Multicomponent flocculating systems based on cationic polyelectrolytes

The kinetics of sedimentation of aqueous kaolin dispersion in the presence of multicomponent flocculating additives was studied. Binary and ternary mixtures based on poly-1,2-dimethyl-5-vinylpyridinium methyl sulfate, poly-N,N-dimethyl-N,N-diallylammonium chloride, and poly-N,N,N-trimethyl-N-methacryloyloxyethylammonium methyl sulfate were used as flocculants. The synergistic effect of the cationic polyelectrolytes in such multicomponent systems was revealed.     

Acceleration of amine/epoxy reactions with N‐methyl secondary amines

Kinetic studies established that the monomethylation of a primary amine leads to significantly higher reaction rates with glycidyl ethers. The relative rates for approximately 25 amines were determined in an alcohol solvent under pseudo‐first‐order conditions (excess epoxy). The rates were referenced to aniline. For the aliphatic amines, reactivity consistently increased upon going from a primary amine to the corresponding N‐methyl secondary amine. This acceleration effect was not seen for aniline. The enhanced reactivity was also seen in curing systems, both with pure methylated amine curing agents and with complex mixtures obtained from the partial methylation of polyamines. Economically viable partially methylated amine curing agents were obtained by the reductive alkylation of commercial polyamines with formaldehyde and by the reaction of monomethylamine with 3‐(N‐methylamino)propionitrile in the presence of hydrogen and a hydrogenation catalyst. Although actual cure performance is based on a complex combination of several factors, the acceleration due to monomethylation could be a useful tool for enhancing amine/epoxy curing reactions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 921–930, 2000     

Photostabilizing activity of tertiary hindered amines

The influence of the N-alkyl group of tertiary hindered amines on the photostabilization of polymers was studied. The photostabilizing effects of the tertiary amine derivatives of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine ( 1a ) in polypropylene were compared. All tertiary amine derivatives having α-H to hindered N showed higher effectiveness than 1a . Model liquid phase photoxidations were carried out by irradiating (UV-lamp) the solutions of tertiary hindered amines containing tert-butyl hydroperoxide as a photoinitiator. The tertiary hindered amines were oxidized more easily than corresponding parent hindered amine and converted to the parent amine, which was identified as its salt, resulting from the carboxylic acid produced from the N-alkyl group by oxidation. The thermal reaction of the tertiary hindered amines with tert-butyl hydroperoxide was also studied in the liquid phase. The tertiary hindered amines decomposed tert-butyl hydroperoxide more rapidly than the parent secondary hindered amine, and generated the parent amine. It was also found that the photostabilizing effects of tertiary hindered amines for polyolefins were higher than that of the parent secondary hindered amine.     

Interaction of bovine serum albumin with chrysotile: spectroscopic and morphological studies

The biodurability of chrysotile fibers, which is related to their cytotoxicity and mutagenic responses, is strongly affected by the surface chemical adsorption of biological molecules. Natural chrysotile is a heterogeneous material in both structure and composition. The availability of synthetic stoichiometric chrysotile of constant structure and uniform morphology has allowed us to investigate its interaction with bovine serum albumin (BSA). By using transmission electron microscopy (TEM) and atomic force microscopy (AFM), we have obtained the first morphological evidence of albumin adsorption onto chrysotile nanocrystals. FTIR spectroscopy was used to quantify modifications of BSA secondary structure that were induced by the surface interaction. The protein transition to beta-turns allows a stronger interaction between the protein hydrophilic side-chains and the charged asbestos surface, which is consistent with hydrogen bonds involving the superficial OH groups. Synthetic stoichiometric chrysotile nanocrystals were shown to be an ideal reference standard with which to study the interaction of asbestos fibers with biological systems, in order to elucidate the chemical mechanisms of asbestos toxicity.     

Preparation and evaluation of a chrysotile asbestos-containing standard material for validating x-ray diffractometric quantitation

A standard material containing chrysotile asbestos for the validation of x-ray diffractometric quantitation was developed using an asbestos-containing building material i.e., perlite board. The board as the base material was crushed, pulverized, and homogenized. The homogeneity of the powder of perlite board was estimated by analysis of variance. The diffraction intensity values of the crystalline phases and the concentrations of elements determined by x-ray diffractometry and x-ray fluorescence analysis were used for analysis of variance. There is no significant difference between the within-bottle variance and the between-bottle variance, indicating that the powdered perlite board was sufficiently homogenous. The concentration of chrysotile in the material was determined using two methods: an internal standard/x-ray diffractometry method and the x-ray diffractometry/Rietveld refinement. The concentration of chrysotile in the material was determined by an internal standard/x-ray diffractometry method and the material had a chrysotile concentration of 24.1 ± 0.2 mass%.     

Installation of amine moieties into a polycyclic anodic product derived from 2,4-dimethylphenol

When 2,4-dimethylphenol is anodically treated, a dehydrotetramer with four contiguous stereocentres is readily obtained on a multi-gram scale. The substitution of a 2,4-dimethyl-phenoxy fragment by several amines was demonstrated, and the best results were obtained with primary amines. Optically pure α-chiral aliphatic amines yield diastereomeric mixtures that can be separated in most cases. The basic amine causes a partial hemiketal-opening of the bisbenzofuran moiety leading to an equilibrium within an α,β-unsaturated cyclohexenone. This dynamic behaviour occurs on the time scale of NMR spectroscopy and is also found by X-ray analysis providing a consistent picture.     

Laser microprobe mass analysis of o-phenylenediamine on asbestos fibres

The adsorption behaviour of o-phenylenediamine and its catalytically formed oxidation products such as 2,3,-diaminophenazine and higher-molecular-weight compounds on different varieties of asbestos is studied by using laser desorption mass spectrometry. The results prove that amosite adsorbs the product more easily than do crocidolite and anthophyllite, whereas U.I.C.C. chrysotile A does not give rise to detectable adsorption, and the adsorption observed for U.I.C.C. chrysotile B is only fair. The method shows potential for the investigation of the surface reactivity of pure and industrially transformed asbestos and other fibrous materials.     

硫酸铝渣制备聚硅酸铝铁絮凝剂及应用性能研究

以硫酸铝渣为原料,研制出了一系列不同A1／Fe／Si物质的量比的聚硅酸铝铁絮凝剂（简称PAFsc）。考察了PAFSC的混凝、除浊、脱色等性能,并研究了A1／Fe／Si物质的量比、pH、投药量等因素对PAFSC性能的影响。处理模拟浊水时,当n（A1）／n（Fe）=2．0～4．0,n（M）／n（SiO2）=0．7～1．3时...     

A critical examination of the salicylaldehyde method for the determination of primary amines in the presence of secondary amines

Summary The salicylaldehyde method for the differentiation of primary and secondary amines in mixtures has been critically evaluated. This method yields best results in acetonitrile. In mixtures of amines one can expect high results for the primary amine with correspondingly low results for the secondary amine. Corrections can be made with known mixtures of the amines.Work performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore Laboratory under contract number W-7405-ENG-48.     

双冠醚研究(Ⅳ)——Schiff碱型和仲胺型双-(苯并15冠-5)对碱金属苦味酸盐的萃取行为

仲胺型双冠醚与四苯硼酸碱金属盐在丙酮溶液中。25℃下的电导说明它们与Na~+可能形成1∶1络合物(冠醚单元∶金属离子),而与K~+、Rb~+、Cs~+离子则形成2∶1络合物。用Schlff碱型和仲胺型双-(苯并15-冠-5)在水-氯仿体系中进行萃取,测量了分配比D和萃取平衡常数K,发现后者的K值均大于前者。双冠醚F_2对K~+的萃取能力最强,选择性最佳。     

Interference of the Simultaneous Presence of Different Biogenic Amines on the Response of an Amine Oxidase–Based Biosensor

Abstract

The application of an amine oxidase–based biosensor, which was selective for several biogenic amines, was examined for the simultaneous detection of cadaverine, putrescine, and histamine. The biosensor response parameters in mixtures containing cadaverine or putrescine were 1.14 times less than the sum of corresponding parameters in single-substrate solutions. Histamine did not cause any change of the biosensor response in the presence of cadaverine and/or putrescine. This “screening” of biosensor signal parameters by putrescine and cadaverine should be considered during calibration of amine oxidase–based biosensors used for the detection of biogenic amines.     

光酶级联一锅法合成手性脂肪胺

对映体脂肪胺在有机合成与化工领域具有广泛的应用, 但其主要依赖于金属催化获得. 我们设计了一种光催化与酶催化级联催化的合成方法, 由脂肪醇出发合成手性脂肪胺. 通过筛选, 发现9-芴酮在可见光激发下可高效催化脂肪醇氧化为脂肪酮, 后者作为反应中间体被转氨酶在胺供体存在下经转氨反应合成手性胺. 在一锅法条件下, 该级联方法转化率可达99%, 目标产物的光学纯度>99%. 此外, 该光催化体系可分别与手性互补的转氨酶级联, 进而获得手性反转的脂肪胺产物. 该光酶级联催化方法充分结合了光催化的高效率与酶催化的立体选择性优势, 为手性脂肪胺类分子的合成提供了一种新型合成方法.     

Competitive adsorption of sodium dodecyl sulfate and polyethylene oxide at the air/water interface

Geoinspired synthetic chrysotile, which represents an ideal asbestos reference standard, has been utilized to investigate homomolecular exchange of bovine serum albumin (BSA), the major plasma protein, between the adsorbed and dissolved state at the interface between asbestos fibers and biological medium. FTIR spectroscopy has been used to quantify BSA structural modifications due to surface adhesion on chrysotile fibers as a function of the surface coating extent. Circular dichroism spectroscopy has been used to investigate the adsorption/desorption equilibrium through analysis of the BSA structural perturbations after protein desorption from chrysotile surface. Data results show clearly that in the solid state BSA modifications are driven by surface interaction with the substrate, following a bimodal adsorption evidenced by two different binding constants. On the other hand, BSA desorbed in solution is able to rearrange, in the lack of substrate, although keeping irreversible modifications with respect to the native species. The lack of regaining its native structure certainly affects albumin interaction with biological environment. The present investigation on the stoichiometric synthetic geoinspired chrysotile nanocrystals is the first approach toward a deeper attempt to use standard synthetic chrysotile reference samples in mimicking the behavior of asbestos fibers and allows to better understand their interaction with a biological environment.     

Identification of Highly Active Flocculant Proteins in Bovine Blood

Synthetic polymeric flocculants are used extensively for wastewater remediation, soil stabilization, and reduction in water leakage from unlined canals. Sources of highly active, inexpensive, renewable flocculants are needed to replace synthetic flocculants. High kaolin flocculant activity was documented for bovine blood (BB) and blood plasma with several anticoagulant treatments. BB serum also had high flocculant activity. To address the hypothesis that some blood proteins have strong flocculating activity, the BB proteins were separated by SEC. Then, the major proteins of the flocculant-active fractions were separated by SDS-PAGE. Identity of the major protein components was determined by tryptic digestion and peptide analysis by MALDI TOF MS. The sequence of selected peptides was confirmed using TOF/TOF-MS/MS fragmentation. Hemoglobin dimer (subunits α and β) was identified as the major protein component of the active fraction in BB; its high flocculation activity was confirmed by testing a commercial sample of hemoglobin. In the same manner, three proteins from blood plasma (fibrinogen, γ-globulin, α-2-macroglobulin) were found to be highly active flocculants, but bovine serum albumin, α-globulin, and β-globulin were not flocculants. On a mass basis, hemoglobin, γ-globulin, α-2-macroglobulin were as effective as anionic polyacrylamide (PAM), a widely used synthetic flocculant. The blood proteins acted faster than PAM, and unlike PAM, the blood proteins flocculants did not require calcium salts for their activity.     

Effect of amine nature on reaction mechanism: aminolyses of o-4-nitrophenyl thionobenzoate with primary and secondary amines

Pseudo-first-order rate constants (k(obs)) have been measured spectrophotometrically for reactions of O-4-nitrophenyl thionobenzoate (2) with a series of primary and acyclic secondary amines. The plots of k(obs) vs amine concentration are linear for the reaction of 2 with primary amines. The slope of the Br?nsted-type plot for the reaction of 2 with primary amines decreases from 0.77 to 0.17 as the amine basicity increases, indicating that the reaction proceeds through a zwitterionic addition intermediate in which the rate-determining step changes from the breakdown of the intermediate to the reaction products to the formation of the intermediate as the amine basicity increases. On the other hand, for reactions with all the acyclic secondary amines studied, the plot of k(obs) vs amine concentration exhibits an upward curvature, suggesting that the reaction proceeds through two intermediates, e.g., a zwitterionic addition intermediate and an anionic intermediate. The microscopic rate constants (k(1), k(-)(1), k(2), and k(3) where available) have been determined for the reactions of 2 with all the primary and secondary amines studied. The k(1) value is larger for the reaction with the primary amine than for the reaction with the isobasic acyclic secondary amines, while the k(-)(1) value is much larger for the latter reaction than for the former reaction. The k(3) value for the reaction with secondary amine is independent of the amine basicity. The small k(2)/k(-)(1) ratio is proposed to be responsible for the deprotonation process observed in aminolyses of carbonyl or thiocarbonyl derivatives.     

Untersuchungen über die emulgierende Wirkung von Natriumcholeat

Toluene-in-water emulsions were prepared using sodium choleate as emulgent. The microscopic data revealed the systems flocculating at appreciable rate on ageing and with electrolyte content. Half lives of the dispersions for different concentration of flocculants were determined. The electrophoretic results and the calculated energy data showed the emulsion with high degree of stability. The reversible flocculation occurring in secondary minima is thus concluded. Adsorption constants and free energy of adsorption etc. at isoelectric point were calculated.

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Enzymatic determination of biogenic amines with transglutaminase

Tyramine, histamine, putrescine and cadaverine, the most common biogenic amines indicating the food quality, were studied in the transglutaminase-catalyzed reaction. Transglutaminase (protein-glutamine gamma-glutamyltransferase EC 2.3.2.13) catalyzes an acyl transfer reaction between a donor substrate and an acceptor substrate (e.g. biogenic amine) and forms a cross-linkage between substrates with a release of ammonia. The reaction can be monitored by measuring the ammonia produced in the reaction. The concentration of produced ammonia was found to be proportional to the concentration of biogenic amine and could hence be used to determination of biogenic amines in food matrixes.     

Investigation of the thermal modification of asbestos wastes for potential use in ceramic formulation

Preliminary research has been carried out on the thermal modification of chrysotile asbestos. Destruction of the tubular structure of asbestos was achieved by calcination at 1000°C. In order to characterize the changes accompanying thermal modification both natural asbestos and calcined asbestos were subjected to thermogravimetric and differential thermal analysis, X-ray analysis and examination by scanning electron microscopy. The possibility of utilization of the calcined asbestos in the presence of a phosphate binder for the manufacture of refractory materials has been demonstrated.     

X射线衍射法测定滑石粉中石棉成分

使用X射线衍射法,通过石棉的2θ特征峰进行判断,分析滑石粉中可能存在的石棉成分。结果表明,样品中不含温石棉、铁石棉和青石棉,并对温石棉和绿泥石进行了有效区分。方法快速,灵敏,可有效用于滑石粉中石棉的测定。     

Study on the thermal decomposition of chrysotile asbestos

This article reports the possibility of detoxification of chrysotile asbestos through a low temperature heating and grinding treatment. The effect of thermal treatment at different temperatures in the range from 500 to 725 °C for 3 h on raw natural asbestos was characterized by thermal analysis, X-ray diffraction, and scanning electron microscopy. It was found that an isothermal treatment at 650 °C caused the complete dehydroxylation of chrysotile Mg₃Si₂O₅(OH)₄. Transformation of the dehydroxylated phase to forsterite Mg₂SiO₄ was obtained by heat treatment in the range 650–725 °C. The study of microstructure changes of heated asbestos show the destruction of characteristic fibers of chrysotile and formation of strips of forsterite. It is easily milled to pulverulent-shape material by mechanical milling in vibratory mill.