Investigations into distribution of lidocaine in human autopsy material

With screening methods in the legal medicine drugs were often detected in autopsy material. In this study the antiarrhythmic and the local anesthetic drug lidocaine could be proved in fifty‐one cases and determined in different autopsy materials. For the first time the comparison of so many distribution patterns of lidocaine in human compartments was possible. A liquid‐liquid extraction procedure, a standard addition method and LC/MS/MS were used for analytics. The measured concentrations in blood were in the therapeutic range or lower. The time between lidocaine application and death was given in twenty‐nine cases. These data were very helpful to estimate and interpret the distribution process of lidocaine between application and death. This time exerted a crucial influence on the distribution of lidocaine in the compartments. Most of the intravenous applicated lidocaine was found in heart blood after a very short time of distribution. Afterwards the highest concentrations were measured in brain. Later the highest concentration was found in the kidney samples or in urine. If the time between lidocaine application and death is known, the results of this study can be used to deepen the knowledge of its pharmacokinetics. If this time is unknown, the circumstances and the causes of death can be better explained. Copyright © 2015 John Wiley & Sons, Ltd.     

Alkyne hydrogenation using Pd–Ag hybrid nanocatalysts in surface‐immobilized dendrimers

A series of Pd–Ag mixed‐metal nanocatalysts were prepared by reduction of Pd–Ag salts in the presence of poly(propylene imine) dendrimers, which were covalently bound to the surface of a silica polyamine composite, BP‐1 (polyallylamine covalently bound to a silanized amorphous silica gel). Three different Pd‐to‐Ag ratios were evaluated (50:50, catalyst 1 ; 40:60, catalyst 2 ; 60:40, catalyst 3 ) with the goal of determining how the amount of Ag effects selectivity, rate and conversion in the selective reduction of alkynes, such as phenylacetylene and 1‐ or 4‐octyne, to the corresponding alkenes. Conditions for the catalysis are reported where there is improved selectivity without a serious reduction in rate when compared with the analogous Pd‐only catalysts. Catalyst 2 worked best for phenylacetylene and catalyst 3 worked best for the octynes. The catalysts could be reused seven times without loss of activity. Copyright © 2015 John Wiley & Sons, Ltd.     

拓扑材料中的超导

近来,人们在凝聚态体系中发现了由拓扑不变量定义的物相,其中最重要的有拓扑绝缘体、拓扑半金属和拓扑超导体等.这些物相的拓扑性质由非平凡的拓扑数描述,相应的材料被称为拓扑材料,具有诸多新奇的物理特性.其中拓扑超导体由于边界上有满足非阿贝尔统计的Majorana零能模,成为实现拓扑量子计算的主要候选材料.除了探索本征的拓扑超导体外,由于拓扑性质上的相似性,在不超导的拓扑材料中调制出超导自然成为了实现拓扑超导的重要手段.目前,人们发展了栅极调制、掺杂、高压、近邻效应调制和硬针尖点接触等多种技术,已经成功地在许多拓扑绝缘体和半金属中诱导出了超导,并对超导的拓扑性和Majorana零能模进行了研究.本文回顾了本征拓扑超导候选材料,以及拓扑绝缘体和半金属中诱导出超导的代表性工作,评述了不同实验手段的优势和缺陷、分析了其超导拓扑性的证据,并提出展望.     

Influence of the Degree of Deacetylation of Chitosan and BMP-2 Concentration on Biocompatibility and Osteogenic Properties of BMP-2/PLA Granule-Loaded Chitosan/β-Glycerophosphate Hydrogels

Compositions based on chitosan/β-glycerophosphate hydrogels with highly porous polylactide granules can be used to obtain moldable bone graft materials that have osteoinductive and osteoconductive properties. To eliminate the influence of such characteristics as chain length, degree of purification, and molecular weight on a designed material, the one-stock chitosan sample was reacetylated to degrees of deacetylation (DD%) of 19.5, 39, 49, 55, and 56. A study of the chitosan/β-glycerophosphate hydrogel with chitosan of a reduced DD% showed that a low degree of deacetylation increased the MSCs (multipotent stromal cells) viability rate in vitro and reduced the leukocyte infiltration in subcutaneous implantation to Wistar rats in vivo. The addition of 12 wt% polylactide granules resulted in optimal composite mechanical and moldable properties, and increased the modulus of elasticity of the hydrogel-based material by approximately 100 times. Excessive filling of the material with PLA (polylactide) granules (more than 20%) led to material destruction at a ~10% strain. Osteoinductive and osteoconductive properties of the chitosan hydrogel-based material with reacetylated chitosan (39 DD%) and highly porous polylactide granules impregnated with BMP-2 (bone morphogenetic protein-2) have been demonstrated in models of orthotopic and ectopic bone formation. When implanted into a critical-size calvarial defect in rats, the optimal concentration of BMP-2 was 10 μg/mL: bone tissue areas filled the entire material’s thickness. Implantation of the material with 50 μg/mL BMP-2 was accompanied with excessive growth of bone tissue and material displacement beyond the defect. Significant osteoinductive and osteoconductive properties of the material with 10 μg/mL of BMP-2 were also shown in subcutaneous implantation.     

g-C3N4催化石墨化碳质材料的制备及光催化性能研究

通常采用以氢氧化物作为造孔剂,过渡金属硝酸盐或氯化物作为石墨化催化剂的传统两步法策略制备多孔石墨化碳材料。然而制备过程中多涉及有毒和腐蚀性试剂,且多步骤的过程耗时较长。本文以双氰胺为原料通过热缩聚反应得到g-C₃N₄,采用高铁酸钾为催化剂一步法实现g-C₃N₄的同步碳化-石墨化,并研究其光催化性能。与传统的两步法相比,该方法耗时少、效率高、无污染。与初始的g-C₃N₄材料相比,石墨化g-C₃N₄衍生碳质材料不仅显著改善了可见光的吸收,而且大大增强了光催化活性。研究了不同石墨化温度对g-C₃N₄衍生碳质材料在可见光下降解甲基橙溶液的影响。700 ℃下制备的衍生碳质材料的降解率为12.4 mg/g。光电化学测试结果表明,多孔g-C₃N₄衍生碳质材料的光生载流子密度、电荷分离和光电流(提高了5.4倍)均得到显著提高。因此,该简便、灵活方法为提高g-C₃N₄衍生碳质材料的吸附和光催化性能提供了一种有前景的、高效的途径。     

ZnO超细纳米线阵列的制备及其电化学性能

以Zn(NO₃)₂· 6H₂O和C₆H₁₂N₄为原材料,采用二步水热法在碳纤维布上合成了形貌尺寸均匀的ZnO超细纳米线阵列。用 X 射线衍射(XRD)和扫描电镜(SEM)对其晶体结构和形貌进行了表征,利用恒流充放电测试等手段对其进行电化学性能测试。测试结果表明,材料表现出优异的电化学性能。在200 mA/g的电流密度下循环150次后,ZnO超细纳米线阵列仍然约有730 mAh/g的充放电比容量,库伦效率保持在95%以上。在1 200 mA/g的大倍率条件下,材料的充放电比容量依旧可达481 mAh/g左右,表现出十分良好的循环稳定性和可逆性能,是一种较为理想的锂离子电池负极复合材料。     

Local atomic and electronic structure in the LiVPO4(F,O) tavorite-type materials from solid-state NMR combined with DFT calculations

⁷Li, ³¹P, and ¹⁹F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO₄F_1-yO_y materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D ⁷Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO₄–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO₄X₂ environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short V^IVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain.     

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)₂) clusters based on coinage metals, [(PPh₃)₂AgO₂CFcCO₂Ag(PPh₃)₂]₂ ⋅ 7 CH₃OH (SC₁: super capacitor) and [(PPh₃)₃CuO₂CFcCO₂Cu(PPh₃)₃] ⋅ 3 CH₃OH (SC₂), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g⁻¹ and 210 F g⁻¹ specific capacitance at 1.5 A g⁻¹ in Na₂SO₄ electrolyte, respectively. The obtained results show that the presence of Cu^I instead of Ag^I improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC₂ ([(PPh₃)₂CuO₂CFcCO₂]_∞), a polymeric structure of SC₂, was synthesized and used as an energy storage electrode. PSC₂ displays high conductivity and gives 455 F g⁻¹ capacitance at 3 A g⁻¹. The PSC₂ as a supercapacitor electrode presents a high power density (2416 W kg⁻¹), high energy density (161 Wh kg⁻¹), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.     

基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

半导体纳米复合材料的制备及其光电催化CO2还原

本实验通过模拟植物光合作用,设计制备了新颖的光电联合催化池3D-ZnO/Ni BiVO4/FTO,用电化学沉积法制备了泡沫镍负载的ZnO纳米棒光电阴极和BiVO4光电阳极,以0.1 mol·L^−1 KHCO3水溶液作为电解质,1 mmol·L^−1曙红Y为光敏剂,在−0.6 V硅太阳电池的电压下光电催化还原CO2得到了乙醇、乙酸和甲醇,总产率22.5μmol·L^−1·h^−1·cm^−2。实现了将太阳能贮存为化学能并减少了空气中的CO2,加深了学生对绿色化学和植物Calvin循环机理的理解。