基于丙二酰胺结构不对称双子表面活性剂的合成及性能

在丙酮溶剂中,氯乙酸十六醇酯（I）与过量的二（3-二甲氨基丙基）丙二酰胺反应,用乙醚洗涤后,再与溴代十六烷季铵盐化,经丙酮-乙腈混合溶剂重结晶,得到了一种新型基于丙二酰胺结构的不对称Gemini表面活性剂（命名为16．18）,收率为51．2％（以I计）,纯度为99．6％。采用IR、1HNMR表征了结构,电导率法测定其CMC值为7．91×10^-5mol／L,滴体积法测定其YCMC为37．87mN／m,其Krafft点小于0℃,研究了其乳化、泡沫性能。     

Use of Self-assembled Monolayers at Variable Coverage to Control Interface Bonding in a Model Study of Interfacial Fracture: Pure Shear Loading

The relationships between fundamental interfacial interactions, energy dissipation mechanisms, and fracture stress or fracture energy in a glassy thermoset/inorganic solid joint are not well understood. This subject is addressed with a model system involving an epoxy adhesive on a polished silicon wafer containing its native oxide. The proportions of physical and chemical interactions at the interface, and the in-plane distribution, are varied using self-assembling monolayers of octadecyltrichlorosilane (ODTS). The epoxy interacts strongly with the bare silicon oxide surface, but interacts only weakly with the methylated tails of the ODTS monolayer. The fracture stress is examined as a function of ODTS coverage in the napkin-ring (nominally pure shear) loading geometry. The relationship between fracture stress and ODTS coverage is catastrophic, with a large change in fracture stress occurring over a narrow range of ODTS coverage. This transition in fracture stress does not correspond to a wetting transition of the epoxy. Rather, the transition in fracture stress corresponds to the onset of large-scale plastic deformation within the epoxy. We postulate that the transition in fracture stress occurs when the local stress that the interface can support becomes comparable to the yield stress of the epoxy. The fracture results are independent of whether the ODTS deposition occurs by island growth (T_dep = 10°C) or by homogeneous growth (T_dep = 24°C).     

布洛芬热分解及其动力学研究

通过布洛芬(ibuprofen)的热分解及其动力学研究,运用简单的热分解动力学方法进行计算分析,求出相关的活化能,指前因子和动力学参数。将布洛芬每个温度范围下的热分解过程分为3个阶段分别进行分析计算,发现每个阶段都满足一级反应方程。从而算出布洛芬热分解过程的活化能,指前因子和相关系数。通过对布洛芬热分解过程的研究,及对布洛芬TG和DTG曲线的研究,得出布洛芬在热分解过程中分为3个阶段,分别进行脱水,C-C键断裂和分子键断裂。并且随着升温速率的提高,布洛芬失重速率会逐渐趋向于温度升高的方向发展,即温度升高,布洛芬最大失重速率越大。     

Efficient Total Chemical Synthesis of 13C=18O Isotopomers of Human Insulin for Isotope‐Edited FTIR

Isotope‐edited two‐dimensional Fourier transform infrared spectroscopy (2 D FTIR) can potentially provide a unique probe of protein structure and dynamics. However, general methods for the site‐specific incorporation of stable ¹³C=¹⁸O labels into the polypeptide backbone of the protein molecule have not yet been established. Here we describe, as a prototype for the incorporation of specific arrays of isotope labels, the total chemical synthesis—via a key ester insulin intermediate—of 97 % enriched [(1‐¹³C=¹⁸O)Phe^B24] human insulin: stable‐isotope labeled at a single backbone amide carbonyl. The amino acid sequence as well as the positions of the disulfide bonds and the correctly folded structure were unambiguously confirmed by the X‐ray crystal structure of the synthetic protein molecule. In vitro assays of the isotope labeled [(1‐¹³C=¹⁸O)Phe^B24] human insulin showed that it had full insulin receptor binding activity. Linear and 2 D IR spectra revealed a distinct red‐shifted amide I carbonyl band peak at 1595 cm^?1 resulting from the (1‐¹³C=¹⁸O)Phe^B24 backbone label. This work illustrates the utility of chemical synthesis to enable the application of advanced physical methods for the elucidation of the molecular basis of protein function.     

Flash Sintering using Controlled Current Ramp

In conventional flash sintering, the current rises nonlinearly to a set current limit, accompanied by a spike in the power density. This sudden power spike may cause hot spot formation, in which current preferentially channels through a small area, causing localized melting while other areas remain unsintered. By using a controlled current ramp early on the sudden power spike can be avoided. In addition, by changing the ramp rate material properties such as porosity, grain size and conductivity can be tuned.     

Adsorption of antifouling booster biocides on metal oxide nanoparticles: Effect of different metal oxides and solvents

Controlling the release rate of biocides (antifouling agents) from a paint coating is a key issue for the development of multi-season antifouling marine coatings. One promising approach is the use of nanoparticles onto which biocides are adsorbed to prevent premature depletion of the biocide. Adsorption of one novel (Medetomidine) and six commercially available and widely used antifouling biocides (Chlorothalonile, Dichlofluanid, Diuron, Irgarol, Seanine, Tolylfluanid) onto oxide nanoparticles (Al₂O₃, CuO, MgO, SiO₂, TiO₂, ZnO) was investigated by HPLC and NMR in different organic solvents. Large differences in adsorption strength depending on the type of nanoparticle and solvent employed were observed. It was shown that nanoparticles coordinate preferentially with the imidazole moiety of Medetomidine. Independent of the type of particle this interaction was considerably stronger in comparison to the other biocides. However, the interaction strength was strongly dependant on the type of solvent, where the largest strongest interaction was achieved in o-xylene. In addition field tests were performed where a considerable decrease in release rate was displayed from coatings containing Medetomidine adsorbed to nanoparticles compared to coatings containing Medetomidine as single additive.     

A comparison of the catalytic performance of the layered oxychlorides of bismuth,lanthanum and samarium in the conversion of methane to ethylene

BiOCl is very efficient as a catalyst for the oxidative coupling of CH₄ to yield C₂ products, conversions of more than 20 percent and ratios of C₂H₄/C₂H₆ from 30 to 60, depending upon the precise conditions, being obtained at ca 700 °C. Its longevity, however, is rather poor: under operating conditions the solid lacks structural stability. Although LaOCl and SmOCl, each of which is isostructural with BiOCl, are inferior catalysts so far as C₂H₄/C₂H₆ ratios are concerned (0.3 to 0.6), they have superior stability. The same is true of the solid-solutions (Bi_0.5,La_0.5) OCl, the structural parameters of which were determined by X-ray powder Rietveld analysis. Both (Bi_0.5, Sm_0.5) OCl and (Bi_0.5, La_0.5) OCl yield C₂H₄/C₂H₆ ratios of close to unity at 700 °C.Paper presented in part at the Royal Society USSR Academy Workshop on Surfaces and Catalysis, Oxford, April 8–10, 1989.