改进黏度在线凝胶色谱的测定结果

黏度在线凝胶色谱是一种同时配备浓度和黏度检测器的凝胶色谱,由于其测定过程简单直接,被越来越多地广泛采用,但因为数据处理方式和仪器精度的问题,其数均分子量、重均分子量与分散度结果存在较大误差.实验表明,选择适当的谱峰叠加处理、改进普适校正曲线精度、调整标样进样方式以及选择合适的积分点等手段可以明显改善存在的问题,从而大幅度地提高数均分子量、重均分子量与分散度的结果准确性.     

一种新型Au(Ⅲ)-吡啶酰胺配合物的合成，表征及其与5′-单磷酸鸟苷的反应研究

利用四氯合金酸和N-4-甲基苯基2-吡啶甲酰胺(HL)反应，合成得到了一种新的Au(Ⅲ)配合物：二氯(N-4-甲基苯基2-吡啶甲酰胺合金(Ⅲ)[Au(L-N，N′)Cl₂]。并通过元素分析、红外光谱、核磁共振谱、质谱及X-射线单晶衍射对其进行了表征。结构分析表明，Au(Ⅲ)由二个氮原子和二个氯原子配位，呈平面四方形结构。质谱研究发现，该化合物与5′-单磷酸鸟苷(5′-GMP)反应生成[Au(L-N，N′)(5′-GMP)₂]。     

无机层状复合氢氧化物中顺铂-DNA模型分子的选择性插入

药物分子的选择性包裹和控制释放是药物研究领域中具有挑战性的研究方向。本文研究表明:顺铂-DNA模型分子cis-[Pt(NH₃)₂(5′-GMP)₂](5′-GMP 5′-单磷酸鸟苷)可插入无机层状复合氢氧化物[Zn_0.68Al_0.32(OH)₂](NO₃)_0.32·mH₂O。但另一种层状复合氢氧化物[LiAl₂(OH)₆]Cl·H₂O由于其阳离子层中正电荷密度较高、阳离子层与层间阴离子之间静电作用较强,因而顺铂-DNA模型分子不能通过离子交换方式插入其层间。光谱数据证实插入层间的顺铂-DNA模型分子结构不变。这可能为铂-DNA分子的传递提供新的方法。     

锐钛相虫蛀状介孔二氧化钛的表征

0IntroductionMesostructuredtitania(TiO2)hasattractedagreatdealofattention,inviewofcontrolleddelivery,catalytic,photocatlytic,orenergyconversionapplica-tions犤1犦.Theuseoftitaniumisopropoxidebis-acetylace-tonateprecursors,combinedwithalkylphosphatean-ionicsurfactantsastemplate,ledtothefirstdocu-mentedpuremesoporousTiO2犤2犦.Insubsequentyears,moresyntheticstrategieshavebeendevelopedusingavarietyofstructure-directingagents,forexample,car-boxylicacids犤3犦,alkylamine犤4犦,aminium犤5犦,blockcop-o…     

三乙胺与2-氯-5-甲氧基对苯醌光电子转移反应的CIDNP研究

用化学诱导动态核极化（CIDNP）方法研究了三乙胺与2-氯-5-甲氧基对苯醌在 C6D6，CH3CN溶剂中的反应机理，实验结果表明反应过程中首先形成基态电荷转移 络合物（CTC），在CD3CN中，光照电荷分离形成离子自由基对，使三乙胺亚甲基产 生发射极化信号。同时用UV-vis实验证实CTC的存在。     

A Mild and Efficient Deprotection of Geminal Diacetates Catalyzed by FeCl3 ·6H2O in Ionic Liquid

The selective deprotection of geminal diacetates promoted by FeCl3·6H2O in the ionic liquid [bmim] [BF4] canbe efficiently achieved in good yields. The ionic liquid and the catalyst can be recycled easily and the process is car ried out under mild conditions.     

规整中孔TiO2微球的均相沉淀合成及其在环戊烯氧化反应中的应用

TiO2作为重要的功能性环保无机材料, 因具有特殊的光电性质和物化性能而广泛应用于介(压)电材料、涂料及催化等领域[1～3]. 戊二醛(Glutaraldehyde)是一种重要的精细化学品, 但其生产工艺复杂、条件苛刻. 邓景发等[4]成功开发了以环戊烯为原料, 双氧水为氧化剂, 均相钨酸为催化剂的新型一步法合成路线, 工艺操作简单, 降低了生产成本. 但由于均相催化剂分离复杂, 其固载化方法正在研究中[5～7]. 本文以TiCl4为前驱体, 在均相醇-水热体系中首次合成了高比表面积和规整中孔结构的TiO2微球(约3.6 μm), 其外壳约100 nm, 空隙壳层约300 nm. 考察了制备条件对TiO2微球结构的影响, 并采用孔分布, XRD, SEM及TEM等手段对该TiO2微球进行了表征, 同时考察了TiO2微球负载的WO3催化剂在环戊烯催化氧化合成戊二醛中的反应行为, 并与其它载体进行了比较.     

1, 1'-双(二苯基膦基)二茂铁介导的芳烃碳氢键芳基化反应制备联芳基骨架

The broad existence of the biaryl linkage in bioactive organic molecules and functional materials makes it an attractive synthesis target via construction of aryl-aryl carbon bonds. Transition metal catalyzed cross-coupling reactions of two pre-functionalized aryl partners, e.g., Suzuki-Miyaura cross-coupling and Negishi cross-coupling reactions, are the main methods typically used for the construction of biaryl linkages. Since the end of the last century, transition metal catalyzed direct C―H arylation of unactivated arenes has emerged as a practical alternative to the well-established cross-coupling strategies. However, the use of transition metal catalysts and/or organometallic reagents would lead to problems, such as the disposal of waste from large-scale syntheses and the removal of heavy metal contaminants from pharmaceutical intermediates. In this regard, the base-promoted homolytic aromatic substitution (BHAS) reaction of aryl halides with unactivated arenes offers a simpler strategy for the synthesis of biaryl scaffolds, and avoids the use of transition metals. Although the BHAS reaction can proceed to a small extent without any additives, particularly at elevated temperatures, the addition of organic promoters would significantly accelerate the reaction rate and improve the overall efficiency of the process. Over the past ten years, a wide variety of N- and O-based organic promoters have been developed to promote the BHAS reaction in the presence of the tert-butoxide base. The mechanism of the BHAS reaction has been studied extensively, and is accepted as occurring via a radical chain process involving an aryl radical. However, the role and mode of initiation of most organic promoters studied remain controversial. The development of more and varied organic promoters will surely promote the mechanistic understanding and further development of the BHAS reaction. Herein, we report that 1, 1'-bis(diphenylphosphino)ferrocene (dppf, or DPPF) can act as a P-based promoter to facilitate the direct arylation of unactivated arenes with aryl iodides using potassium tert-butoxide as the base and electron donor. A broad range of aryl iodides and arenes reacted smoothly under the optimized reaction conditions, giving arylated products in good yields and with high regio-selectivity. Intramolecular C―H arylation also worked well following a sequence of single electron transfer (SET)/initiation, 5-exo-trig aryl radical addition, ring expansion, deprotonation, and re-aromatization/propagation. A mechanistic study indicated that the diphenylphosphino group of dppf played a vital role in the initiation step by enhancing the SET-inhibiting ability of the tert-butoxide anion. A primary kinetic isotope effect was observed in the parallel reactions between 4-methoxy-iodobenzene with benzene and deuterated benzene, implying that the deprotonation of the cyclohexadienyl radical intermediate by tert-butoxide was the rate-determining step in the radical chain pathway.     

脊椎状NiCo2O4纳米棒的制备及其析氧和氧还原性能研究

以水热法并进一步焙烧合成脊椎状NiCo₂O₄纳米棒,通过透射电子显微镜（TEM）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）和热重分析仪（TG）等来表征其结构形态及热稳定性.采用线性扫描法（LSV）、循环伏安（CV）研究所制备催化剂的在玻碳和旋转圆盘电极上的电催化活性：在0.1 mol·L^-1 KOH溶液中的电催化析氧反应（OER）和电催化氧还原反应（ORR）.研究结果表明,所制备的脊椎状NiCo₂O₄纳米棒有大量的不饱和态,200℃焙烧制备的脊椎状NiCo₂O₄纳米棒析氧过电位最小可达309 mV,Tafel斜率145.6 mV/dec,其氧还原极限电流密度在1600 rmp可达到5.095 mA·cm^-2,电子转移数在3.2~3.8之间,接近四电子转移机理,其优良电化学性能可能是由于暴露了更多的边缘缺陷的缘故.     

溶解有机质对光照自然水体生物膜体系中H2O2生成的影响

通过模拟实验研究了生物膜胞外聚合物(EPS)和乙二胺四乙酸(EDTA) 2种典型溶解有机质(DOM)成分对自然水体生物膜体系中过氧化氢(H₂O₂)生成特征的影响, 并研究了体系初始pH值、 DOM浓度、 溶解氧(DO)等因素的影响. 结果表明, DOM的存在对自然水体生物膜体系中H₂O₂的生成有明显影响. 光照能促使EPS产生H₂O₂, 而EPS的存在对生物膜产生H₂O₂的直接影响不显著, EPS与生物膜共存体系中的H₂O₂由二者共同产生; EDTA本身不产生H₂O₂, 且对H₂O₂分解影响很小, 但会显著抑制生物膜产生H₂O₂, 且浓度越高抑制作用越明显. 体系pH值、 DOM浓度和DO均能不同程度影响EPS产生H₂O₂及EDTA抑制生物膜产生H₂O₂的作用.