高油酸花生油酶促酯交换合成类可可脂工艺优化

为促进高油酸花生油的高值化利用,在无溶剂体系中以高油酸花生油为原料,棕榈酸乙酯、硬脂酸乙酯为酰基供体,酶促酯交换合成类可可脂。以目标甘三酯1,3-二棕榈酸-2-油酸(POP)、1-棕榈酸-2-油酸-3-硬脂酸(POS)、1,3-二硬脂酸-2-油酸(SOS)含量,硬脂酸指数和酰基位移率为评价指标,在单因素实验的基础上采用响应面法对酶促酯交换合成类可可脂的工艺条件进行优化。结果表明：酶促酯交换合成类可可脂的最佳工艺条件为硬脂酸乙酯与棕榈酸乙酯物质的量比1.3∶1、酰基供体与高油酸花生油物质的量比12∶1、加酶量2.7%(以底物质量计)、反应温度60℃、反应时间7 h,在该条件下产物甘三酯中POP、POS、SOS的含量分别为14.55%、48.87%、25.17%,硬脂酸指数为0.56,酰基位移率为7.35%。产物的目标甘三酯组成和脂肪酸组成与可可脂相近,可作为可可脂替代品应用。     

Anti-oxidative characterisation of NaN3-induced common bean mutants

The contents of total phenolics, total anthocyanins, total proanthocyanidins and antioxidant activities were measured using 2,2-diphenyl-1-picrylhydrazyl radicals scavenging activity, ferric reducing antioxidant power, lipid peroxidation inhibition ability and ABTS⁻ radical-scavenging activity assays. These were compared in the seed coats of common bean (Phaseolus vulgaris L.) cultivar Hwachia and its eighteen NaN₃-induced mutants. NaN₃-induced mutants generally accumulated more total phenolics (19% more), total anthocyanins (65% more) and total proanthocyanidins (4% more) than Hwachia (containing 29.94 mg g⁻¹ total phenolics, 0.31 mg g⁻¹ total anthocyanins and 12.94 mg g⁻¹ total proanthocyanidins, respectively). Anthocyanidins including delphinine, cyanidin and pelargonidin were detectable in seed coat, each with different levels depending on the tested accessions. Significant correlations (average of 0.847 across all comparisons, p < 0.01) were found between the tested antioxidant activities, total phenolics, total anthocyanins and total proanthocyanidins. Mutants SA-11-2, SA-13-2 and SA-34-2 that are enriched with antioxidants may be useful in food and other applications.     

Biotransformation of glycidol by the unspecific wax ester synthase/acyl‐CoA:diacylglycerol acyltransferase of Acinetobacter baylyi ADP1

Glycidol was biologically derivatized by the unspecific wax ester synthase/acyl coenzyme A (acyl‐CoA): diacylglycerol acyltransferase (WS/DGAT) from Acinetobacter baylyi ADP1 into glycidyl acyl ester. Catalysis of in vitro conversion of glycidol to glycidyl acyl ester by the WS/DGAT from A. baylyi was verified by (i) a radiometric assay, (ii) thin‐layer chromatography and (iii) also by ESI‐MS. A specific activity of 50 nmol·mg^–1·min^–1 was obtained when 10 mM glycidol and 5 µM palmitoyl‐CoA were used. In vivo synthesized glycidyl acyl esters in recombinant E. coli were detected and quantified by staining with the epoxide‐specific reagent 4‐(4‐nitrobenzyl)‐pyridine. Of glycidyl acyl esters, 1.5 mg/L was obtained from the culture in the presence of 10 mM glycidol and 10 mM oleate.     

“Click Peptide“: pH‐Triggered in Situ Production and Aggregation of Monomer Aβ1–42

Into neutral : We demonstrate the unique features of a pH click peptide based on an O‐acyl isopeptide method. Under acidic conditions, the click peptide remains in a monomeric form. Upon increase of the pH to 7.4, the click peptide is quickly able to convert into Aβ1–42 through an O‐to‐N intramolecular acyl migration. Further study using this pH click peptide would elucidate the pathological role of Aβ1–42 in Alzheimer's disease.

     

The effect of microencapsulation with nitrocellulose on thermal properties of sodium azide particles

Based on the coacervation principle a solvent/non-solvent method has been used for microencapsulation of sodium azide (NaN₃) with fibrous nitrocellulose (NC). Scanning electron microscopy (SEM) was employed to examine the coating morphology. The thermal behavior of solid samples has been studied by means of thermogravimetry (TG) and differential scanning calorimetry (DSC). The results of TG–DTA analysis revealed that the main thermal degradation for the pure NC and NaN₃ occurs in the temperature ranges of 192–220 and 415–420 °C, respectively. The effects of some parameters, such as NC to NaN₃ weight ratio and volume and addition time of non-solvent, on coating quality and thermal properties have been investigated by SEM and thermal methods. The results of these experiments showed that the decomposition temperature of most stabilized coated sodium azide is about 50 °C higher than that of the pure sample. The DSC experiments were conducted to study the influence of the heating rate (5, 10, 15 and 20 °C/min) on the thermal decomposition processes of the pure NC, coated and pure NaN₃ samples. The results revealed that, as the heating rate was increased, decomposition temperature of the compounds was increased. Also, the kinetic parameters such as activation energy and frequency factor of the decomposition processes were obtained from the DSC data by non-isothermal methods proposed by ASTM E696 and Ozawa. Our finding showed that coated NaN₃ has lower decomposition rate with respect to the pure one.     

叠氮甲烷二聚体分子间相互作用的abinitio研究

运用ab initio方法,在HF水平6-311G**基组下求得叠氮甲烷二聚体势能面上六种优化构型和电子结构.经MP2电子相关和基组叠加误差(BSSE)以及零点能(ZPE)校正,求得分子间相互作用能;结合能(9.49 kJ*mol-1)最大的二聚体为存在两个CHN氢键的六元环构型,属于D2h群.探讨了甲基内旋转对相互作用能的影响.由自然键轨道(NBO)分析揭示了相互作用的本质.对单体和六种二聚体优化构型进行简谐振动分析,研究了IR光谱变化规律.此外还基于统计热力学求得273.15～800.00 K温度范围从单体形成二聚体的热力学性质变化.     

海藻酸钠磁性微粒的制备及对漆酶的固定化

利用化学共沉淀法制备纳米级磁性Fe3O4粒子,通过乳化作用把该粒子与海藻酸钠结合制备了磁性海藻酸钠微粒,将该磁性微粒进行表面修饰生成酰氯基团,并通过化学共价法固定漆酶。用正交实验优化了固定化条件,在此条件下获得了固定化漆酶;与游离漆酶相比,固定化漆酶与底物ABTS亲和力降低,最适pH值、最适温度相同,热稳定性显著提高,具有良好的循环使用性和贮藏稳定性,对染料刚果红的降解率也较高。结果表明,表面改性的海藻酸钠磁性微粒是一种良好的固定化漆酶载体。     

Core–shell type multi‐arm azide polymers based on hyperbranched copolyether as potential energetic materials in solid propellants

A series of novel multi‐arm azide copolymers (POGs) with the same hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] core (PEHO‐c) and different content of linear glycidyl azide polymer shell (GAP‐s) have been synthesized by sequential cationic ring‐opening polymerization and azidation. Detailed structural information of these copolyethers was deduced from Fourier transform infrared, ¹H NMR and inverse gated decoupled ¹³C NMR spectroscopies, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, gel permeation chromatography and elemental analysis. The molecular weight of POG having GAP‐s and PEHO‐c with a molar ratio 14.95:1 (R_s/c) was around 31 000 g mol^?1, far above that of linear GAP (around 4000 g mol^?1). The apparent viscosity and glass transition temperature (?51 to ?23 °C) decreased first and then slightly increased with increasing molecular weight. Thermal analysis revealed that all the obtained POGs exhibited excellent resistance to thermal decomposition up to 220 °C. Moreover, the energetic properties, investigated using oxygen bomb calorimetric measurements, indicated that the enthalpy of formation of the POGs was higher than that of general linear GAP, but similar to that of branched GAP under reasonable R_s/c. The compatibilities of the POGs with common materials used in solid propellants were studied using differential scanning calorimetry and the results indicated that the POGs had good compatibility with these materials. © 2017 Society of Chemical Industry     

Effects of metal oxide nanoparticles on combustion and gas-generating performance of NaN3/Al composite powders ignited using a microhotplate platform

We investigated the effects of different metal oxide (MO) nanoparticles (e.g., CuO, KIO₄, Fe₂O₃) on the combustion and gas-generating characteristics of sodium azide microparticle (NaN₃ MP; gas-generating agent) and aluminum nanoparticle (Al NP; heat source) composite powders. The NaN₃ MP/Al NP/MO NP composite powders were stably ignited using a microhotplate (MHP) heater. The addition of CuO and KIO₄ to the NaN₃ MP/Al NP composite powders resulted in relatively high burn rates and high pressurization rates upon MHP-assisted ignition. This suggests that the highly reactive CuO and KIO₄ NPs significantly increased the combustion of the Al NPs; as a result, sufficient heat energy was generated via the active aluminothermic reaction to thermally decompose the NaN₃ MPs. Finally, the gas generating properties of NaN₃ MP/Al NP composite powders mixed with various MO NPs were tested using homemade inflatable small airbags. The airbags were fully inflated within ~20 ms when CuO and KIO₄ NPs were added to the NaN₃ MP/Al NP composite powders. However, the addition of Fe₂O₃ NPs to the NaN₃ MP/Al NP composite powder resulted in a slow and only partial inflation of the airbag due to an incomplete aluminothermic reaction, which was due to a slow combustion reaction between the Al NPs and relatively weak oxidizer of the Fe₂O₃ NPs. This suggests that the rapid, stable, and complete thermal decomposition of NaN₃ MP/Al NP composites can be effectively achieved by employing highly reactive nanoscale oxidizers.     

绿色起爆药的研究进展

斯蒂芬酸铅和叠氮化铅等传统起爆药含有重金属,对环境污染大,其应用受到了很大的限制。绿色起爆药是一类不含铅、汞等重金属,具有一定安定性且爆轰性能优异的起爆药品种,是当前火工药剂研究领域里的热门课题之一。从绿色起爆药的合成、性能及应用等角度对其近年来的研究进展进行了综述,梳理了绿色起爆药研究的发展方向和趋势,指出今后研究的几点重要方向:努力探索、寻找新的合成线路,并优化其工艺条件,实现绿色起爆药安全化、规模化、稳定化制备;进一步建立、健全绿色起爆药理论设计、性能评估、演示验证等方面的规范和标准;继续开发新型绿色高能起爆药的设计、合成与应用基础研究,进一步改善起爆药的综合性能;设计和选择合适的配体与金属离子以及控制反应条件等因素,对系统研究高氮杂环配位化合物类绿色起爆药的结构与性能具有重要的意义。