Direct separation of the enantiomers of cetirizine and related compounds by reversed-phase chiral HPLC

Summary Direct separations of the enantiomers of cetirizine and related compounds have been achieved by reversed-phase HPLC on the Chiralcel OD-R, a polysaccharide-derived chiral stationary phase; the mobile phase was usually perchlorate solution supplemented with acetonitrile. Resolution of the enantiomers of cetirizine and related compounds was good. The effect of the acetonitrile content of the mobile phase was investigated, and the effect of the structure of the chiral compounds on their behavior on the Chiralcel OD-R column is discussed.     

Hydrothermal Synthesis and Crystal Structure of a Cadmium（Ⅱ） Polymer with One-dimensional Chain Structure： [Cd（MDPPz）（BDC）（H2O）]n

A metal-organic coordination compound formulated as [Cd(MDPPz)(BDC)(H2O)]n 1 (MDPPz=11-methyldipyrido[3,2-a:2',3'-c]phenazine,BDC=1,4-benzenedicarboxylate) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system,space group C2/c,with a=30.673(8),b=9.623(3),c=20.784(6) ,β=98.646(3)o,V=6065(3)3,C27H17CdN4O5,Mr=589.85,Dc=1.292 g/cm3,μ(MoKα)=0.757 mm-1,F(000)=2360,Z=8,the final R=0.0381 and wR=0.0855 for 4191 observed reflections (I>2σ(I)). 1 exhibits blue fluorescence property at room temperature.     

Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4′-dicarboxylate： Effect of Lanthanide Contraction on Structures

Four lanthanide coordination polymers with benzophenone‐4,4′‐dicarboxylic acid (H₂bpndc) and 1,10‐phenanthroline (phen), [Ln₂(bpndc)₃(phen)] (Ln=La (1), Pr (2) and Tb (3)), [Yb(bpndc)₁₅(phen)].05H₂O (4) were obtained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(III) ions in 1, 2 and 3 are all eight‐ and ten‐coordinated, respectively, and thus the Ln(III) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(III) ions are eight‐coordinated and connected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(III) to Yb(III) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes.     

肉桂酸类分子非线性光学效应的理论研究

计算了一系列肉桂酸（苯基丙烯酸）类化合物的二阶非线性光学系数，系统地研究了取代基的电子性质和取代位置对其非线性光学性质的影响，并且探讨了该类化合物的饱和取代效应．研究表明，该类化合物的非线性光学性质与其分子结构有着密切的关系．     

马来酸酐与1，2－环己烷二羧酸二异丁酯的气液平衡

采用小沸点仪测定了马来酸酐和1,2－环己烷二羧酸二异丁酯二元系统在不同配料组成条件下的温度与压力数据，并通过内插法得到不同压力下的温度与配料组成的数据.进一步采用单纯形法优化NRTL方程参数，推算了平衡气液相组成，发现该二元系统具有最高压力恒沸点，且该恒沸点随压力的变化显著.当压力降低至20 kPa时, 由温度随气相组成的变化趋势知该恒沸点将趋于消失.     

Selective Oxidation of Methane to Methanol Using Molecular Oxygen on MoOx／（LaCoO3＋Co3O4） Catalysts

Comparatively high CH3OH selectivity (60.0%) and yield (6.7%) were obtained on MoOx/(LaCoO3 Co3O4) catalysts in selective oxidation of methane to methanol using molecular oxygen as oxidant. The interaction between MoOx and La-Co-oxide modified the molecular structure of molybdenum oxide and the ratio of O^-/O^2- on the catalyst surface, which controlled the catalytic performance of MoOx/(LaCoO3 Co3O4) catalysts.     

Inorganic—Organic Hybrid 18—Molybdodiphosphate Nanoparticles Bullk—modified Carbon Paste Electrode and Its Electrocatalysis

A kind of inorganic‐organic hybrid 18‐molybdodiphosphate nanoparticles ([(C₄H₉)₄N]₆P₂Mo₁₈Q₆₂·4H₂O) was firstly used as a bulk‐modifier to fabricate a three‐dimensional chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the solid nanoparticles dispersed in the CPE in acidic aqueous solution was characterized by cyclic and square‐wave voltammetry. The hybrid 18‐molybdodiphosphate nanoparticles bulk‐modified CPE (MNP‐CPE) displayed a high electrocatalytic activity towards the reduction of nitrite, bromate and hydrogen peroxide. The remarkable advantages of the MNP‐CPE over the traditional polyoxometalates‐modified electrodes are their excellent reproducibility of surface‐renewal and high stability owing to the insolubility of the hybrid 18‐molybdodiphosphate nanoparticles.     

磷钼钒杂多酸在苯直接羟化反应中的催化作用——O2活化机理的探讨

磷钼钒杂多酸在有供电子体存在下具有活化氧和使苯直接羟化的催化性能。以抗坏血酸和亚硫酸钠为还原剂的实验表明不同的还原体系吸氧动力学和羟化活性不同。根据氧化还原滴定、循环伏安法、电解还原羟化反应以及光谱实验等测定结果, 对这两个不同体系提出了各自可能的氧的活化机理。认为在以抗坏血酸为还原剂的情况下, 杂多酸阴离子通过三电子传递过程直接络合氧, 氧与阴离子形成中间络合物为控制步骤。在以亚硫酸钠为还原剂的情况下, 供电子体可能先与阴离子络合活化, 直接参与氧的活化过程, 供电子体与阴离子的还原络合为控制步骤。     

吸热碳氢燃料裂解镧改性混合型催化剂的研究

制备了吸热型碳氢燃料NNJ-150和镧离子交换改性的USY、ZSM-5分子重申及混合分子筛，考察了NNJ-150在USHY、HZSM-5和两者混合物以及镧改性单分子筛和混合分子筛催化剂上的裂解反应。结果表明，ZSM-5分子筛中添加镧，对NNJ-150的单分子裂解反应有明显影响；混合分子两种分子筛之间存在协同作用，低温（500℃）下，LaUSY LaZSM-5（75：25）混合分子筛对低碳烯烃的选择性较高（41.48％），催化剂寿命较长（35min以上），能有效提高吸热型碳氢燃料NNJ-150的吸热能效。     

Total synthesis of crotophorbolone

As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C₂₀ and C₄.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.