The intercalation of cetyltrimethylammonium cations into muscovite by a two-step process: II. The intercalation of cetyltrimethylammonium cations into Li-muscovite

The alkylammonium cations were successively intercalated into the interlayer of muscovite. It was achieved by inorganic-organic ion exchange in the hydrothermal reaction of the LiNO₃-treated muscovite with cetyltrimethylammonium bromide solution. One-dimensional Patterson plots and electron density calculations show that hydrated Li⁺ and CTA⁺ cations entered the interlayer of muscovite successively. The CTA⁺-intercalated muscovite was characterized by powder X-ray diffraction and elemental analysis, in conjunction with FTIR, nuclear magnetic resonance, X-ray photoelectron spectra, high-resolution transmission electron microscopy, etc. The experiments show that organo-muscovite composite with ordered structure has been obtained. The CTA⁺ headgroups are distributed in the interlayer uniformly. However, the arrangement and conformation of CTA⁺ chains are strongly dependent upon the reaction temperature. At lower reaction temperature, the chains of CTA⁺ ions adopt a little more disordered arrangement and have higher gauche/trans conformer ratio, resulting in the disturbance to the interlayer symmetry. Whereas at higher reaction temperature, the sample with paraffin-like arrangement of CTA⁺ chains could be obtained, in which the methylene chains of CTA⁺ adopt a fully stretched, all-trans conformation.     

利用压电频移法测定水中的痕量亚硝酸盐

提出了利用压电频移法测定亚硝酸盐的方法。方法以碘离子与亚硝酸根之间的氧化还原反应为依据，通过测定由反应生成的碘所引起的压电晶体频率的变化，在被萃取水相中亚硝酸盐浓度为０．００９￣２．３ｍｇ／Ｌ范围内，频移值与浓度成正比：ΔＦ＝５．８＋２．５×１０＾３Ｃ（ｍｇ／Ｌ），ｒ＝０．９９０１。方法简便，用于天然水中亚硝酸盐的测定，结果令人满意。     

Effect of deacetylation rate on gelation kinetics of konjac glucomannan

Effect of deacetylation rate on the gelation behaviors on addition of sodium carbonate for native and acetylated konjac glucomannan (KGM) samples with a degree of acetylation (DA) range of 1.38-10.1 wt.% synthesized using acetic anhydride in the presence of pyridine as catalyst was studied by dynamic viscoelastic measurements. At a fixed alkaline concentration (C(Na)), both the critical gelation times (t(cr)) and the plateau values of storage moduli (G'(sat)) of the KGM gels increased with increasing DA. While at a fixed ratio of alkaline concentrations to values of DA (C(Na)/DA), the similar t(cr) and (G'(sat)) values independent of DA were observed. On the whole, increasing KGM concentration or temperature shortened the gelation time and enhanced the elastic modulus for KGM gel. The effect of deacetylation rate related to the C(Na)/DA on the gelation kinetics of the KGM samples were discussed.     

Direct optical detection of singlet oxygen from a single cell

Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.     

Thermal degradation of wood treated with guanidine compounds in air: Flammability study

Wood has been treated with guanidine phosphate, guanidine nitrate, guanidine carbonate and guanidine chloride to impart flame retardancy. The samples were subjected to differential thermal analysis (DTA) and thermogravimetry (TG) from ambient temperature to 800°C in air to study their thermal behaviors. From the resulting data, kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy was found to decrease from 116 to 54 kJ mol^–1; the char yield was found to increase from 5.6 to 34.9%, LOI from 18 to 41.5, which indicated that the flame retardancy of treated wood was improved. Effects of the different compounds on the degradation and flammability of wood have also been proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene

A fluorescence ratiometric sensor for pH determination is described in this paper. The sensor incorporated the pH-sensitive dye meso-5,10,15,20-tetra-(4-allyloxyphenyl)porphyrin (TAPP) as an indicator and a pH-insensitive dye N-(2-methacryloxyethyl)benzo[k,l]thioxanthene-3,4-dicarboximide (MBTD), a benzothioxanthene derivative, as a reference for fluorescence ratiometric measurement. To prevent leakage of the dyes, both were photocopolymerized with acrylamide, hydroxyethyl methacrylate, and triethylene glycol dimethacrylate on the silanized glass surface. The reproducibility and response time of the prepared sensor were sufficient. Most common coexisting inorganic ions and organic compounds did not interfere with pH sensing. In the acidic pH range from 1.5 to 5.0 the fluorescence intensity ratio of the two dyes varied linearly as a function of pH. The sensing membrane was found to have a lifetime of at least one month. The sensor was applied to the analysis of waste water and artificial samples.     

三元无规芳—脂族聚酯酰胺的热致液晶行为

采用低湿溶液缩聚的方法合成了对苯二甲酰氯，二甲基联苯胺和己二醇为单体的芳酯族液晶聚酯酰胺。用ＤＳＣ，Ｘ光衍射分析和偏光显微镜等手段研究了该系列聚酯酰胺的热致液晶行为，确认了二甲基联苯胺单体用量在２０％（ｍｏｌ）的情况下，所得聚酯酰胺仍为向列型液晶聚合物。由于聚酯酰胺分子间聚酰胺链段之间的氢键作用，随着二甲基联苯胺用量增加至６０ｍｏｌ％时，所得的聚酯酰胺己无液晶转变温度，其液晶区间即从熔融温度直至分     

钴膦簇合物的催化环丙烷化反应

本文首次利用碳基钴簇合物ＰｈＰＣｏ_３（ＣＯ）_９催化剂，在常压和－２０℃－０℃，用苯乙烯和重氮乙酸乙酯进行环丙烷化反应，合成了菊酸酯，重氮乙酸乙酯可全部转化，酯的选择性可达８５％。产物经减压分馏后，由ＩＲ和￣１ＨＮＭＲ分析，确证了产物为菊酸酯，表明了羰基钴簇合物对苯乙烯的环丙烷化反应有良好的催化性能，为四面体异核簇合物用于不对称催化反应打下了基础。     

Supramolecular assemblies of a naturally derived sophorolipid

Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees.     

膦化聚2,6—二甲基1,4—苯醚负载钯催化剂的表征及其催化性能

报道了四种不同P/Pd摩尔比的膦化聚2,6-二甲基1,4-苯醚负载把催化剂的加氢和异构化性能;通过XPS、电镜和远红外对催化剂进行了表征;并考察了溶剂和温度对催化剂活性的影响.