Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

从头算法对甲基磺酸拉曼光谱振动频率指认

对液态的甲基磺酸进行了拉曼光谱测定。采取从头算法用各种不同的基组 (最大的基组为MP2 / 6 -311+G( 2d ,2 p) )对甲基磺酸的结构和光谱进行了计算 ,得到了甲基磺酸的结构参数及稳定构象信息。采用一个具有Ci 对称的二聚体模型解释了甲基磺酸的液态光谱。对单体和二聚体的甲基磺酸进行了简正坐标计算 ,结果表明二聚体结构是液态甲基磺酸聚积态分子的合理模型。     

噻二唑二聚物/丁氧基三乙二醇复合物的合成

合成了噻二唑二聚物/丁氧基三乙二醇复合物。反应物的摩尔比及反应温度影响产物作为添加剂加入到润滑脂中的抗烧结性能。在最佳反应条件下,即n(噻二唑二聚物)∶n(丁氧基三乙二醇)=0.5∶1.0,反应温度125℃时,产率为85%。通过分子模拟、红外光谱、13C核磁共振及N、S元素的含量测定,探讨了产物的结构及反应机理。结果表明,噻二唑二聚物与丁氧基三乙二醇的摩尔比越大,在金属表面形成配位的噻二唑环的个数就越多,就会表现出更强的吸附特性,从而表现出更高的抗烧结性能。     

横向光泵获得S_2紫外激光

用ＸｅＣｌ准分于激光器（３０８．１ｎｍ）横向泵浦Ｓ２激光器，又成功地实现了Ｓ２Ｂ－Ｘ态近ＵＶ波段的激光振荡。在波长３３０．９～３９０．０ｎｍ范围内观测到６条近ＵＶ激光输出。测量了有关的激光参数。     

Zeolite‐catalyzed isomerization of oleic acid to branched‐chain isomers

Branched‐chain (bc) saturated fatty acids (SFA) have potential as oleochemical intermediates since they have better oxidative stability than linear unsaturated fatty acids (UFA) and have better low‐temperature properties than linear SFA. Previous studies in converting UFA to bc‐FA using clay catalysts have resulted in only modest yields and conversions. Recent reports, however, have suggested that certain zeolites can be effective catalysts for converting UFA to bc‐FA in higher yields and conversions. In this work, we examined the scope and potential of the zeolite‐catalyzed synthesis of bc‐FA starting from readily available monounsaturated linear FA. Our results show that common UFA such as oleic acid can be converted to bc‐isomers using modified Ferrierite zeolite catalysts with high conversions (98%) and high selectivity (85%) and that the zeolite catalysts are reusable for at least three cycles. The positions of branching (methyl) on the FA chain were determined from the GC‐MS spectra of the picolinyl esters of the bc‐FA.     

1，3－取代方酸衍生物的光谱研究及二聚体、簇集体的形成

本文合成了１，３－取代方酸衍生物：１，３－双［４－二甲胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＭＣＳ），１，３－双［４－双十六烷胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＨＣＳ）。研究了ＤＭＣＳ和ＤＨＣＳ在不同溶剂中的光物理行为，估算了ＤＭＣＳ、ＤＨＣＳ的基态与激发态之间偶极矩差值。在ＣＴＡＢ胶束中，除ＤＭＣＳ单体分子外，ＤＭＣＳ形成了二聚体。在二氧六环－水体系中，研究了ＤＨＣＳ的簇集行为，并测定了ＤＨＣＳ的临界簇集组成（Ｃ＿ψ）及临界簇集浓度（Ｃ＿Ａ）     

咔唑腙为荧光指示剂的亚硝酸根传感器

合成了一种共轭的咔唑二聚体荧光载体9-乙基-3-咔唑亚甲基-咔唑腙(ECCH),用PVC包埋的方法可以将它固定在光纤传感器的表面,在溶液pH值为2.0时,亚硝酸根(NO2-)与过量的碘离子(I-)反应生成的碘三离子(I3-)能猝灭此ECCH光极膜的荧光.得到了可以检测NO2-的传感器,并讨论了此传感器的传感机理.传感器具有较好的稳定性、重现性和选择性,使用寿命长等优点.NO2-测定的线性范围为1.0×10-6~1.0×10-4mol.L-1;检出限为4.0×10-7mol.L-1.将传感器用于水样中NO-2的直接测定,回收率在96.0%~103.6%.     

Synthesis and characterization of polyamides based on dimer acid

A series of dimer acid-based polyamides were synthesized by melt-polycondensation of dimer acid and various aromatic diamines, and were characterized by Fourier transform infrared spectrum (FT-IR) and nuclear magnetic resonance (¹H NMR). The physical properties of the polyamides, such as glass transition temperature, melting temperature, decomposition temperature and mechanical properties were also investigated. The polyamides’ intrinsic viscosity ranges from 1.8 dL·g⁻¹ to 2.2 dL·g⁻¹, and the melting temperature ranges from 140 °C to 181 °C. The glass transition temperatures, observed from dynamic mechanical analysis, fall in the range of 34.8–48.2 °C. The physical and mechanical properties of the resultant polyamides are similar to those of the PA1212. The heat resistance and mechanical properties of poly (4, 4′-diphenylsulfone dimeramide) (PSD) and poly(4, 4′-diphenyl dimeramide) (PPDI) are comparable to those of PA1212.     

一个簇基无机-有机杂化材料的合成与表征

对簇基无机-有机杂化材料的制备方法及表征手段进行了研究。利用水热合成技术制备了一个具有新颖结构的簇聚物(H_2en)_2(H_3O)_(12)[Si_2Mo_(14)~(VI)Mo_2~VV_2~VV_(10)~(IV)O_(84)](1,en=乙二胺),采用元素分析、红外光谱、X射线光电子能谱、电子顺磁共振、TG及X射线单晶衍射等技术对晶体结构进行了分析。结构分析显示,簇基杂化材料是由两个高还原态的二帽Keggin型簇阴离子[Si(1)Mo_6~(VI)Mo_2~VV_6~(IV)O_(42)]~(10-)和[Si(2)Mo_8~(VI)V_2~VV_4~(IV)O_(42)]~(6-)通过(μ_2-O)_2双桥氧原子连接成以簇阴离子二聚体为结构单元的1-D链,相邻的1-D链再经质子化的水分子通过氢键连接成新颖的3-D簇阴离子超分子网络,质子化的乙二胺和水分子填充于网络之中。磁性研究表明化合物1金属离子间存在反铁磁性相互作用。     

Simulation of dimer diffusion on metal fcc (001)surfaces by molecular dynamics

We study systematically the dimer diffusion on metal fcc (001) surfaces through molecular dynamics calculations based on embedded atom method. Besides the conventional hopping and exchange mechanisms, some other interesting diffusion mechanisms are observed, such as the exchange rotation mechanism, the cooperative hopping mechanism, and the cooperative exchange mechanism. On the different kinds of metal surfaces, we find that not only the dominant diffusion mechanism but also the physical model for the exchange mechanism is different.