Total synthesis of (+)-aspidospermidine: a new strategy for the enantiospecific synthesis of aspidosperma alkaloids

A new strategy was developed for the enantiospecific synthesis of aspidosperma alkaloids. The key steps involve a novel ketene-lactonization reaction of a chiral vinyl sulfoxide to efficiently set up the quaternary carbon center, and a tandem Michael addition-alkylation reaction sequence to form the polycyclic core structure. This new strategy was employed in the total synthesis of natural product (+)-aspidospermidine.     

双酚-S-双(3-甲基丙烯酰氧基-2-羟丙基)醚的聚合及其应用

以MMA为起始原料经转变为GMA,再与双酚-S反应合成了一种新的含有砜基的交联剂BisS-GMA。这种双酚-S型交联剂与MMA可以顺利地用紫外光或BPO-胺体系引发聚合。新的双酚-S型交联剂BisS-GMA与双酚-A型交联剂Bis-GMA相比,具有活性高与粘结强度高两个显著优点。它还可以和二氧化硅填料混合组成复合树脂,经光引发或BPO-DHET体系引发聚合,得到的复合树脂其物性已达到国外同类产品的水平。DHET作为促进剂要比DMT性能好,前者配制的交联剂液体组份贮存稳定性好,经半年后而不“失活”,后者配制的液体组份则在较短的时间内“失活”。     

A spectroscopic study of cobalt(III) furyldioximates

Summary The electronic properties of a series of cobalt(III)trans-furyldioximato-complexes of the type [CoB(FH)₂X] (B=NH₃, X=Cl, Br, I or NO₂; B=pyridine (py) or thiocarbamide (thio), X=Cl or Br; B=imidazole (imid), X=Br), [Co(FH₂)(FH)Cl₂] and [Co(thio)₂(FH)₂]NO₃ were studied by i.r., u.v. and¹H and¹³C n.m.r. spectra The results were compared with those from the corresponding dimethylglyoximato-complexes. It was concluded that -conjugation over the equatorial plane in the furyldioximates is greater than in the dimethylglyoximates. There is some evidence of thetrans-influence of the anionic ligands in the ammines which are in the order NO ₂ ^– >Br^–>Cl^–.     

Cellulose hydrolysis using zinc chloride as a solvent and catalyst

Cellulose gel with < 10% of crystallinity was prepared by treatment of microcrystalline cellulose, Avicel, with zinc chloride solution at a ratio of zinc chloride to cellulose from 1.5 to 18 (w/w). The presence of zinc ions in the cellulose gels enhanced the rate of hydrolysis and glucose yield. The evidence obtained from X-ray diffraction, iodine absorption experiments; and Nuclear Magnetic Resonance spectra analysis suggested the presence of zinc-cellulose complex after Avicel was treated with zinc chloride. Zinc-cellulose complex was more susceptible to hydrolysis than amorphous cellulose. Under the experimental condition, cellulose gels with zinc ions were hyrolyzed to glucose with 95% theoretical yield and a concentration of 14% (w/v) by cellulases within 20 h. The same gel was hydrolyzed by acid to glucose with 91.5% yield and a concentration of 13.4% (w/v).     

Synthesis of 2‐Dihydrooxadiazolinyl Chromones

Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac₂O. All target compounds were characterized through elemental analysis and IR, ¹H NMR, MS.     

Stationary phase evaluations of quantum rate constants

We compute the quantum rate constant based on two extended stationary phase approximations to the imaginary-time formulation of the quantum rate theory. The optimized stationary phase approximation to the imaginary-time flux-flux correlation function employs the optimized quadratic reference system to overcome the inaccuracy of the quadratic expansion in the standard stationary phase approximation, and yields favorable agreements with instanton results for both adiabatic and nonadiabatic processes in dissipative and nondissipative systems. The integrated stationary phase approximation to the two-dimensional barrier free energy is particularly useful for adiabatic processes and demonstrates consistent results with the imaginary-time flux-flux correlation function approach. Our stationary phase methods do not require calculation of tunneling paths or stability matrices, and work equally well in the high-temperature and the low-temperature regimes. The numerical results suggest their general applicability for calibration of imaginary-time methods and for the calculation of quantum rate constants in systems with a large number of degrees of freedom.     

Classification of Cm I energy levels using PCA-BPN and PCA-NLM

Two pattern recognition (PR) techniques, principal component analysis-back propagation networks (PCA-BPN) and principal component analysis-nonlinear mapping (PCA-NLM), have been applied to the problem of classifying unknown energy levels of the first spectrum of curium (Cm I) according to their configurations. In comparison, with those reported by early PR techniques and counter propagation neural networks (CPN's), PCA-BPN has been demonstrated to possess much more prediction accuracy as to its performance on test sets. Obtained results further confirm the most previous assignments with these energy levels given by some early PR techniques and CPN. Moreover, the obtained results definitely reassign some energy levels' electronic configurations which were ambiguously conjectured in previous work.     

芳香叔胺引发丙烯腈光聚合的引发机理

芳香叔胺引发丙烯腈(AN)光聚合是通过形成激基复合物(exciPlex)进行的。紫外光谱和荧光光谱表明,芳香叔胺在基态可以和AN形成电荷转移复合物(CTC),而在激发态可和AN形成exciplc(称定域激发)。CTC经光照亦可激发(称CTC激发)。 定域激发引起光聚合速率为CH_3C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2>HOCH_2·C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2,与芳胺荧光被AN淬灭的Stern-Vo-lmer常数顺序一致。CTC激发引起的光聚合顺序为:CH_3C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2>HOCH_2C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2,与芳胺上取代基推电子能力一致。端基分析表明聚合物有芳胺端基。     

温跃层边界提取的组合算法*

本文提出一种用于海洋温跃层边界提取的组合算法,该算法基于调整判定阈值后的垂直梯度法和一种改进函数模型几何形态后的拟阶梯函数逼近法。为验证该算法对于温跃层边界提取的适应性、客观性,利用中国Argo实时资料中心发布的全球海洋Argo网格资料集（BOA_Argo）,选取2018年夏季0°~30°N,135°E~165°E所在的太平洋区域的温度剖面数据进行处理,结果表明,该算法对低纬度海区温度剖面拟合质量较好,拟合均方根误差普遍低于1.3℃,而且提取到的温跃层上下边界在纬向更加平缓,然而对于中高纬度海区的温度剖面,组合算法的处理效果不佳,更适合直接通过垂直梯度法进行温跃层的提取。