2-Cyanoacrylates in the conjugate addition of trifluoroacetic acid and nucleophilic reagents

In the presence of trifluoroacetic acid, ethyl 2-cyanoacrylate readily reacts with nucleophilic reagents, such as 2-chloro-1,3,2-benzodioxaphosphole, (EtO)₃P, (EtO)₂PCl, Ph₂PCl, Ph₃P, and thiourea. In these reactions the acid proton enters position 2 of the cyanoacrylate, whereas the nucleophilic component enters position 3, in accordance with the electron density distribution in the acrylate. In the absence of trifluoroacetic acid the above reagents, except 2-chloro-1,3,2-benzodioxaphosphole, cause ethyl 2-cyanoacrylate polymerization. The interaction of ethyl 2-cyanoacrylate with 2-chloro-1,3,2-benzodioxaphosphole and trifluoroacetic acid is the first example of a 2-cyanoacrylate taking part in the acid-initiated electrophilic conjugate addition of a weak nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1245–1247, July, 1993.     

Alkynenitriles: stereoselective chelation controlled conjugate addition-alkylations

Chelation-controlled conjugate addition of Grignard reagents to γ-hydroxyalkynenitriles stereoselectively generates tri- and tetra-substituted alkenenitriles. t-BuMgCl-initiated deprotonation of hydroxyalkynenitriles followed by addition of a second Grignard reagents triggers a facile conjugate addition leading to a cyclic magnesium chelate. Protonation of the chelate stereoselectively generates trisubstituted nitriles whereas the addition of t-BuLi causes conversion to an ‘ate’ complex that allows alkylation with aldehyde electrophiles. The chelation-controlled conjugate addition-alkylation generates tri- and tetra-substituted alkenenitriles that are otherwise difficult to synthesize.     

YBa2Cu3O7 electro-magnetic optic effects in Ba L2,3 X-ray absorption near Tc

The onset of electro-magnetic optic effects, observed at the Ba L_2,3 edges synchrotron X-ray absorption by a YBa₂Cu₃O₇ single crystal, 20 K above the transition temperature to superconductivity, T_c ∼ 92 K is used to identify the role played by the Ba donor layer in the transition to superconductivity in the CuO₂ layers. Negative permeability leads to Faraday rotation of the transmitted beam below T = 112 to 56 K for the 22 μm thick single crystal (c-axis orientation of 8π/18 relative to ε_X-rays) and sharp changes in the density of empty final states lead to zero transmitted radiation in an interval ΔE at the given orientation. The temperature dependence: ΔE(L₂) = 1.4, 3.5 and 3.9 eV, while ΔE(L₃) = 5.3, 6 and 7 eV at T = 92, 74 and 63 K, respectively, indicates that the width of the empty final states bands increases as T decreases. ΔE(L₃)/ΔE(L₂) = 3.8 at 92 K to 1.8 at 63 K also indicates that the d_5/2 symmetry bands fill faster than those of d_3/2 symmetry below T_c, providing the first experimental evidence of unpaired spin-orbit states in the Ba donor layer of a superconductor. These effects, characteristic of ferromagnetic and anti-ferromagnetic materials near a resonance absorption, signal the onset of a Mott transition. The interaction between the layer states is described using 1D conjugate molecular orbitals.     

A modified steepest descent method with applications to maximizing likelihood functions

In maximizing a non-linear function G(), it is well known that the steepest descent method has a slow convergence rate. Here we propose a systematic procedure to obtain a 1–1 transformation on the variables , so that in the space of the transformed variables, the steepest descent method produces the solution faster. The final solution in the original space is obtained by taking the inverse transformation. We apply the procedure in maximizing the likelihood functions of some generalized distributions which are widely used in modeling count data. It was shown that for these distributions, the steepest descent method via transformations produced the solutions very fast. It is also observed that the proposed procedure can be used to expedite the convergence rate of the first derivative based algorithms, such as Polak-Ribiere, Fletcher and Reeves conjugate gradient methods as well.     

Unusual Reactivities of ortho-Hydroxy-β-nitrostyrene

Nitrostyrene derivatives are widely used in organic syntheses as a substrate for Michael addition, photoisomerization and cycloaddition. In contrast, ortho-hydroxy derivatives exhibit unusual behaviors in these reactions. Conjugate addition proceeded upon treatment of the ortho-hydroxy-β-nitrostyrene with an amine; however, subsequent C–C bond cleavage readily occurred to afford the corresponding imine. Moreover, conversion of the trans-isomer to a cis-isomer did not occur efficiently, even when UV light was irradiated. We studied these unusual behaviors of β-nitrostyrene, focusing on the role of the ortho-hydroxy group.     

基于改进NAS-RIF的三维显微图像盲复原

对二维NAS-RIF算法进行了改进,并将它用于三维显微图像复原,分别用模拟样本和真实生物样本进行了实验。针对原算法对噪声有放大作用,提出了基于中值滤波去噪的改进。在支持域的确定、最小点的搜索上进行改进,提高复原质量。改进了原算法仅适用于均匀背景的不足,扩大了应用范围。实验结果表明,该算法在三维显微图像盲复原中具有较好的效果。     

基于解码技术的全息显微术研究

提出了一种利用解码技术对全息显微畸变图像进行校正的方法。把全息记录中的显微镜预放大过程作为物光波产生畸变的编码过程;在波前再现过程中,用全息记录中的预放大显微镜对再现的赝实像再次放大进行解码,从而获得清晰的全息显微图像。实验验证了该方法的有效性。     

改进的约束共轭梯度闪光照相图像重建算法

针对闪光照相图像信噪比低的特点,提出了一种改进的约束共轭梯度闪光照相图像重建算法。该算法在约束共轭梯度迭代重建的基础上,提出了新的预优矩阵选取方案,减小了重建图像的轴线噪声,利用松弛迭代步长代替共轭梯度法中的最优迭代步长,并采用了新的收敛准则,在保证算法收敛的同时,减少了重建算法的计算量。数值试验表明,与传统约束共轭梯度重建算法相比,改进算法稳定收敛,迭代速度更快,并能有效提高重建质量。     

An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation

Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems.     

?-3-O-酰基-2-O-苄基-甘油二烷基磷酸酯的合成和结构表征

?-3-O-酰基-2-O-苄基-甘油二烷基磷酸酯的合成和结构表征; ?-O-酰基-O-苄基-甘油二烷基磷酸酯;磷脂类似物;生物活性物质