Promotional Effect of Bismuth as Dopant in Bi-Doped Vanadyl Pyrophosphate Catalysts for Selective Oxidation of n-Butane to Maleic Anhydride

Bismuth-promoted （1% and 3%） vanadyl pyrophosphate catalysts were prepared by refluxing Bi（NO3）4.5H2O and VOPO4.2H2O in isobutanol. The incorporation of Bi into the catalysts lattice increased the surface area and lowered the overall V oxidation state. Profiles of temperature programmed reduction （TPR） in H2 show a significant shift of the maxima of major reduction peaks to lower temperatures for the Bi-promoted catalysts. A new peak was also observed at the low temperature region for the catalyst with 3% of Bi dopant. The addition of Bi also increased the total amount of oxygen removed from the catalysts. The reduction pattern and reactivity information provide fundamental insight into the catalytic properties of the catalysts. Bi-promoted catalysts were found to be highly active （71% and 81% conversion for 1% and 3% Bi promoted catalysts, respectively, at 703 K）, as compared to the unpromoted material （47% conversion）. The higher activity of the Bi-promoted catalysts is due to that these catalysts possess highly active and labile lattice oxygen. The better catalytic performance can also be attributed to the larger surface area.

STUDY ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY POLYPROPYLENE-BASED VANADYL POLYIMIDODIACETATE——THIOUREA REDOX SYSTEM

The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the temperature range from 25 to 40℃. The polymerization rate was measured by varying the concentrations of monomer, vanadyl polyimidodiacetate, thiourea and sulfuric acid. The overall rate of polymerization was summarized asRp=2.2×10~5e^(-6.560/RT) [AN]^(1.0)[PV]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)The molecular weight of polyacrylonitrile based on the experimental data was:(?)=k 1/T [pv]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)These results indicated that the chain radicals are terminated by combination and/or disproportionation rather than chain transfer. The cooperation effect of carboxylic groups and the macromolecular field effect of polymer supporter are the characters of vanadyl polyimidodiacetate such as the case reported in early paper.

"CAGE" VANADYL POLYCARBOXYLATE-THIOUREA COMPLEX FOR THE POLYMERIZATION OF ACRYLONITRILE

The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by ' cage ' vanadyl polycarboxylate (P=VO)-thiourea (TU) complex was investigated. The overall rate ofpolymerization isThe relationship between the induction period (τ) and the temperature of polymerization as well as the concentrations of reactants can be expressed as follows :The molecular weight of polyacrylonitrile increases with increasing monomer concentration and decreases with increasing temperature of polymerization and concentrations of vanadyl polycarboxylate and thioureaThe polymerization mechanism was proposed and discussed.

Determination of Vanadyl Porphyrins by Liquid-liquid Microextraction and Nano-baskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonye Carboxamide] and Di-(1-propoxy) in Ortho-cone Conformation

Dispersive liquid-liquid microextraction technique was introducd to remove the centrifuging step and conduct inclusion microextraction of charged porphyrins by nano-baskets. For nano-baskets of p-tert-calix[4]arene bearing di-[N-（X）sulfonyl carboxamide] and di-（1-propoxy） in ortho-cone conformation was synthesized and used. The related parameters including ligand concentration, the volume of water disperser, salt effect, and extraction time were optimized. The linear range, detection limit（S/N=3） and precision（RSD, n=6） were determined to be 0.2―50, 0.07 μg/L and 5.3%, respectively. The results reveal that the new approach is competitive analytical tool and an alternative of the traditional methods in the crude oil and related systems.

DFT Study on Structural Distortion and Vibronic Coupling of Vanadyl Porphyrin Anion and Cation

The geometries of one-electron reduced/oxidized species （[TOP]-/[VOP] ＋） of vanadyl por- phyrin （VOP） have been calculated with PBE1PBE method. The results show that for both [VOP]- and [VOP]＋ the ground states are triplet, in which one of the two unpaired electron occupies the dxy orbital of the V atom while the other occupies the n-orbital of porphyrin ring. Thus both [VOP]- and [VOP]＋ can be considered as n-radicals. The ground state of neutral VOP molecule is doublet with the unpaired electron occupying dxy orbital of V atom. In contract to the C4v symmetry of neutral VOP molecule, [VOP]- anion has a ＂rectangular＂ distorted C2v structure due to Jahn-Teller effect. The linear vibronic coupling constants for the Jahn-Teller active modes of [TOP]- were evaluated and the node patterns of frontier KS orbitals are used to explain the reason why the distortion occurs along specific modes. The ground state [VOP]＋ has a porphyrin ring with pronounced bond length alternation due to pseudo-Jahn-Teller effect, causing its symmetry declined from C4v to Ca. The bond length alternation is well explained with the node patterns of re-constructed frontier KS orbitals.

Vanadyl Sulfate Based Hole-Transporting Layer Enables Efficient Organic Solar Cells

It remains an urgent task to develop alternative hole-transporting layer(HTL)materials beyond commonly used PEDOT:PSS to increase the shelf-life of organic solar cells(OSCs).Inorganic metal oxide type materials,such as NiO_(x),CoO_(x)and VO_(x),with suitable work functions have attracted numerous research attention recently.In this work,more abundant and easily accessible oxygenated salt,vanadyl sulfate(VOSO_(4))has been demonstrated to be excellent choice as HTL for OSCs.The VOSO_(4)-based HTL can be readily processed by spin-coating from the precursor solution with subsequent thermal annealing and UVO treatment.As a consequence,a high power conversion efficiency(PCE)of 18.72%can be achieved for PM8:L8-BO based OSCs with the VOSO_(4)-based HTL.High transmittance,smooth film surface,suitable energy level and high conductivity were revealed to contribute to the high OSC performance.More importantly,compared to device with PEDOT:PSS,VOSO_(4)-based OSCs exhibit improved stability when stored in the N_(2)filled glove box.After being stored for 600 h,VOSO_(4)-based device can retain 89%of its initial efficiency.Notably,VOSO_(4)can be used as general HTL in PM6:BTP-BO-4Cl and PM6:IT-4F based OSCs,yielding high PCEs of 17.87%and 13.85%,respectively.

Anti-diabetic vanadyl complexes reduced Alzheimer's disease pathology independent of amyloid plaque deposition

Association of Alzheimer's disease(AD) with cerebral glucose hypometabolism, likely due to impairments of insulin signaling,has been reported recently, with encouraging results when additional insulin is provided to AD patients. Here, we tested the potential effects of the anti-diabetic vanadium, vanadyl(IV) acetylacetonate(VAC), on AD in vitro and in vivo models. The experimental results showed that VAC at sub-micromolar concentrations improved the viability of neural cells with or without increased β-amyloid(Aβ) burden; and in APP/PS1 transgenic mice, VAC treatment(0.1 mmol kg-1 d-1) preserved cognitive function and attenuated neuron loss, but did not reduce brain Aβ plaques. Further studies revealed that VAC attenuated Aβpathogenesis by(i) activation of the PPARγ-AMPK signal transduction pathway, leading to improved glucose and energy metabolism;(ii) up-regulation of the expression of glucose-regulated protein 75(Grp75), thus suppressing p53-mediated neuronal apoptosis under Aβ-related stresses; and(iii) decreasing toxic soluble Aβ peptides. Overall, our work suggested that vanadyl complexes may have great potential for effective therapeutic treatment of AD.

Role of vanadyl acetylacetonate-induced elevation of reactive oxygen species in the regulation of lipolysis and glucose metabolism in 3T3L1 adipocytes

In the present study, we investigated the role of reactive oxygen species（ROS） elevation induced by an anti-diabetic vanadium compound, vanadyl acetylacetonate（VO（acac）2）, in the regulation of lipolysis and glucose metabolism using differentiated 3T3L1 adipocytes as a model system. By confocal laser scanning microscopy, we found that VO（acac）2 induced ROS generation under high glucose stimulation, and the pretreatment of NADPH oxidase inhibitors could significantly reduce the elevated ROS level. Meanwhile, the decreased phosphorylated levels of AKT and the two key modulators of lipolysis（HSL and perilipin） were observed by western blot analysis. We also found that the contents of glycerol release were further reduced as well. In addition, the levels of key regulatory proteins, AS160 and GSK3β, in glucose metabolism pathway were correspondingly reduced. These findings demonstrated that ROS induced by vanadium compounds could act as a metabolic signal to activate AKT pathway to inhibit lipolysis and promote glucose transport and glycogen synthesis rather than by direct action by themselves. Our study contributed to elucidate the anti-diabetic effects of vanadium compounds and provided a theoretical basis for the further development of new vanadium complexes in the prevention and therapeutics of diabetes.

Characterization of vanadyl phthalocyanine based surface-type capacitive humidity sensors

This study presents the fabrication and characterization of novel surface-type capacitive humidity sensors using vanadyl phthalocyanine（VOPc） as the active material.The devices,which comprise three different thicknesses, have been fabricated using the thermal evaporation technique.A thin film of VOPc is deposited on thoroughly cleaned glass substrates with pre-patterned Ag electrodes.The capacitive effect of the samples under humidity has been investigated. Comparison of the samples with different thicknesses shows that the thinnest device seems more sensitive towards humidity.The humidity dependent capacitance properties of the sensor make it beneficial for use in commercial hygrometers.

DISCOVERY OF SPECIAL PREDOMINANCE OF VANADYL PORPHYRIN AND HIGH ABUNDANCE OF Di-DPEP IN NONMARINE STRATA

By means of TLC, UV-Vis, HPLC and MS analyses, the types, structure and fingerprint distribution of porphyrin compounds in the nonmarine strata of China have been studied herein. It is revealed that the predominance of vanadyl porphyrin in lacustrine sediments of the Ordos Basin resulted from the high maturity, while the abnormal high content of Di-DPEP in the boghead-cannel coal from Guizhou Province was probably related to its abundant source input, the weakly oxidizing condition during the early diagenesis and the consequent reducing environment.

Ag_(2)Sb合金单层上多层酞菁氧钒分子的组装

利用低温扫描隧道显微镜(STM)研究了各种覆盖度下酞菁氧钒(VOPc)分子在Ag_(2)Sb/Ag(111)上的吸附行为和组装结构.不同于Ag(111)表面,当分子覆盖度在一个单层之内,吸附的VOPc分子均组装为有序的薄膜,呈现出规则排列的空隙和正方形单胞.通过扫描亚分子分辨的STM形貌图,揭示了正方形单胞由一个中心分子和四个对称排列的角分子组成;所有VOPc分子均采用O-up构型,并呈现出两种吸附取向,分子横轴相对于单胞侧边分别旋转约11°和21°.因分子间的偶极-偶极相互作用,进一步沉积的VOPc分子组装为具有O-down和O-up构型交替堆积的分子膜,在分子层内分子轨道沿π堆积方向发生重叠.该研究为调控金属表面功能有机分子组装膜的结构和组装行为提供了一种新途径.

铜氧化层上钒氧酞菁分子的吸附构型及组装结构

近年来,有机功能分子的调控因其在提高纳米光电器件内部载流子迁移率方面的突出贡献,已逐渐成为材料科学的热门领域之一.本文利用低温扫描隧道显微镜系统地研究了钒氧酞菁(VOPc)分子在干净Cu(110)和铜氧化层表面的吸附构型和组装结构.在Cu(110)表面,初始时VOPc分子孤立吸附且氧原子向上和向下的构型共存.而在CuO-(2×1)表面,VOPc分子在初始时形成扩展的分子链,随后组装为有序的分子膜,在分子膜中两种吸附构型仍然共存且随机排布.在Cu_(5)O_(6)-c(6×2)表面,初始时VOPc分子的两种构型共存且形成无序结构.在覆盖度接近一个单层时,结构有序的组装分子膜逐渐形成,此时主要采用氧原子向上的分子构型,因偶极相互作用,随后的分子层生长遵循两种分子构型交替堆垛.研究还发现当Cu(110)表面上两种氧化结构共存时,第2层分子更倾向于吸附在Cu_(5)O_(6)-c(6×2)表面担载的分子膜上,主要是由分子层间的偶极相互作用导致的.本研究表明金属表面的氧化层在改变分子吸附构型和组装结构方面的重要性,可能将影响电子器件制造中分子膜中的电荷输运过程.

Determination of vanadyl sulfate ion-pair dissociation constant at 298.15 K by Fuoss method

Vanadium battery has fast and large capacity charge and discharge characteristics, and the concentration and stability of the battery electrolyte are the key to the electrolyte performance. In actual, with higher acidity and higher concentration of the vanadium battery electrolyte, the ion-pair is dominant. The ion-pair dissociation constant is one of the important thermodynamic data related to battery performance. The vanadyl sulfate conductivity in aqueous solution was determined using the conductance method at 298.15K. Using the origin data fitting, the limiting molar conductance is obtained, and then by the improved Ostwald dilution law and the Davies equation, the activity coefficient is solved so as to obtain the ionic strength of the true solution. Using the Fuoss method, the dissociation constant of vanadyl sulfate ion-pair was calculated. At last, the vanadyl sulfate limiting molar conductance (Λ 0 ) is 174.8251748 S·dm2·mol?1, and the vanadyl sulfate ion-pair dissociation constant K d is 0.002636367, and then other thermodynamic properties can be studied.

Electrochemical studies of tetraphenylporphyrin and vanadyl porphyrin

The electrochemical reductions and oxidations of tetraphenylporphyrin (TPP) and vanadyl por-phyrin (TPP-VO) were investigated in dimethylformamide at platinum,glass carbon and microdisk electrodes.A new eleetrode reaction mechanism of TPP and TPP-VO is proposed.The kinetic parameters have also been determined.In addition,the theory of molecular hybrid orbitals is used to explain the reduction and oxidation regularity of the transition metal porphyrms

Comparison of intestinal absorption of two insulin-mimic vanadyl complexes using Caco-2 monolayers as model system

Intestinal absorption of two oxovanadium complexes, vanadyl acetylacetonate (VO(acac)2) and bis (maltolato)-oxovanadium (VO(ma)2), has been compared using Caco-2 monolayers as a model system. The two compounds are similar in chemical structures but different in glucose-lowering effects. Our experimental results show that they are both transported via passive diffusion with apparent permeabilty coefficients (apical→basolateral) of (82.0 ± 6.7)× 10-7 and (14.6 ± 0.7)× 10-7 cm· s-1, respec-tively. This suggests that absorptivity of VO(acac)2 is much higher than that of VO(ma)2. This difference may be related to the metabolism of either compound, or its ligand, or both in the course of the transport. However, This difference in absorption will cause the great difference in bioavailability,which might account for better efficacy of VO(acac)2 than VO(ma)2 as the insulin-mimic agent.

科研实验转化成综合化学教学实验的探索

探索了由生物无机化学中较为成熟的科研实验"羧酸氧钒化合物的制备与表征"设计转化成研究型综合化学实验。采用芳香羧酸配体与简单的钒原料化合物反应,通过探索与优化实验过程中各步骤的最佳反应条件、处理方法以及适当的实验时间,以达到现象稳定、重复性好的教学实验要求。同时对制备的目标产物羧酸氧钒化合物,采用红外光谱和热重分析手段进行表征工作。该实验可以帮助学生巩固配合物制备基本原理,掌握旋转蒸发仪、微波炉、红外光谱仪、热重分析仪的工作原理及操作技能,培养学生相关的化学基础知识、实验操作、仪器分析等方面的综合能力以及相关的科学素质和研究能力。

纳米二氧化钒粉体的合成

应用氧钒(Ⅳ)碱式碳酸铵前体热分解合成了粒度约20nm的VO2粉体.研究了不同热分解条件对粉体组成和结晶度的影响.

硫酸氧钒对糖尿病大鼠血糖和血脂的影响

目的:探讨硫酸氧钒对糖尿病大鼠高脂血症的治疗作用,并初步探讨其作用机制。方法:选用Wistar大鼠,腹腔内注 射链脲佐菌素制备糖尿病模型。经饮水中加入1g/L硫酸氧钒,连续6周。结果:糖尿病大鼠的血糖、果糖胺、血脂、饮水量等明 显下降,而血浆胰岛素水平未增加。结论:硫酸氧钒可以通过增加胰岛素作用效率,发挥降糖、降血脂的治疗作用。

电感耦合等离子体原子发射光谱法测定钒电池硫酸氧钒中钒和硫酸根

全钒液流电池是一种应用广泛的新能源技术,固体硫酸氧钒(VOSO4·nH2O,n=3~5)则是制备钒电解液的基础原料,钒及硫酸根含量及其比例关系决定着电解液乃至钒电池的品质,因此建立了电感耦合等离子体原子发射光谱法(ICP-AES)测定钒电池硫酸氧钒中钒和硫酸根的方法。优选了待测元素灵敏度适中的分析谱线,满足了同时测定钒电池硫酸氧钒中含量范围变化较大的钒和硫酸根的需要,并且优化了分析谱线的积分区域、同步背景校正区域等仪器检测条件,改善方法检测性能。以钒和硫酸根的混合标准溶液系列绘制校准曲线,使用基体匹配法消除基体效应的影响。方法中钒和硫酸根的测定范围分别为15.0%~30.0%和35.0%~50.0%;校准曲线线性相关系数大于0.9999。实验方法用于测定2个硫酸氧钒样品中钒和硫酸根,结果的相对标准偏差(RSD,n=11)小于0.50%;回收率为96%~104%。分别使用本法测定3个硫酸氧钒样品中钒和硫酸根,并与使用过硫酸铵氧化-硫酸亚铁铵滴定法测定钒、硫酸钡重量法测定硫酸根的结果进行比对,测定结果比较吻合。

轮古常渣及其组分中金属钒卟啉的分离与鉴定

采用改进的溶剂萃取方法对轮古常渣及其组分中的金属钒卟啉进行分离。结果表明,从轮古常渣中分离出的卟啉钒的质量分数为18.5%,从轮古常渣正庚烷可溶质和沥青质中分离出的卟啉钒的质量分数分别为68.0%和9.2%。用紫外-可见光谱对萃取出来的金属钒卟啉和甲磺酸脱金属后得到的游离卟啉进行表征。结果表明,轮古常渣及其正庚烷可溶质和沥青质中的金属钒卟啉主要是初卟啉。对轮古常渣中的游离卟啉进行基质辅助激光解吸电离飞行时间质谱分析证明,轮古常渣中的金属钒卟啉主要是初卟啉。