一类基于1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸-酰肼结构的新型含钆磁共振对比剂的设计、合成及性能表征（英文）

磁共振成像技术被广泛应用于诊断医学和软组织成像,而磁共振对比剂有助于提高成像对比度.报道了一类共十二种基于钆-1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸(DOTA)-酰肼结构的新型磁共振对比剂的设计、合成及性能表征. 0.5 T磁场下测得的弛豫率结果显示,对比剂5d、5h和5l的纵向弛豫率优于临床使用对比剂Gd-DOTA,分别达到4.67、4.85和5.33L·mmol-1·s-1.进一步动物活体体内肝靶向磁共振成像研究显示,对比剂5d具有作为肝靶向磁共振对比剂的应用潜力.     

一种大环类双核非离子型磁共振对比剂的合成及弛豫性能(英文)

磁共振成像技术被广泛应用于诊断医学和软组织成像,而磁共振对比剂有助于提高成像对比度.报道了一种基于钆-DOTA-酰肼结构(DOTA=1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸)的新型双核非离子型磁共振对比剂(Gd-DOTAH)2-SBDC的设计、合成及弛豫性能.在0.5 T磁场下,测得其纵向弛豫率为每分子10.6 L·mmol~(-1)·s~(-1)或5.3L·mmol~(-1)·Gd~(-1)·s~(-1),高于目前临床使用的单核大环对比剂钆-DOTA.体外磁共振成像研究显示该磁共振对比剂具有提高诊断灵敏度和准确度的特点.同时,该对比剂分子中含有能与髓鞘特异性结合的二苯乙烯结构,具有成为髓鞘靶向磁共振对比剂的应用潜力.另外,探讨了该对比剂的两条合成路线(A和B),总收率分别为70%和75%.综合考虑适用性,合成路线B更优.     

电/离子导体双包覆的LiNi0.8Co0.1Mn0.1O2锂离子电池阴极材料及其电化学性能

高镍三元材料LiNi_0.8Co_0.1Mn_0.1O₂ (NCM)比容量高且成本低, 但材料结构在电化学循环过程中的不稳定性影响了其大规模的应用, 可采用表面包覆的策略来改善材料的结构稳定性, 从而提高其电化学性能. 本工作结合高速固相包覆法和高温烧结法, 分别将电子导体氧化锡锑(ATO)和锂离子导体偏磷酸锂(LOP)共同包覆在NCM材料表面. 双包覆后的NCM材料的电子电导率从2.17×10^-3 Ѕ•cm^-1提高至1.02×10^-2 Ѕ•cm^-1, 锂离子扩散系数也从7.05×10^-9 cm²•s^-1提高至2.88×10^-8 cm²•s^-1. 同时, NCM表面的双包覆层可以在循环过程中阻止电极材料与电解液发生氧化还原反应, 抑制材料不利相变, 减少氧的析出, 稳定材料结构. 电化学性能测试表明, 经过表面包覆后, NCM材料在1 C (180 mA•g^-1)的电流下和2.7~4.3 V (vs. Li/Li⁺)的电压范围内, 循环150周后容量为161.1 mAh•g^-1, 保持率为87.1%, 而在10 C的充放电倍率下具有133 mAh•g^-1的可逆比容量.     

两种具有高弛豫率的双核非离子型磁共振对比剂（英文）

磁共振成像技术被广泛应用于诊断医学和软组织成像,而磁共振对比剂有助于提高成像对比度.报道了两种基于钆-DOTA-酰肼结构的新型双核非离子型磁共振对比剂[(Gd-DOTAH)2-DYMB和(Gd-DOTAH)2-DYMBP]的设计、合成及弛豫性能.在0.5 T磁场下,测得其纵向弛豫率分别为每分子11.4和11.7 L·mmol~(-1)·s~(-1)或5.7和5.9 L·mmol~(-1)·Gd~(-1)·s~(-1),高于目前临床使用的单核大环对比剂钆-DOTA.体外磁共振成像研究显示该两种磁共振对比剂具有提高诊断灵敏度和准确度的应用潜力.     

基于稀土阳离子和多酸阴离子的系列纯无机离子液体的合成及性质

本工作报道了系列钛取代Keggin型钨磷酸稀土盐KLnH₃PTi₂W₁₀O₄₀•xH₂O [Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Er (7), Yb (8)]的合成和性质. 这些无机离子型化合物在4~65 ℃范围表现为流动性很好的液态, 呈现离子液体行为. 微量的水是该系列离子液体组成中不可缺少的组分, 完全失去水后变为无定型的透明固体. 该系列离子液体在室温时具有良好的导电性, 电导率均高于10 mS•cm^-1, 而且其电导率随温度发生明显的变化. 当从室温升高到65 ℃时, 含Ce的离子液体2电导率从13.3 mS•cm^-1逐渐增大至22.6 mS•cm^-1, 但从65 ℃升温至90 ℃时, 电导率明显降低. 研究还发现, 在室温环境下该系列离子液体与水均不互溶呈两相, 加热后混溶为均一相, 表现出上临界溶解温度(UCST)相行为. 据我们所知, 这种纯无机离子液体是非常少见的.     

Gd3+与RGD共修饰量子点用于胰腺癌细胞的荧光及MR双模态成像

结合磁共振成像(MRI)和荧光成像技术,以钆离子(Gd3+)、量子点及精氨酸(R)-甘氨酸(G)-天冬氨酸(D)(RGD)多肽等为功能单元,采用纳米载体组装技术构建了MRI弛豫率/荧光效率高和靶向性强的Gd3+与RGD共修饰的量子点双模态纳米探针(QDs@Gd3+-RGD),并将其用于胰腺癌细胞的双模态成像.实验结果表明,QDs@Gd3+-RGD双模态纳米探针具有较高的弛豫率,且能对胰腺癌patu8988细胞进行荧光和T1-weighted MR成像.     

一种新型磁共振成像造影剂的制备及性能

通过酰化反应将窄分子量分布的低聚壳聚糖(CS_n, n＝6, 8, 11)引入到二乙三胺五乙酸(DTPA)中得到新型配体, 再与Mn²⁺配位得到3种顺磁性Mn(Ⅱ)基配合物, 其结构用IR、元素分析及电感耦合等离子体发射仪(ICP-AES)进行表征. 测定了配合物的纵向弛豫率(r₁), 结果表明, 这类造影剂的弛豫率高于商业化医用的磁共振成像对比剂Gd-DTPA. 通过等温滴定微量热法(ITC)测定了功能配合物与牛血清白蛋白(BSA)相互作用的热力学参数.     

Gd@C82(OH)16的合成及其核磁共振成像

采用电弧放电法合成和HPLC 2步分离法,得到了纯度为95％以上的Gd@C82。以四丁基氢氧化铵(TBAH)为催化剂,用NaOH溶液对Gd@C82进行羟基衍生化,并利用同步辐射XPS分析其C(12)确定Gd@C82羟基化产物的羟基数,得到水溶性的Gd@C82(OH)16。对Gd@C82(OH)16进行了体外弛豫率及体内的核磁共振成像研究。结果表明,与(NMG)2-Gd-DTPA相比,在相同Gd浓度下,Gd@C82(OH)16的质子弛豫率R1提高约3倍,R2提高约7倍。体内核磁成像结果也显示,Gd@C82(OH)16提高了核磁成像对比的效果,其信号在2 h内维持稳定。说明Gd@C82(OH)16在作为磁共振增强剂方面具有较大的潜力。     

α-MnO2纳米棒/多孔碳正极材料的制备及水系锌离子电池性能研究

针对水系锌离子电池锰基正极材料存在比容量低、循环稳定性差等问题, 本工作利用水热法制备出棒状结构的α-MnO₂, 通过柠檬酸钠高温碳化制备多孔碳, 进而通过超声分散等处理制备出α-MnO₂/PCSs复合材料. 三维的多孔网络有助于提高电子导电性, 提供一个稳定的支撑;α-MnO₂纳米棒均匀地附着在多孔碳纳米片层表面, 有效地避免α-MnO₂的团聚, 从而提高锌离子传输效率. 得益于α-MnO₂/PCSs独特的结构优势, 将其作为锌离子电池正极材料, 在电流密度为0.1 A•g^–1的条件下循环100次后, 其可逆容量为350 mAh•g^–1, 在1 A•g^–1的大的电流密度下, 经过1000圈循环后, 容量可达160 mAh•g^–1, 展现了优异的循环稳定性能, 有望成为高性能锌离子电池的潜在正极材料.     

肝靶向性聚天冬酰胺磁共振成像造影剂

用吡哆胺(PM)作为肝靶向基团,先与DTPA双N-羟基琥珀酰亚胺活性酯(SuO-DTPA-OSu)反应生成含一个吡哆胺的DTPA单N-羟基琥珀酰亚胺活性酯(SuO-DTPA-PM),再分别与α,β-聚(2-羟乙基)-L-天冬酰胺和α,β-聚(2-胺乙基)-L-天冬酰胺反应,合成了2类肝靶向性大分子配体,并制备了它们的Gd(Ⅲ)配合物.对所合成的大分子配体以及钆配合物进行了表征.测试了配合物的弛豫率.初步测试大分子载体PHEA和PAEA及其钆配合物的细胞毒性.研究了大分子配体在小白鼠体内分布和大分子钆配合物对大白鼠肝脏造影成像性能.结果表明,与临床广泛应用的小分子磁共振成像造影剂Gd-DTPA相比,以上2类大分子造影剂的弛豫率有明显的提高,并且具有较好的肝靶向性和肝脏成像对比度及清晰度.     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

Synthesis of Some Novel Class of Bis(isoxazoline) and Bis(aziridine) Derivatives

Synthesis of some new bis(isoxazoline) derivatives has been described from terepthaldehyde derived bis(nitrones) using microwave irradiation via 1,3‐dipolar cycloaddition reaction. Bis(isoxazoline) derivatives in turn successfully converted into new bis(aziridine) derivatives via Baldwin rearrangement. Simple reaction methodology, non involvement of catalysts, and good to excellent yields are the important features noticed in this synthesis.     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂。本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望。     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

Sample preparation and current applications of liquid chromatography for the determination of non-structural carbohydrates in plants

This article summarizes the current methods of determination of non-structural carbohydrates (NSCs) in plant samples based on liquid chromatography (LC). NSCs comprise several types of carbohydrates: sugar alcohols (e.g., sorbitol), monosaccharides (e.g., glucose and fructose), disaccharides (e.g., sucrose), oligosaccharides (e.g., raffinose) and polysaccharides [e.g., starch and polyfructans (e.g., inulin)]. NSCs are important in plant metabolism and have to be strictly distinguished from all sorts of structural carbohydrates (e.g., polysaccharide cellulose) that make up the backbone of the plants. Consequently, preservation of structural carbohydrates is a crucial step during sample preparation for NSC determination and is therefore addressed.Sugar alcohols, monosaccharides, disaccharides and those oligosaccharides that are easily soluble in polar solvents can be analyzed directly by high-performance LC. They are also referred to as free carbohydrates (FCs).However, polysaccharides are generally submitted to hydrolyzation into monomers prior to their quantitative analysis. This can be done either chemically, using acids, or enzymatically - both methods are discussed. For identification and quantification of the NSCs after LC separation, the following detectors are used: pulsed amperometry, refractive index, evaporate light scattering and finally, mass spectrometry.     

Electrochemically selective determination of dopamine in the presence of ascorbic and uric acids on the surface of the modified Nafion/single wall carbon nanotube/poly(3-methylthiophene) glassy carbon electrodes

A voltammetric method based on a combination of incorporated Nafion, single-walled carbon nanotubes and poly(3-methylthiophene) film-modified glassy carbon electrode (NF/SWCNT/PMT/GCE) has been successfully developed for selective determination of dopamine (DA) in the ternary mixture of dopamine, ascorbic acid (AA) and uric acid (UA) in 0.1M phosphate buffer solution (PBS) pH 4. It was shown that to detect DA from binary DA-AA mixture, the use of NF/PMT/GCE was sufficient, but to detect DA from ternary DA-AA-UA mixture NF/SWCNT/PMT/GCE was required. The later modified electrode exhibits superior electrocatalytic activity towards AA, DA and UA thanks to synergic effect of NF/SWCNT (combining unique properties of SWCNT such as high specific surface area, electrocatalytic and adsorptive properties, with the cation selectivity of NF). On the surface of NF/SWCNT/PMT/GCE AA, DA, UA were oxidized respectively at distinguishable potentials of 0.15, 0.37 and 0.53 V (vs. Ag/AgCl), to form well-defined and sharp peaks, making possible simultaneous determination of each compound. Also, it has several advantages, such as simple preparation method, high sensitivity, low detection limit and excellent reproducibility. Thus, the proposed NF/SWCNT/PMT/GCE could be advantageously employed for the determination of DA in real pharmaceutical formulations.     

The development and application of guidance on equipment qualification of analytical instruments

 This paper describes the development of guidance for the equipment qualification (EQ) of analytical instruments. EQ is a formal process that provides documented evidence that an instrument is fit for its intended purpose and kept in a state of maintenance and calibration consistent with its use.     

Determination of carcinoembryonic antigen using a novel amperometric enzyme-electrode based on layer-by-layer assembly of gold nanoparticles and thionine

Electrochemical sensing of carcinoembryonic antigen(CEA)on a gold electrode modified by the se- quential incorporation of the mediator,thionine(Thi),and gold nanoparticles(nano-Au),through co- valent linkage and electrostatic interactions onto a self-assembled monolayer configuration is de- scribed in this paper.The enzyme,horseradish peroxidase(HRP),was employed to block the possible remaining active sites of the nano-Au monolayer,avoid the non-specific adsorption,instead of bovine serum albumin(BSA),and amplify the response of the antigen-antibody reaction.Electrochemical ex- periments indicated highly efficient electron transfer by the imbedded Thi mediator and adsorbed nano-Au.The HRP kept its activity after immobilization,and the studied electrode showed sensitive response to CEA and high stability during a long period of storage.The working range for the system was 2.5 to 80.0 ng/mL with a detection limit of 0.90 ng/mL.The model membrane system in this work is a potential biosensor for mimicking the other immunosensor and enzyme sensor.