液相色谱-串联质谱法检测雄蜂蛹粉中50种抗生素残留

建立了液相色谱-串联质谱检测雄蜂蛹粉中50种抗生素残留（大环内酯类、喹诺酮类、磺胺类、四环素类、硝基咪唑类、林可霉素和氯霉素）的方法。样品经高氯酸溶液和醋酸铅溶液提取沉淀蛋白质，清液用磷酸氢二钾溶液调节pH值至8，经固相萃取净化后进行仪器分析。采用多反应监测正离子或负离子模式检测，可以一次完成对雄蜂蛹粉中50种目标化合物的定性和定量测定。50种抗生素的加标回收率为70.2%~118.3%，相对标准偏差（RSD）为1.8%~13.6%。该方法操作简便，灵敏度高，适用于雄蜂蛹粉中多种兽药残留的分析确证。     

CexTi1-xO2复合氧化物表面结构和体相结构的演变

利用X射线衍射、N₂吸附等温线、X射线光电子能谱、X射线吸收谱、H₂-程序升温还原、甲基橙选择化学吸附和等电点测定等方法研究了共沉淀方法制备的一系列Ce_xTi_1-xO₂复合氧化物的结构. 成功发展了甲基橙选择化学吸附和等电点方法研究Ce_xTi_1-xO₂复合氧化物的最外层表面结构, 并定义了“等价CeO₂表面覆盖度”来描述Ce_xTi_1-xO₂复合氧化物的最外层表面结构. Ce_xTi_1-xO₂复合氧化物 (x ≥ 0.7)形成立方萤石相固溶体, Ce_0.3Ti_0.7O₂表现出纯的单斜相, 而其它复合氧化物表现出混合相. Ce_xTi_1-xO₂复合氧化物最外层表面结构的演变行为不同于其体相结构.Ce_0.7Ti_0.3O₂立方萤石相固溶体最外层表面已经部分形成了单斜相Ce_0.3Ti_0.7O₂, 随Ce含量的降低, 单斜相Ce_0.3Ti_0.7O₂从最外层表面向体相生长. Ce_xTi_1-xO₂复合氧化物立方萤石相固溶体和单斜相Ce_0.3Ti_0.7O₂分别在相对较低和较高的温度表现出好的还原性能. 上述结果提供了全面和深层次的Ce_xTi_1-xO₂复合氧化物结构信息.     

Magnetic mixed hemimicelles solid‐phase extraction coupled with high‐performance liquid chromatography for the extraction and rapid determination of six fluoroquinolones in environmental water samples

In this study, a mixed hemimicelle solid‐phase extraction method based on Fe₃O₄ nanoparticles coated with sodium dodecyl sulfate was applied for the preconcentration and fast isolation of six fluoroquinolones in environmental water samples before high‐performance liquid chromatography determination. The main factors affecting the extraction efficiency of the analytes, such as amount of surfactant, amount of Fe₃O₄ nanoparticles, extraction time, sample volume, sample pH, ionic strength, and desorption conditions, were investigated and optimized. The method has detection limits from 0.05 to 0.1 ng/mL and good linearity (r ≥ 09948) in the range 0.1–200 ng/mL depending on the fluoroquinolone. The enrichment factor is ～200. The recoveries (at spiked levels of 1, 5, and 50 ng/mL) are in the range of 79–120%.     

负载型二乙酰氧碘苯与功能离子液体协同氧化醇为醛酮

将聚苯乙烯树脂(PS)先碘化再乙酰基化,制得了负载型二乙酰氧碘苯(PS-DIB)作为氧化剂。2,2,6,6-四甲基-N-氧自由基哌啶醇(TeMPO)与1,4-二溴丁烷反应生成4-溴丁氧基-2,2,6,6-四甲基-哌啶-1-氧化物,再与N-甲基咪唑发生季铵化反应,生成的溴化季铵盐与四氟硼酸钠进行离子交换制得氟硼酸型2,2,6,6-四甲基-N-氧自由基哌啶负载离子液体(TeMPO-IL)。室温下,以离子液体1-甲基-3-丁基咪唑四氟硼酸盐([bmim]BF4)为溶剂,PS-DIB为氧化剂,TeMPO-IL为催化剂,选择性协同氧化各种醇为相应的醛或酮。在实验条件范围内未检测到羧酸副产物。氧化剂、催化剂和溶剂均可循环使用,在苯甲醇的氧化中,循环使用5次,反应的转化率和收率均保持基本不变。     

利用电化学微分质谱在燃料电池的阴极研究碳载体的氧化

利用电化学微分质谱,在双薄层流动电解池中,通过检测二氧化碳产物的信号研究氧气与铂纳米粒子对碳载体氧化机理与动力学的影响．研究发现,碳载体可以在不同的电位区间内被氧化;氧气可以加速碳的氧化,在相同的电位下碳氧化生成二氧化碳产物的速率在氧气饱和溶液中是在氮气饱和溶液中的两倍;铂纳米粒子可以催化碳的氧化,在碳电极上,担载的铂纳米粒子可以大大降低碳氧化的过电势．讨论了铂与氧气促进碳氧化的机理．     

磁性壳聚糖-聚丙烯酸微球的制备及表征

壳聚糖通过与丙烯酸接枝共聚制得壳聚糖聚丙烯酸悬浮液,在铁磁流体(Fe3O4)与聚乙二醇(分散剂)存在下通过与戊二醛交联,制备了磁性壳聚糖聚丙烯酸微球。用扫描电镜、红外光谱对合成的高分子微球进行形貌观察和结构表征,并进行了元素分析和磁性能测试,研究了磁性微球对牛血清白蛋白(BSA)的吸附效果。结果表明,合成的磁性微球外表呈球形,粒径为100～400nm;当Fe含量为2.47%时,磁性微球的饱和磁化强度约为1.30emug,磁矫顽力为280Oe,磁化率为2.16×10-4(常温下),属于顺磁性材料;其对BSA有较好的吸附效果,饱和吸附量约为400mgg。     

Frontispiz: Mild and Versatile Nitrate‐Promoted C?H Bond Fluorination

A novel and facile C H bond fluorination proceeds under remarkably mild conditions (close to room temperature in most cases). Both aromatic and olefinic C(sp²) H bonds with a wide range of electronic properties are selectively fluorinated in the presence of a catalytic amount of simple, cheap, and nontoxic nitrate as the promoter. A Pd^II/Pd^IV catalytic cycle that is initiated by an in situ generated cationic [Pd(NO₃)]⁺ species was proposed based on preliminary mechanistic studies.     

Direct evidence for hydrated protons as the active species in artificial photocatalytic water reduction into hydrogen

Photocatalytic water reduction to hydrogen over oxide semiconductors is one of the most extensively investigated artificial photocatalytic reactions, but the nature of the active species has not yet been elucidated. Here, we successfully prepared Pt/rutile TiO_2(110) surfaces with hydrated proton species via co-adsorption of hydrogen and water and observed the photocatalytic reduction of hydrated protons to H_2 upon UV light illumination. These results provide experimental evidence to prove hydrated protons as the active species for photocatalytic water reduction to hydrogen and demonstrate the occurrence of photocatalytic reduction of hydrated protons to H_2 within the H-bonding network on the catalyst surface instead of directly on the catalyst surface. The Pt-TiO_2 interface is capable of dissociating water to form hydroxyl groups that facilitate the formation of H-bonding network on the catalyst surface to enhance the photocatalytic H_2 production. Our results greatly advance fundamental understanding of artificial photocatalytic water reduction.     

新型咔唑衍生物的合成及其晶体结构

通过9-乙基咔唑-3-甲醛与4-氨基-3,5-二甲基-1,2,4-三氮唑反应,合成了一种新型咔唑衍生物-- 9-乙基咔唑-3-甲醛缩4-氨基-3,5-二乙基-1,2,4-三氮唑(1),其结构经1H NMR, IR和X-射线单晶衍射表征.1属单斜晶系,P2(1)/n空间群,晶胞参数为:a=8.829(8)(A), b=9.863(10)(A), c=19.530(15)(A), β=101.65(5)°, V=1 666(3)(A)3, Dc=1.266 g·cm-3, Z=4, F(000)=672, μ=0.079 mm-1.最终偏离因子R1=0.075 6.     

Facile and practical synthesis of a cannabinoid-1 antagonist via regio- and stereoselective ring-opening of an aziridinium ion

A scalable synthetic strategy of a chiral, trisubstituted imidazolidinone (1), a novel cannabinoid-1 antagonist, starting from a commercially available mandelic acid (5) is described. The key step involves a regio- and stereoselective ring-opening of an aziridinium ion by an aniline nucleophile (3). A mechanistic study revealed the insight into rate amplification at a lower temperature for vicinal diamine 12 formation via a aziridinium ion 14. Although most intermediates are not isolable by crystallization due to their intrinsic physical properties (oil or foamy solid), the reported synthesis furnished pure 1 without any chromatography purification throughout the entire synthesis. Employing green chemistry principles, this novel synthesis appears to be highly efficient for the manufacturing of multi-kilogram quantities of an optically-pure active pharmaceutical ingredient.