Absolute Configuration of the Phenylpropanoid Isolated from Peperomia tetraphylla

A recently identified phenylpropanoid isolated from Peperomia tetraphylla was synthesized in enantiopure forms using an aldol condensation of enantiopure （R）-N-acetyl 4-phenyl-oxazolidin-2-one as the key step. With the aid of the single crystal X-ray crystallographic analysis of the synthetic sample, the configuration for the natural product was unambiguously established. Corrected/updated ^13C NMR and optical rotation are also presented.     

二甲氨基乙氧基氧杂硼烷对环氧树脂的潜伏固化活性

以3种含分子内N→B配位键的环状结构的二甲氨基乙氧基氧杂硼烷:β,β'-二甲氨基乙氧基-4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷(PDB)、β,β'-二甲氨基乙氧基-5,5-二甲基-1,3,2-二氧杂己硼烷(NDB)和β,β'-二甲氨基乙氧基-1,3,2-苯并二氧硼烷(CDB)为研究对象,采用敞口观察法测定其水解稳定性,通过差示扫描量热法(DSC)、烘箱固化实验、恒温潜伏性实验及红外光谱(FTIR)分析,研究3种氧杂硼烷对环氧树脂的固化活性和潜伏性能,采用Ozawa-Avrami法估算固化反应的表观活化能(E a).结果表明,苯环π电子共轭效应、烷氧基给电子效应以及氧杂硼烷空间结构差异等因素影响了3种二甲氨基乙氧基氧杂硼烷上硼原子电子云密度及N→B配位络合强度,导致其水解稳定性及对环氧树脂的固化活性顺序为NDBPDBCDB,潜伏性能则正好相反.E51与PDB组成的单组分环氧树脂在常温放置3个月后,环氧基的转化率为0.22.     

耦合火焰自加速传播的氢气云爆炸超压预测

通过揭示当量比对氢气云爆炸火焰形态、火焰半径和爆炸超压峰值的影响规律,本文拟建立耦合火焰自加速传播的氢气云爆炸超压预测模型。结果表明:氢气云爆炸火焰传播速度由大至小对应的当量比依次是Φ=2.0、Φ=1.0和Φ=0.8。Le＜1.0和Le＞1.0的氢气云爆炸火焰表面均出现胞格结构,胞格结构的出现必然会增加火焰燃烧表面积,进而出现“火焰自加速”现象。对于特定的当量比,随着压力监测点和点火位置间距的增加,爆炸超压峰值的正值和负值绝对值均单调减小;对于特定的压力监测点,爆炸超压峰值的正值和负值绝对值随当量比的关系存在些许差异;不同当量比和监测点位置的爆炸超压峰值的负值绝对值大都高于正值。耦合火焰自加速传播的氢气云爆炸超压预测模型可成功预测不同压力监测点薄膜破裂前氢气云爆炸超压的发展过程。     

Substitutional alloy of Bi and Te at high pressure

Being a best known thermoelectric material and a topological insulator at ambient condition, magic bismuth telluride (Bi2Te3) under pressure transforms into several superconducting phases, whose structures remain unsolved for decades. Here, we have solved the two long-puzzling low high-pressure phases as seven- and eightfold monoclinic structures, respectively, through particle-swarm optimization technique on crystal structure prediction. Above 14.4 GPa, we experimentally discovered that Bi2Te3 unexpectedly develops into a Bi-Te substitutional alloy by adopting a body-centered cubic disordered structure stable at least up to 52.1 GPa. The continuously monoclinic distortion leads to the ultimate formation of the Bi-Te alloy, which is attributed to the Bi→Te charge transfer under pressure. Our research provides a route to find alloys made of nonmetallic elements for a variety of applications.     

Mild and Efficient Allylation of Indoles and Amides Using Amberlyst-15 as a Recyclable Heterogeneous Catalyst

A mild and efficient allylation of indoles and amides in the presence of a catalytic amount of Amberlyst-15 has been described in this context. The recyclable heterogeneous catalytic system is practical and facile for the synthesis of C- and N-allylated derivatives and would be of importance for the development of the accordingly functional complex molecules.     

Controllable synthesis and up-conversion properties of tetragonal BaYF5:Yb/Ln (Ln=Er, Tm, and Ho) nanocrystals

The nanocrystals (NCs) of tetragonal barium yttrium fluoride (BaYF(5)) doped 1 mol% Ln(3+) (Ln=Er, Tm, Ho) and 20 mol% Yb(3+) with different morphologies and sizes have been successfully synthesized through a facile hydrothermal method. The influences of pH values of the initial solution and fluorine sources on the final structure and morphology of the products have been well investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) were used to characterize the size, structure and morphology of these samples prepared at different conditions. And it is found that BaYF(5):Yb/Ln NCs prepared at pH value of 10 using NaBF(4) as F(-) source have a uniform spherical morphology with average diameter of 25 nm. Additionally, the up-conversion (UC) properties of Yb/Er, Yb/Tm, and Yb/Ho doped BaYF(5) nanoparticles were also discussed. Under 980 nm laser excitation, the BaYF(5):Yb/Er, BaYF(5):Yb/Tm, and BaYF(5):Yb/Ho NCs exhibit green, whitish blue, and yellow green UC luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Influence of oxidation on space charge dynamics in DC aged low-density polyethylene

In this study, low-density polyethylene (LDPE) samples were aged under different oxygen concentration (0, 20%, and 50%). The ageing was implemented with an average external DC electric field of 50 kV/mm at 40 °C for 1000 h. It was found that augmentation of charge accumulation and suppression of charge dissipation were enhanced with increasing of oxygen concentration. The capture capability of trap sites got stronger with higher oxygen contents, which could be attributed to oxidation product newly generated during DC ageing. These trap sites acted as trap centers to capture the injected carrier while it was on the way towards the opposite electrode and decrease the apparent mobility. FTIR absorption spectra showed that new elements between 1680 and 1750 cm^?1 corresponding to ketone and aldehyde occurred due to oxidation. The bipolar charge injection model was implemented to simulate space charge transport in aged LDPE samples. It was shown that more carriers were captured and the traps gradually filled up when the oxygen concentration in the ageing test increased. A higher oxygen concentration seemed to result in a deeper average trap depth, which increased the amount of trapped charge because it was not easy to detrap. These simulation result corresponded to the experimental measurement.     

Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by 13C-2H Dual Isotope Tracer

To elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, ¹³C-²H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from Ginkgo biloba L. by feeding D-glucose-[6-²H₂], coniferin-[α-¹³C], and phenylalanine ammonia-lyase (PAL) inhibitor. The abundant detection of ¹³C and ²H confirmed that D-glucose-[6-²H₂] and coniferin-[α-¹³C] were involved in the normal metabolism of ginkgo cambial cells that had been effectively labelled with dual isotopes. In the ginkgo CW-DHP, ketal and ether linkages were formed between the C-α of lignin side chains and carbohydrates, as revealed by solid state CP/MAS ¹³C-NMR differential spectroscopy. Furthermore, the DMSO/TBAH ionic liquids system was used to fractionate the ball-milled CW-DHP into three lignin-carbohydrate complex (LCC) fractions: glucan–lignin complex (GL), glucomannan–lignin complex (GML), and xylan–lignin complex (XL). The XRD determination indicated that the cellulose type I of the GL was converted into cellulose type II during the separation process. The molecular weight was in the order of Ac-GL > Ac-GML > XL. The ¹³C-NMR and ¹H-NMR differential spectroscopy of ¹³C-²H-enriched GL fraction indicated that lignin was linked with cellulose C-6 by benzyl ether linkages. It was also found that there were benzyl ether linkages between the lignin side chain C-α and glucomannan C-6 in the ¹³C-²H-enriched GML fraction. The formation of ketal linkages between the C-α of lignin and xylan was confirmed in the ¹³C-²H-enriched XL fraction.     

三聚氰胺-甲醛树脂包裹环氧树脂微胶囊的制备及表征

针对环氧树脂基材料的自修复,选取四氢邻苯二甲酸二缩水甘油酯作为芯材,采用三聚氰胺-甲醛树脂为壁材,对其进行微胶囊化包裹.结果表明,制得的具有单囊结构的环氧树脂微胶囊,胶囊粒径较小(约6.7μm)、囊壁较薄(约0.2μm)、芯含量较高(83.2 wt%),囊壁内、外表面光滑致密,胶囊具有良好的密闭性和耐热性;在微胶囊化过程中,三聚氰胺-甲醛树脂的缩聚反应动力学起关键作用,芯材没有参与囊壁形成的交联反应;包裹后的芯材活性保持不变,胶囊被复合到材料过程中囊芯活性也保持不变;胶囊的强度较高,能承受与基体材料复合过程中的外力作用,且与基体材料间粘结良好,在裂纹形成过程中能够随基体同时开裂.