2,3-二羟基萘钼多酸有机衍生物的合成及1H NMR和IR谱学研究

本文对二种新合成的2，3－二羟基萘二钼和四钼多酸有机衍生物[n-Bu)4N]2[Mo2O5(OC10H6O)2](Ⅰ）和[n-Bu)4N]2[Mo4O10(OC10H6O)2(OCH3)2](Ⅱ)进行了红外光谱与核磁共振波谱研究，发现[Mo2O5]^2 中钼氧多桥键的红外振动频率较[Mo4O10(OCH3)2]^2 中钼氧多桥键的红外振动频率红移，而在配合物Ⅱ中2，3－二羟基中芳环的^1H化学位移较配合物Ⅰ中向低场移动。同时还发现含二钼配位中心[Mo2O5]^2 的[Mo2O5(OC10H6O)2]^2-与含四钼配位中心[Mo4O10(OCH3)2]^2 的[Mo4O10(OC10H6O)2(OCH3)2]^2-生成条件的差异仅仅只在反应体系的pH值的微小变化，说明钼多酸有机衍生物阴离子是对体系酸碱度极为敏感的物质。     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

橙皮素A的NMR研究

橙皮素A是从中药北沙参(Glehnia littoralis Fr. Schmidt ex Miquel)的正丁醇萃 取物中分离得到的一种8-O-4′-型异木脂素苷类化合物. 通过化学方法和波谱分析鉴 定了该 化合物的结构. 采用2D NMR技术对其NMR信号进行了全归属. DMSO-d₆代替CD₃OD作为溶剂，并利用重水交换，能准确读出偶合常数J_7,8值.      

用峰面积判据改善Delsuc法预测的谱

基于Prony算法的Delsuc谱预测是目前NMR LPSVD(Linear Prediction SingularValue Decomposition)法中比较实用的方法。但在高噪声的条件下,时有失峰和假峰出现且要事先知道谱的峰数。本文通过跟踪迭代过程发现Delsuc法的判别因子r_(mis) 很难选定。如果它太小会失峰,而过大又会出现假峰。同时,由于噪声的影响,弱信号的采样点之间的相关性比强信号小,从而在迭代过程中会增加数值不稳定性。文中引入峰面积判据来改善Delsuc法,经模拟与实验均证明结果有效。     

Pseudo cyclic ionophores: ‘Binary-effect’ of quinolinyloxy groups at both ends of oligoethylene glycols on the conformational stabilization of their complexes with alkali metal salts

A series of noncyclic neutral ionophores has been synthesized by the reaction of oligoethylene glycol dihalides with 8-quinolinol. Complexation properties for alkali metal picrates were evaluated from solvent extraction and bulk liquid membrane transport experiments. Complexation profiles of the newly synthesized ionophores with a hexyl chain were similar to those of their homologues without the hexyl chain in the extraction experiments. Among them, the pentaethylene glycol derivatives showed the highest extraction efficiency and selectivity towards potassium ion. From the¹H NMR spectra (400 MHz), the change in chemical shifts of the aromatic protons upon the addition of alkali metal thiocyanates suggested the existence of a stabilization effect which is caused by intramolecular stacking conformations between the quinoline rings during complexation. Aryl stacking interactions depend on the size of the cations and on the chain length of the oligoethylene glycol. The relationship between transport ability towards alkali metal cations and lipophilicity of these ionophores is also discussed.     

应用LiNbO_3声表面波驱动的全光纤声光频移器

介绍一种工作在10.7MHz的全光纤声光频移器.它由在LiNbO_3基片上制作的叉指电极换能器产生的声表面波驱动.当驱动电功率1.5W时,频移光转换效率达35％.     

Ab initio predictions of zeolite structures and Si NMR chemical shifts

A recent shell-model potential parameterized on ab initio data is used for predicting the all-silica structures of zeolites MFI, MEI, MTW, TON, FAU and of α-quartz. Cluster models are defined around each site and the ²⁹Si NMR shielding constants are calculated by ab initio techniques (GIAO-HF). Good agreement with observed ²⁹Si NMR chemical shifts is found. Comparison is made with shifts calculated for observed structures. The structures predicted by the ab initio shell-model potential prove as accurate as the observed ones when judged on the quality of the calculated ²⁹Si NMR spectra.     

Effect of surfactants on the voltammetric response and determination of an antihypertensive drug

The effect of adding surface-active agents to electrolytes containing terazosin, an antihypertensive drug, on the voltammetric response of glassy carbon electrode was studied. The current signal due to the oxidation process was a function of the amount of terazosin, pH of the medium, type of surfactant, and accumulation time at the electrode surface. Two surfactants were used, an anionic type, sodium dodecyl sulfate (SDS) and a cationic type, cetyl trimethyl ammonium bromide (CTAB). Addition of SDS to the terazosin-containing electrolyte was found to enhance the oxidation current signal while CTAB showed an opposite effect. Beside the interfacial interaction of the surfactant with the electrode surface in reference to the bias applied potential and the charge of surfactant, terazosin-surfactant interaction in the electrolytic solution was found to be critical to the magnitude of current signal. Addition of SDS to terazosin-containing buffer solution resulted in a decrease in the drug absorption spectrum both in the ultra-violet and visible (UV-vis) regions. Moreover, NMR measurements showed considerable chemical shifts for the aromatic protons of the quinazolinyl moiety of the terazosin in presence of SDS. The affected aromatic protons are positioned next to the interacting protonated amino-group of the terazosin with the charged sulfonate-group of SDS. On the other hand, addition of CTAB did not cause noticeable changes both to the UV-vis and NMR spectra of the drug. The use of SDS in the electrochemical determination of terazosin using linear sweep voltammetry and differential pulse voltammetry at solid glassy carbon electrode enhanced the detection limit from 6.00 × 10⁻⁷ mol L⁻¹ in absence of surfactant to 4.58 × 10⁻⁹ mol L⁻¹ when present. The validity of using this method in the determination of drug active ingredient in urine samples and tablet formulations was also demonstrated.     

几种N-取代马来酰胺酸辅酶模型的核磁共振研究

我们对8种N-取代马来酰胺酸辅酶模型与不同类型的亲核试剂反应后生成的产物进行了¹H、¹³C NMR的研究, 测得¹H、¹³C谱化学位移,研 究探讨其规律性, 并测试了IR谱和元素分析.