高熵氧化物的设计及其在锂离子电池中的应用研究进展

储能技术的革命性变化对下一代锂离子电池(LIBs)负极材料提出了更高的要求。近年来,一类具有复杂化学计量比的新型材料——高熵氧化物(HEOs)逐渐进入人们的视野并走向繁荣。理想的元素可调节性和吸引人的协同效应使 HEOs有望突破传统阳极的综合性能瓶颈,为电化学储能材料的设计和发展提供新的动力。本文分别从化学成分调控和结构设计2个方面结合本课题组近年来的研究及国内外重要文献,综述了HEOs作为LIBs负极材料的研究进展。在化学成分调控方面通过金属杂原子掺杂、非金属杂原子掺杂来提高HEOs的本征活性。在结构设计方面,通过构建一维结构、二维结构、三维结构、空心结构以及复合碳材料来增加HEOs的反应活性位点数量,从而提高储锂性能。最后,对HEOs在LIBs领域的发展进行了展望。     

预处理气氛对CuO/CeO2/γ-Al2O3催化剂表面性质及“NO+CO”反应性能的影响

用不同的预处理气氛制备了CeO₂/γ-Al₂O₃载体以调节表面Ce的价态,并以Cu(CH₃COO)₂为前驱体制备了CuCeAl催化剂。XRD和H₂-TPR的结果表明在还原气氛下处理的CeO₂/γ-Al₂O₃载体具有更多的活性氧原子,因此相应的CuCeAl催化剂表面有更多分散态的Cu²⁺/Cu⁺物种。NO+CO反应的结果表明分散态的Cu²⁺/Cu⁺是NO转化的活性物质,而Cu⁰在低温下具有较好的N₂选择性。因此,同时含有分散态Cu²⁺/Cu⁺和少量晶相Cu⁰的催化剂具有最好的催化性能。     

稀土化合物TbCl3对成骨细胞系MC3T3-E1增殖、分化和矿化功能的影响

在细胞和分子水平上,研究了稀土化合物氯化铽(TbCl₃)对成骨细胞MC3T3-E1增殖、分化及矿化功能的影响。结果表明,细胞水平上,浓度为0.0001、0.001、0.01、0.1、1和10 μmol·L^-1的TbCl₃均促进MC3T3-E1细胞的增殖、分化及其矿化功能,然而,当浓度升至为100和1000 μmol·L^-1时,TbCl₃表现出抑制作用。分子水平上,浓度为0.0001和0.1 μmol·L^-1的TbCl₃明显上调成骨分化相关基因骨形成蛋白2(BMP-2),碱性磷酸酶(ALP),骨涎蛋白(BSP),Ⅰ型胶原蛋白(Col Ⅰ),骨钙素(OCN)和runt 相关转录因子2(Runx2)的表达。浓度为1 000 μmol·L^-1的TbCl₃则抑制上述成骨分化相关基因的表达。浓度为0.000 1、0.1和1 μmol·L^-1的TbCl₃促进成骨分化相关蛋白Runx2,BMP-2和OCN的表达;结果显示,低浓度的TbCl₃促进MC3T3-E1细胞的成骨分化及矿化功能,而高浓度TbCl₃则呈现出抑制作用。TbCl₃通过调控Runx2的表达刺激早期成骨分化相关基因BMP-2、Col Ⅰ和晚期成骨分化相关基因ALP、OCN的表达,从而诱导MC3T3-E1成骨分化。     

黄渤海近岸海域酚类内分泌干扰物分布特征及其来源解析

在黄渤海近岸海域采集了34个水体样品,利用HPLC-MS/MS分析了双酚A、辛基酚、壬基酚、2,4-二氯酚、对叔丁基苯酚和对特辛基苯酚等6种酚类内分泌干扰物的含量,并探讨了其分布特征及来源.结果表明,中国北部近岸海域6种酚类内分泌干扰物的含量范围在5.25～1351.20ng/mL之间.结合因子分析和层次聚类分析结果,说明渤海、黄海近岸海域中酚类化合物主要以辛基酚、壬基酚、2,4-二氯酚为主,局部海域伴有双酚A的高残留;从整个海域范围看,黄渤海近岸海域水体中酚类化合物污染状况具有区域特征,整体呈现出南高北低的特点,且酚类物质分布具有明显的地区特性,一定程度上具有聚集性;来源解析结果表明黄渤海近岸海域中酚类内分泌干扰物主要来源为生活污水和工业废水.     

光谱分析法研究瓜环对苯并咪唑衍生物的分子识别

利用紫外吸收光谱法、荧光光谱法测定了三种苯并咪唑衍生物与六、七、八元瓜环的相互作用,计算出了主客体配合物的稳定常数,并考察了酸度对苯并咪唑衍生物与瓜环相互作用的影响,最后用紫外吸收光谱法测定了瓜环对三种客体化合物的回收率。实验结果表明:在一定的pH范围内,用紫外吸收光谱法、荧光光谱法可以很明显的观察到瓜环与三种客体的相互作用。六元瓜环与客体相互作用形成1∶1的包结配合物,七、八元瓜环与客体相互作用分别形成1.5∶1和1∶2的包结配合物,六、八元瓜环与三种客体相互作用形成的主客体配合物的稳定常数分别在103～104L·mol-1和1011～1012L2·mol-2范围内。瓜环对三种客体的回收率在98%～105%之间。     

Voltammetric methods of reboxetine analysis and the mechanism of its electrode reactions

Reboxetine (RBX) electrochemical redox behavior at hanging mercury drop (HMDE) and glassy carbon electrodes (GCE) was studied in various pH Britton-Robinson universal buffers using cyclic voltammetry and square-wave voltammetry. RBX was reduced at the HMDE and oxidized at the GCE with reversible adsorption controlled and irreversible diffusion controlled processes respectively. The anodic peak is due to the amine and the cathodic peak may correspond to oxygen protonation. An oxidation reaction mechanism is proposed. The linear relation between peak currents and RBX concentration allowed simple, sensitive, precise and inexpensive voltammetric procedures to be developed. The limit of detection was 0.04 µM RBX. The procedures were successfully applied to human urine and RBX tablet assay. Therapeutic RBX concentrations in human serum were not detected due to strong drug-protein binding. Using bovine serum albumin, the methods were used to investigate the effect of serum protein binding on RBX determination.      

Voltammetric behavior of rutin at a boron-doped diamond electrode. Its electroanalytical determination in a pharmaceutical formulation

This paper examined for the first time, the possibilities of the usage of a boron-doped diamond electrode for the redox behavior of rutin using cyclic and adsorptive stripping voltammetry. The cyclic voltammograms showed a pair of redox peaks at lower potentials followed by an irreversible oxidation peak at higher positive potential. Using square-wave adsorptive stripping voltammetry, the compound yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 4.0 at +0.48 V (vs. Ag/AgCl) (after 60 s accumulations at a fixed potential of 0.2 V). The calibration curve was linear in the concentration range from 0.01 µg mL^?1 to 0.1 µg mL^?1 (1.64×10^?8 M ? 1.64×10^?7 M). A detection limit of 0.0017 µg mL^?1 (2.78×10^?9 M) was observed without any chemical modifications and electrochemical surface pretreatments. As an example, the practical applicability of boron-doped diamond electrode was tested with the measurement of rutin in dietary supplement products.      

Optimization of chemical and instrumental parameters in hydride generation laser-induced breakdown spectrometry for the determination of arsenic,antimony, lead and germanium in aqueous samples

A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L⁻¹, 1.0 mg L⁻¹, 1.3 mg L⁻¹ and 0.2 mg L⁻¹ were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments.     

Investigation of Some Functionalization Reactions of 4‐Benzoyl‐5‐phenyl‐1‐(4‐methoxyphenyl)‐1H‐pyrazole‐3‐carbonyl Chloride and Their Antimicrobial Activity

The 1H‐pyrazole‐3‐carboxylic acid 1 was converted via reactions of its acid chloride 3 with various asymmetrical disubstituted urea and alcohol derivatives into the corresponding novel 4‐benzoyl‐N‐(N′,N′‐dialkylcarbamyl)‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxamide 4a , b and alkyl 4‐benzoyl‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxylate 7a‐c , respectively, in good yields (57%‐78%). Friedel‐Crafts reactions of 3 with aromatic compouns for 15 min.‐2 h led to the formation of the 4‐3‐diaroyl‐1‐(4‐hydroxyphenyl)‐5‐phenyl‐1H‐pyrazoles 9a‐c , 4‐benzoyl‐1‐(4‐methoxyphenyl)‐3‐aroyl‐5‐phenyl‐1H‐pyrazoles 10a , b and than from the acylation reactions of 9a‐c were obtained the 3,4‐diaroyl‐1‐(4‐acyloxyphenyl)‐5‐phenyl‐1H‐pyrazoles 13a‐d . The structures of all new synthesized compounds were established by NMR experiments such as ¹H, and ¹³C, as well as 2D COSY and IR spectroscopic data, and elemental analyses. All the compounds were evaluated for their antimicrobial activities (agar diffusion method) against eight bacteria and two yeasts.     

The Pharmacokinetic Profiles of Pre-Operative Prophylactic Cefepime Application in Pregnant and Non-Pregnant Women Undergoing Surgical Interventions Using a Fully Validated Liquid Chromatographic Method

Pregnancy alters pharmacokinetic profile of many drugs, because of altering body volume and metabolism rate. Therefore, dosage rates and concentrations of drugs must be controlled during pregnancy. Here, we identified the pharmacokinetic profile of pre-operatively given cefepime in caesarean section and gynecological operations using a simple, rapid, cost-effective and valid liquid chromatographic method. The chromatographic separation was performed using 40 mM, pH 3.2 phosphate buffer containing 6 % methanol as mobile phase at 0.30 mL min^?1 flow rate. Gradient elution with methanol was applied to get shorter analysis time without any interference from plasma endogens. During analyses, temperature of column, autosampler and detector were set as 30, 10 and 40 °C, respectively. The detection wavelength was 260 nm and ceftizoxime was used as internal standard. At the optimum conditions, the cefepime analysis from plasma samples was completed in 7 min. Cefepime was extracted from plasma samples using perchloric acid with a very high recovery rate (99.3 %). The method was fully validated according to the Food and Drug Administration guidelines for bioanalytical method validation, and found to be selective, linear, repeatable, reproducible and robust. After validation studies, the method was applied to five caesarean-sectioned and four non-pregnant sectioned women treated with pre-operative, prophylactic single intravenous dose of cefepime (1 g Maxipime^®) in order to determine pharmacokinetic profile of cefepime. Peak serum concentrations of cefepime in caesarean-sectioned women at the arterial port after infusion was 70.11 ± 10.74 μg mL^?1. The mean elimination half-life, volume of distribution and calculated area under the concentration–time curve (AUC)_0–∞ were 1.10 ± 0.23 h, 14.22 ± 2.29 L and 101.55 ± 10.99 μg h mL^?1 for caesarean-sectioned women; and 1.14 ± 0.21 h, 14.76 ± 2.92 L and 104.71 ± 36.34 μg h mL^?1 for non-pregnant sectioned women, respectively. The area under curve, elimination half-life, maximum plasma concentration and the mean distribution volume of cefepime were not changed in case of pregnancy.