The mechanism of asymmetric reduction catalyzed by a C2 symmetric bis-amino alcohol catalyst

By means of¹H,¹³C,¹¹B NMR, polar transfer DEPT135, DEPT90 and 2D NMR experiments, IR, etc, the structure of the diaminodihydroxyl ligand and its derivatives used in the asym-metric reduction of prochiral ketones were detected. The catalysts derived from the ligand and borane formedin situ were also studied and the structure transformations in solution were monitored. The structure of the catalyst was proved to be a new type of dual-centered catalyst — bisoxazaborolidine.     

密频系统振动控制的状态估计

首先在研究了重频系统中状态可观察的必要条件基础上,给出了设计重频系统状态估计器的方法,使得状态估计的误差能以事先指定的速率衰减。随后给出两种方法将上述重频系统的估计器用到密频系统上去：一种是直接用重频系统估计器来估计密频系统状态,另一种是用按重频系统设计得到的估计矩阵构造密频系统的观察器,并分析由此引起的误差。分析表明,第一种方法简单易行,并且在频率分散度比较小时可以得到理想的结果;第二方法的精度较高,其误差与状态变量本身无直接关系。数值例子表明,用提出的状态估计器,并按相应的状态控制器,可以使密频系统的振动按事先给定的衰减程度趋向于零。     

一类抛物型方程的粘性解

讨论一类退化、奇异抛物型方程的初边值问题. 通过构造上下解 ,利用粘性解的比较原理和 Perron方法 ,证明了这类问题粘性解的存在性和唯一性.     

二茂铁甲酰基1,1'-二烷基二茂铁的合成与性质

在研制丁羟固体推进剂的高效不迁移燃速催化剂中 ,我们设计的目标物的结构为ＦｃＣＨ (ＯＨ)Ｆｃ′Ｒ2 (Ｆｃ =Ｃ5Ｈ5ＦｅＣ5Ｈ4 ,Ｆｃ′=Ｃ5Ｈ4 ＦｅＣ5Ｈ3,Ｒ为烷基 ) .该类化合物的特点是两个二茂铁核连在同一碳上 ,且含有羟基官能团 ,它们似应具有高效和不迁移的燃速催化性能[1].此类化合物的合成是由二茂铁甲酰基 1,1′ 二烷基二茂铁化合物的羰基还原为羟基实现的 .为此 ,我们较为详细地研究了 5种二烷基二茂铁在三氯化铝催化下的二茂铁甲酰化反应 .此项工作未见报道 .二烷基二茂铁的茂环有α(与烷基相邻 )和 β(与烷基相间 )两种Ｈ原…     

Preparation and Characterization of Aluminum Alkoxides and their Application to Ring‐Opening Polymerization of ϵ‐Caprolactones

The reaction of 2‐methoxybenzyl alcohol with one molar equiv of R₂AIX in diethyl ether at 0°C gives [(2‐MeOC₆H₄CH₂‐μ‐O)AlRX]₂ ( 1 : R = Et, X = Cl, 2 : R = X = Et). In addition, 2,4‐di‐tert‐butylphenol reacts with ⁱBu₃Al affording a four‐coordinated aluminum compound [(μ‐2,4‐^tBu₂‐C₆H₄O)Al(ⁱBu)₂]₂ ( 4 ). Single crystal X‐ray structure analysis of 4 shows a C_2h‐symmetry with a planar Al₂O₂ core. Ring‐opening polymerization (ROP) of caprolactones initiated by 1, 4 and [(μ‐OCH₂C₆H₄OMe)Al(ⁱBu)₂]₂ ( 3 ) is performed and polyesters with narrow molecular weight distributions were obtained from the “living” ROP of caprolactones. ¹H NMR spectroscopic studies of PCL reveal that the initiator of 1 and 3 is through the Al‐OAr function, but the initiator of 4 is through the Al‐ ⁱBu group.     

Extraction of Uranium(VI) by N-Octanoylpiperidine in Toluene

The extraction of uranium(VI) from nitric acid by N-octanoylpiperidine (OPPD) in toluene has been investigated at varying concentrations of nitric acid, extractant, salting-out agent LiNO₃ and at different temperatures. The mechanism of extraction is discussed in the light of the results obtained. The extracted species have also been investigated using FT-IR spectrometry. The related thermodynamic functions were calculated.     

X-射线荧光光谱测定氧化铍中杂质元素

拟定了ＢｅＯ中１２种痕量杂质元素的Ｘ－射线荧光光谱测定方法,采用光谱纯试剂人工合成校准标样,粉末压块法制备分析样片。考虑到ＢｅＯ对Ｘ射线的透明性,在样片与样品盒支架之间垫置钼片消除试样盒发射线的干扰并产生附加激发以提高灵敏度。本文分析结果与等离子民发射和原子吸收光谱对照相吻合。     

One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip)<Subscript>2</Subscript>(OH<Subscript>2</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> Cations and DBA<Superscript>2−</Superscript> Anions via Hydrogen-bonding and π–π Interactions

Abstract One new mononuclear manganese complex of [Mn(4,4′-bip)₂(OH₂)₄](DBA) · 4H₂O (1) (4,4′-bipyridine, 4,4′-bip; H₂DBA, benzene-1,3-dicarboxylic acid) has been obtained from the hydrothermal reaction of MnCl₂ · 4H₂O, 4,4′-bipyridine and H₂DBA in the solvent of H₂O at 140 °C for 3 days, characterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π–π interactions. Graphical abstract One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip) ₂ (OH ₂ ) ₄ ] ²⁺ Cations and DBA ²⁻ Anions via Hydrogen-bonding and π–π Interactions Ying Liu, Bao Zhang, Jian-min Dou, Da-qi Wang, Da-cheng Li, Lei Zhou One new mononuclear manganese complex of [Mn(4,4’-bip)₂(OH₂)₄](DBA) · 4H₂O (1) (4,4’-bipyridine, 4,4’-bip; H₂DBA, benzene-1, 3-dicarboxylic acid) has been obtained and haracterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π-π interactions.      

Study on Stiffness of the Symmetry Energy at High Densities by π－/π+ Ratio

using the isospin–and momentum–dependent transport model, for three different symmetry energies, we have calculated the π^–/π⁺ ratio as a function of time and tranverse–momentum in central 132sn+124 sn collision at e_beam/A=400mev. the results show that the π^–/π⁺ ratios is very sensitive to the stiffness of the symmetry energy. thus we can probe the stiffness of the symmetry energy at high densities by using the π–/π+ ratio at different time or transverse momentum more accurately than before. comparing experimental data with the calculations will reveal crucial information about the stiffness of the symmetry energy more accurately.hadronic transport model, symmetry energy, π–/π+ ratio     

原位漫反射红外光谱中采用新的实验手段研究煤岩显微组分中的氢键

首次提出采用小瓷片反应器,结合增大载气流量的方法进行产生挥发组分固体的原位漫反射红外光谱实验,研究了两种煤的镜质组和丝质组中的氢键分布及热稳定性.两种显微组分间氢键分布的规律相似;镜质组中SH-N、羧酸二聚体和自缔合羟基等的热稳定性比丝质组中的高.但对OH-N、羟基四聚体和OH-OR₂的热稳定性随煤岩组分的变化无明显规律;随着温度的升高,OH-π含量先升高后降低,于350～380℃达最大值,其中镜质组OH-π的含量增加较快.显微组分中氢键的变化规律反映了其结构上的差异.