Thermal degradation and flame retardance in copolymers of methyl methacrylate with diethyl(methacryloyloxymethyl)phosphonate

Methyl methacrylate (MMA) has been free radically copolymerized, both in bulk and in solution, with diethyl(methacryloyloxymethyl)phosphonate (DEMMP), to give polymers which are significantly flame retarded when compared with PMMA, as indicated by the results of limiting oxygen index (LOI) measurements, UL 94 tests, and the results of cone calorimetric experiments. The physical and mechanical properties of the copolymers are similar to those of PMMA, except that the bulk copolymers are slightly crosslinked, and are better than those of PMMA flame retarded to a similar extent by some phosphate and phosphonate additives. Examination of the some of the gaseous products of pyrolysis and combustion, and of chars produced on burning, show that flame retardation occurs in the copolymers by both a condensed-phase and a vapour-phase mechanism. The condensed-phase mechanism is shown to involve generation of phosphorus acid species followed by reaction of these with MMA units giving rise to methacrylic acid units. The methacrylic acid units subsequently form anhydride links, which probably impede depolymerization of the remaining MMA sequences, resulting in evolution of less MMA (the major fuel when MMA-based polymers burn). By undergoing decarboxylation, leading to interchain cyclisation and, eventually, to aromaticisation, the anhydride units are probably also the principal precursors to char.     

Study on the effect of different acids on the structure and photocatalytic activity of mesoporous titania

Nanocrystalline mesoporous titania was synthesized via a combined sol–gel process with surfactant-assisted templating method using cetyltrimethyl ammonium bromide (CTAB) as the structure-directing agent. The process was catalyzed by different acid (hydrochloric acid, nitric acid, sulfuric acid, or phosphoric acid). The prepared samples were characterized by XRD, TEM, BET and FT-IR. The photocatalytic activity of the samples was determined by degradation of phenol in aqueous solution. Results showed that different acid had different effect on the structure and crystal phase of the samples. The sample adjusted by phosphoric acid showed highest surface area and photocatalytic activity. The formation mechanism of the samples catalyzed by different acid was also discussed.     

Parahydrogen-based NMR methods as a mechanistic probe in inorganic chemistry

The study of reactions by NMR spectroscopy is normally limited by the poor detection limits offered by the method. An overview is presented of how chemical reactions can be studied using parahydrogen-assisted NMR spectroscopy, where detected signals can have strengths that exceed those normally available by factors that approach 31,000.     

嗜铅菌对水中重金属Pb~(2+)的吸附研究

研究了实验室提供的嗜铅菌对水中铅离子吸附的条件和机理.讨论了吸附时间、pH、铅离子的质量浓度和菌的质量浓度对吸附的影响.结果表明,在pH=7.0、铅离子初始质量浓度为25mg/L、离心湿菌的质量浓度为1.06g/L、吸附时间为60min时,铅离子的吸附率达96.88%;实验条件下超标25倍的含Pb~(2+)废水,可迭排放标准;Pb~(2+)的最大吸附量为150mg/g.数学模型Langmuir和Freundlich方程均能很好地描述嗜铅菌对Pb~(2+)的吸附过程.对Pb~(2+)吸附前后的红外光谱表征表明,嗜铅菌表面多糖、蛋白质的羟基峰和羰基峰均有不同程度的紫移,羟基峰、糖苷峰等峰宽略增,说明菌体吸附,主要是表面基团的作用所致.用原子力显微镜对吸附前后的嗜铅菌检测可见,吸附后菌体的弹性变小、粘性变大、部分茵体有一定的收缩,说明以表面吸附为主的吸附过程,对菌细胞的聚合度有影响,菌体内部对铅也有一定的生物积累.     

Unprecedented acid-catalyzed Wurtz-type coupling of meso-bromoindodicarbocyanine dyes

meso-Bromosubstituted indodicarbocyanine dyes produce dimeric molecules, together with the debrominated species, under acid catalysis. The relationship between the dimerization and hydrodebromination routes depends on the aryl substitution of the dyes. A possible reaction mechanism is also proposed.     

三峡工程坝址花岗岩体缓倾角结构面成因综合研究

本文对长江三峡工程坝址花岗岩体中缓倾角结构面成因进行了全面的综合研究。从野外地质调查人手,在大量野外勘测的基础上进行宏观分析,同时辅之以扫描电镜、透射电镜、包体温度测定等方法进行微观构造组构、差异应力等的研究。在地质力学宏观分析的基础上,利用地质力学物理模拟进行相似条件下的反演,并利用非线性有限元数值模拟进行验证。同类研究在国内外均未见先例,可为同类工程研究借鉴。     

Two isolated intermediates of the Tröger's base: synthesis and mechanism

By controlling the amount of catalyst 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride, two new intermediates of Tröger's bases (11, 1,6-dimethyl-3-(4-methylphenyl)-1,4-dihydroquinazolin-3-ium tetrafluoroborate and 12, 8-methyl-2,5-bis-(4-methylphenyl)-3,5,6,7-tetrahydropyrimido[5,6,1-ij]quinazoline-2-ium tetrafluoroborate) were simply obtained from the one-pot reaction of aromatic amine and formaldehyde in ionic liquid at ambient temperature. These results support the mechanism for Tröger's base formation supposed by Fernando Coelho and co-workers. However, the crystal structure of 12 and correlative quantum chemistry calculation results are not reconciled with their report.     

Synthesis and characterisation of medium-sized ring systems by oxidative cleavage. Part 2: Insights from the study of ring expanded analogues

Variable temperature NMR analysis and computational methods have been used to develop a detailed understanding of the ¹H NMR spectra of a family of medium-sized ring containing compounds. The family consists of analogues containing 10-, 11- and 12-membered rings and in all cases the NMR spectra at room temperature showed a series of diastereotopic methylene signals despite the lack of a stereogenic centre in these systems. On repeating the NMR analysis at higher temperatures, all the signals coalesced for the 12-membered ring system consistent with full interconversion of ring conformers. This was not observed in the analogous 10- and 11-membered ring systems with the interchange of conformers remaining slow on the NMR timescale. However, 1D gs-NOESY/EXSY NMR experiments showed that in the smaller ring systems interconversion of diastereotopic protons did occur. Computational studies suggest that the dynamic process observed by NMR for the 10- and 11-membered rings systems is different from that observed in the 12-membered ring containing compound.     

The chemical reactivity of a known anti-psoriasis drug. Part 1: Further insights into the products resulting from oxidative cleavage

The oxidative cleavage of the known anti-psoriasis drug 1 to give 2 has been reported previously. Due to the importance of accessing medium-sized ring containing systems via oxidative cleavage, this reaction has been revisited revealing additional information about the structure of 2. Alternative reaction products were identified when the reaction was carried out in the presence of water. The conversion of 1 to 2 has also been carried out using ruthenium tetroxide. A detailed variable temperature NMR and computational study of the restricted rotation of the N-aryl ring in 2 is presented.