Hydrophilic interaction liquid chromatography with indirect ultraviolet detection for the separation and quantification of pyrrolidinium ionic liquid cations

A method of hydrophilic interaction liquid chromatography with indirect ultraviolet detection was developed to determine three pyrrolidinium ionic liquid cations, i.e. N-methyl-N-ethyl pyrrolidinium cation ([MEPy]⁺), N-methyl-N-propyl pyrrolidinium cation ([MPPy]⁺) and N-methyl-N-butyl pyrrolidinium cation ([MBPy]⁺). Chromatographic separation was achieved on a hydrophilic column using imidazolium ionic liquids and organic solvents as the mobile phase. The effects of the background ultraviolet absorption reagents, the imidazolium ionic liquids, detection wavelength, organic solvents, column temperature and the pH value of the mobile phase on the separation and determination of pyrrolidinium cations were investigated and the retention behaviors in hydrophilic interaction chromatography were discussed. The optimized chromatographic conditions were selected. Under the optimal conditions, the detection limits (S/N = 3) for [MEPy]⁺, [MPPy]⁺ and [MBPy]⁺ were 0.59, 0.53 and 0.46 mg/L, respectively. The method has been successfully applied to the determination of the three ionic liquids synthesized in our chemistry laboratory. This research results may improve the analytical method of ionic liquid cations.     

Capillary electrophoretic and thin-layer chromatographic characterization of rhenium complexation with 1-hydroxyethylidenediphosphonic acid

1-Hydroxyethylidenediphosphonic acid (HEDP) labeled by short-lived radionuclides with the nuclear properties suitable for the therapeutical purposes (¹⁸⁶Re, ¹⁸⁸Re, ¹⁶⁶Ho) is similar to the other phosphonates widely applied in the radiopharmaceutical field for the treatment of palliative bone metastases. One of the important steps for the preparation of compounds of radiopharmaceutical interest is the quality control comprehending the radiochemical and chemical purity determination. Chromatographic methods as TLC and HPLC are mostly used for this purpose. Our experiments were focused on the application of capillary electrophoresis with UV detection to the study of rhenium complexation with HEDP. The influence of pH, concentration of the ligand and the reaction time were determined. Taking in account our previous results, the Re:SnCl₂ molar ratio 1:500 (for 0.1 mM Re) was applied to reduce perrhenate to lower oxidation states which enables the Re–HEDP complexation. Different background electrolytes were tested. The mixture of 40 mM Na₂HPO₄ with 15 mM HEDP adjusted to pH 8 was selected as the most suitable system because it enabled the separation of different forms of Re–HEDP complexes. The results obtained in this study were compared to those obtained by thin-layer chromatography with radiometric detection.     

C and H nuclear magnetic shielding and spin–spin coupling constants of C-enriched bromomethane in the gas phase

¹³C and ¹H NMR spectral parameters are investigated for ¹³CH₃Br in gaseous matrices. It is found that both the ¹³C and ¹H chemical shifts of ¹³CH₃Br are linearly dependent on solvent density. Similar dependence is also detected for one-bond spin–spin coupling, ¹J(CH). For the first time the ¹³C and ¹H magnetic shielding constants and ¹J(CH) spin–spin coupling are obtained for an isolated ¹³CH₃Br molecule together with the coefficients responsible for solute–solvent molecular interactions in gaseous matrices. The present experimental results confirm the accuracy of some recent ab initio calculations of nuclear magnetic shielding performed for bromomethane.     

A new approach to all—cis triquinane synthesis and a new route to the C16—hexaquinane system

A new synthesis of all-cis triquinanes is presented. The examples bear a cis substituent on the fifth position of the central ring, and are thus all-cis pentasubstituted cyclopentanes. The stereo-controlled addition of organometallics of 7-ketonorbornenes is considered, as is “reductive solvolysis” of such adducts to the corresponding hydrocarbons. The preparation of trans-3,4-dimethoxycyclopentyl chloride is given, as is that of the corresponding organolithium. The use of quinoxaline derivatives in aldol-type reactions is considered, with examples. A new approach to the C₁₆-hexaquinane system is developed. The ring systems reported include: tricyclo-[8.2.1.0^2,9]tridecane, tricyclo[6.3.0.0^3,7]undecane, tetracyclo-[10.1.0.0^2,9.0^10,13]tridecane, pentacyclo[8.5.1.0^2,6.0^7,16.0^11,15]hexadene and hexacyclo(8.5.1.0^2,6.0^3,14.0^7,16.0^11,15]hexadecane.     

尖吻蝮蛇毒抗凝血因子Ⅱ的稀土离子荧光探针研究

尖吻蝮蛇毒抗凝血因子(ACF)分子中有两个钙离子结合位点,钙离子对ACF的内源荧光有增强作用,稀土离子(Nd³⁺,Sm³⁺,Eu³⁺,Gd³⁺和Tb³⁺)能取代ACF分子中的钙离子,并对ACF的内源荧光有不同程度的猝灭作用,其中Tb³⁺接受ACF分子中Trp残基传递的能量后,特征荧光增强.稀土离子与ACF荧光滴定表明,ACF分子中有两个稀土离子结合位点,稀土离子和钙离子在ACF分子中两个结合部位是共同的竞争结合部位.ACF与不同稀土离子之间有相近的表观结合常数K₁或K₂.Tb³⁺与RE³⁺(RE=Nd,Sm,Eu或Gd)间线性自由能关系表明,稀土离子与ACF结合时,没有明显的空间效应.ACF分子中的两个结合位点在结构上都有较大的柔性,这种结构柔性为钙离子在ACF与活化凝血因子X的结合反应中起到的促进作用提供了结构基础.     

MRSDCI STUDIES OF LOW-LYING ELECTRONIC STATES OF THE N_2F~+ MOLECULE

Ab initio electronic structure calculations are reported for low-lying electronic states,X ~1Σ~+andA ~1Π of the N_2F~+ molecule.Geometric parameters for the ground state X ~1Σ~+ are predicted by means of mul-tireference single and double excitation configuration interaction(MRSDCI)calculations with a double zeta pluspolarization(DZ+P)basis set.Vertical excitation energy for these two electronic states is determined usingMRSDCI/DZ+P calculations at the ground state equilibrium geometry.The oscillator strength for the X~1Σ+→A ~1Π transition and the radiative lifetime for the A~1Π state are calculated based on the MRSDCI wavefunc-tions.     

自然丰度氮-15核磁共振的研究(Ⅰ)——哌啶衍生物中4-位取代基对15N化学位移的远程相互作用及其与13C化学位移的关系

测定了8个4-位取代的2,2,6,6-四甲基哌啶的自然丰度¹⁵N核磁共振谱及¹³C谱,发现4-位取代基对¹⁵N化学位移有一定的远程相互作用,¹³C化学位移与4-位卤素取代基的原子电负性有近似的线性关系。     

Effect of Zn2+ Ions on Upconversion Emission of Er3+ in Zn/Er:LiNbO3 Crystal

The effect of Zn2+ ions codoped on the upconversion emission of Er3+ ions in Er:LiNbO3 crystal under different excitation wavelength was reported.The upconversion emission spectra of Zn/Er:LiNbO3 follo...     

构象转换型传感器对汞、铅、锶离子的同时检测

将核酸构象转换与纳米孔膜技术联用设计了一种新型高灵敏电化学传感器, 实现了对Hg ²⁺, Pb ²⁺和Sr ²⁺的分步同时检测. 使用2种分别能与Hg ²⁺及Pb ²⁺, Sr ²⁺结合的核酸适体, 将其固定在氧化铝纳米孔膜孔道内以阻碍铁氰化钾离子传导. 利用核酸适体包裹目标物时的蜷缩状态与目标物被洗脱剂洗脱后核酸适体的伸展状态之间的构象转换, 控制纳米孔通道的“开”和“关”, 使铁氰化钾溶液的氧化还原电流发生改变. 通过监测铁氰化钾溶液的电信号变化值, 可实现同时检测此3种金属离子的目的. 实验结果表明, 该传感器对3种金属离子具有很高的灵敏度和选择性, 检测的线性范围均为0.051.50 nmol/L, 对Hg ²⁺, Pb ²⁺和Sr ²⁺的检出限分别为0.013, 0.017和0.022 nmol/L(S/N=3).     

The complete assignment of the h and C nmr spectra of the alkali metal salts of salinomycin and narasin

The preparation of the alkali metal salts of salinomycin and narasin, apart from lithium narasin, is described. The complete assignment of their ¹H spectra based on two dimensional COSY and NOESY spectra is reported. These asignments are then used in two dimensional ¹³C/¹H correlations via direct and long range couplings to assign the ¹³C spectra. Assignments in the ¹³C spectrum of sodium salinomycin differ in important details from those in a previous report.     

高催化活性M-BHT(M=Co， Cu)电催化还原CO2为CH4的密度泛函理论研究

具有独特电子结构和丰富催化位点的二维金属有机框架材料是具有高活性的CO₂还原反应的电催化剂. 本文基于密度泛函理论(DFT)计算, 发现单层Co-BHT(BHT=benzenehexathiol, 苯六硫醇)将CO₂还原为CH₄时具有很高的催化活性. 吉布斯自由能变化计算结果表明, 在Co-BHT上将CO₂还原成CH₄的最佳反应路径为CO₂→^*COOH→^*CO→^*CHO→^*CHOH→^*CH→^*CH₂→^*CH₃→CH₄; 整个反应的速度控制步骤为^*CO→^*CHO; 速度控制步骤的吉布斯自由能变化(ΔG_L)为0.66 eV, 比在二维Cu-C₃N₄(ΔG_L=0.75 eV)和传统的Cu(211) 表面(ΔG_L=0.74 eV) 将CO₂还原为CH₄的吉布斯自由能变化都小. 而在单层Cu-BHT表面的反应路径和速度控制步骤 (CO₂→^*COOH)与Co-BHT均不同, 且ΔG_L为0.76 eV. 与Cu-BHT相比, Co-BHT将CO₂还原为CH₄的ΔG_L更低, 这可能归因于Co-BHT的d能带中心高于Cu-BHT, 导致Co-BHT与中间体的相互作用更强.     

Ab initio study of the electronic spectrum of dichlorocarbene CCl2

The equilibrium geometries, excitation energies, force constants and vibrational frequencies for seven low-lying electronic states X ¹A₁, ¹B₁, ³B₁, ¹A₂, ³A₂, ¹B₂ and ³B₂ of dichlorocarbene CCl₂ have been calculated at the MRSDCI level with a double-zeta plus polarization basis set. Our calculated equilibrium geometry for the X ¹A₁ state, excitation energy for X ¹A₁ → ¹B₁ and vibrational frequencies for the X ¹A₁ and ¹B₁ states are in good agreement with experimental data. The electronic transition dipole moments, oscillator strengths for the ¹B₁ → X ¹A₁ and ¹B₂ → X ¹A₁ transitions, radiative lifetimes for the ¹B₁ and ¹B₁ states are calculated using MRSDCI wavefunctions, predicting results in reasonable agreement with experiment.     

Theoretical and experimental studies of radiative lifetimes of excited electronic states in CO

The electronic dipole transition moment functions of the A ²Π-X ²Σ⁺, B ²Σ⁺-X ²Σ⁺ and B ²Σ⁺-A ²Π transitions and the dipole moment function of the X ²Σ⁺ state of CO⁺ have been calculated using large contracted CI wavefunctions. The computed transition moment functions together with experimental potential energy curves were used to obtain radiative lifetimes of the excited electronic states B ²Σ⁺ and A ²Π. Radiative lifetimes of vibrational levels of the X ²Σ⁺ state were derived from the calculated dipole moment function. The high-frequency deflection technique was used to obtain radiative lifetimes of the ν′ = 0, 1,2 and 3 vibrational levels of the B ²Σ⁺ state and also radiative lifetimes of individual rotational levels of ν′ =0. The calculated radiative lifetimes are shorter than the measured ones by about 10%. The experimental ν′ dependence is reproduced by theoretical calculation. The calculated radiative lifetimes for the A ²Π state are in excellent agreement with lifetimes measured with an ion trap technique.     

Reactivity and electronic property of decaphenylmetallocenes of Mo and W atoms

The perphenylmetallocene complexes (η⁵-C₅Ph₅)₂W (1), [(η⁵-C₅Ph₅)₂W]⁺I₃⁻ (1⁺I₃), (η⁵-C₅Ph₅)₂Mo (2) and [(η⁵-C₅Ph₅)₂Mo]⁺I₃⁻ (2⁺I₃) have been prepared. Hydrogenation of 1 in THF produces (η⁵-C₅Ph₅)₂WH₂ (4), while (η⁵-C₅Ph₅)₂WHCl (3) is afforded in 1,2-dichloroethane solvent. Carbonylation of 1 produces (η⁵-C₅Ph₅)₂W(CO) (5). Treatment of 1 with the strong acid CF₃SO₃H leads to the dicationic species [(η⁵-C₅Ph₅)₂W]⁺²[CF₃SO₃]⁻₂ (1⁺²Tf₂) after crystallization. The structures of 2⁺I₃ and 1⁺²Tf₂ have been determined by an X-ray diffraction study. The magnetic susceptibility study indicates a ³E_2g ground-state for 1 and 2, and a ⁴A_2g ground-state for 1⁺ and 2⁺.     

Tunnel effects on inter- and intramolecular hydrogen transfer reactions of transient dihydro- and hexahydrocarbazoles

We examine inter- and intramolecular hydrogen-transfer processes in two related metastable dihydrocarbazoles in nonpolar solvents of different viscosity and compare them with similar transfer processes in transient hexahydrocarbazoles. N-ethyldiphenylamine (A′) and N-ethyl-2,6-dimethyldiphenylamine (A) photocyclize in their triplet states, yielding the triplet states of the zwitterionic dihydrocarbazoles ³Z′* and ³Z*, respectively, which subsequently relax to their metastable singlet ground states ¹Z′ and ¹Z′. In spite of their similarity, the two transients ¹Z′ and ¹Z stabilize by completely different pathways: the unsubstituted transient ¹Z′ is converted into N-ethylcarbazole (C) and an N-ethyltetrahydrocarbazole (THC) by a bimolecular disproportionation reaction. The methylsubstituted intermediate ¹Z is converted into a stable dihydrocarbazole (D) by a sigmatropic, intramolecular [1,8]-H-shift and by an intermolecular, mutual hydrogen-exchange reaction within the encounter complex ¹(ZZ) which yields two molecules of D. The rates of the intra- and of the intermolecular transfer reaction of ¹Z are governed by tunnel effects. The rate of the intramolecular tunnel process does not depend on solvent friction and becomes temperature independent at low temperatures. The rate of the intermolecular, reaction-controlled exchange reaction ¹(ZZ) → 2 ¹D becomes also temperature independent if the solvent is fluid enough. In more viscous solvents the reaction becomes diffusion controlled and, therefore, strongly temperature dependent. The intermolecular disproportionation reaction 2 ¹Z′ → C + THC is also reaction controlled but no tunnel effects are observed.     

Ab initio molecular orbital study of potential energy surface for the H2NO(B1)→NO(Π)+H2 reaction

The mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction has been examined using ab initio molecular orbital methods. Ground-state and first-excited-state potential surfaces were plotted at the FOCI/cc-pVTZ level of theory as functions of two appropriate internal degrees of freedom. A conical intersection was found on the C_s pathway that is symmetric with respect to the plane perpendicular to the molecular plane of C_2v H₂NO(²B₁). It is therefore considered that trajectories that start from H₂NO(²B₁) towards the product region detour around the conical intersection, pass through the neighborhood of the transition state that is located at the saddle point on the C_s pathway, and finally reach the products, NO(²Π)+H₂. Thus we can explain the mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction, which has remained unclear to date.     

Wavelength independence of Eu quantum yields

A quantitative comparison between the excitation and absorption spectra of Eu³⁺ in aqueous solution is given which leads to the conclusion that fluorescence quantum yields are independent of the excitation wavelength. Use is made therefore of the series of homologous lines ⁵D₃, ⁵D₂, ⁵D₁, ⁵D₀ → ⁷F₁.     

A self consistent field molecular orbital study of the lithium-formaldehyde system

The nature of the lithium—oxygen bond in the lithium—formaldehyde system (a prototype of the ketyl radical—alkali metal ion pairs) is examined by unrestricted Hartree—Fock calculations using minimum and extended Slater-type bases and ghost orbital methods. Two states of the equilibrium C_2v symmetry structure are considered: ²B₁, which is a π radical, and ²A₁, Which is a σ radical. In contrast with the results of Ha et al. [10], the ²B₁, state is found to have a slightly lower energy than ²A ₁, When only s-type basis functions are used for the lithium atom; the ²B₁, state is further stabilized if 2p functions at the lithium centre are included. Inclusion of 2p orbitals on lithium greatly exaggerates the charge density at the lithium atom in single-ζ basis calculations on the ²B₁ state, and earlier calculations by Bernardi and Pedulli [8, 9] are found severely to underestimate the polarity of this state. A much better wave-function is obtained from double-ζ basis calculations, and it is concluded that the net charge of Li in the ²B₁, state is close to + 1. The ²A₁, state, on the other hand, is essentially homopolar.     

Automatic F positron source supply system for a monoenergetic positron beam

A system which supplies an intense ¹⁸F (half life 110 min) positron source produced by an AVF cyclotron through ¹⁸O(p,n)¹⁸F reaction has been constructed. Produced ¹⁸F is transferred to a low background experiment hall through a capillary. It is electro-deposited on a graphite rod and used for a source of a slow positron beam. In the meantime the next batch of target ¹⁸O water is loaded and proton irradiation proceeds. This system makes it possible to perform continuous positron beam experiments using the ¹⁸F positron source.     

抗癌光敏剂ZnPcSP在溶液中的存在状态及其对活性的影响

研究了两亲性抗癌光敏剂磺基邻苯二甲酰亚胺甲基酞菁锌(ZnPcSP)单体与聚集体的可见吸收光谱特征以及溶剂组成对其聚集平衡的影响,得到了ZnPcSP在一系列溶剂中的聚集平衡常数.进而研究了存在状态对ZnPcSP的S₁₈₀肿瘤抑瘤率的影响.ZnPcSP在生理盐水中主要以三聚体形式存在,而在CEL溶液中,则主要以单体形式存在,后者对S180的抑瘤率是前者的8倍