquid chromatography (HPLC) and gas chromatography (GC) are introduced for analysis of polymer lubricants (stearamide, oleamide and erucamide). In the HPLC method, a reverse phase octadecylsilane (ODS) column along with acetonitrile/methanol (60:40) as a mobile phase were used. Detection of analytes was performed by a UV detector at 202 nm. The analysis time was less than 8 min. In the GC method, polar capillary column and flame ionization detector (FID) were used for separations and detection, respectively. The analysis time by GC was longer than HPLC and was about 30 min. Limits of detection, linear range and repeatability of both methods are similar, but determination of oleamide in real samples by HPLC method is difficult due to complexity of the initial part of HPLC chromatogram in polyethylene samples. That problem is not observed in the GC method. Detection limits in both methods for all analytes are lower than 0.003% which are much lower than the amount of lubricants in commercial polymers (0.05–0.2%).  相似文献   
59.
Summary Bis(cyclopentadienyl)titanium(IV) diisothiocyanate [(Cp)2-Ti(NCS)2] reacts with MCl2 (M = Cu, Pd or Pt), [CuCl(PPh3)3], [RuCl2(PPh3)3] and [RuCl2(DMSO)4] (DMSO = dimethylsulphoxide) giving solid compounds of stochiometry [(Cp)2Ti(-NCS)2MCl2] (M = Cu, Pd or Pt), [(Cp)2Ti(-NCS)2CuCl(PPh3)], [(Cp)2Ti(-NCS)2-RuCl(PPh3)2]Cl and [(Cp)2Ti(-NCS)2RuCl2(DMSO)2]. These products have been characterized by physicochemical and spectroscopic methods.  相似文献   
60.
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