A fluorophore‐labelled copper complex: crystal structure,hybrid cyclic water–perchlorate cluster and biological properties

A fluorophore‐labelled copper(II) complex, aquabis(dimethylformamide‐κO )(perchlorato‐κO )[2‐(quinolin‐2‐yl)‐1,3‐oxazolo[4,5‐f ][1,10]phenanthroline]copper(II) perchlorate monohydrate, [Cu(ClO₄)(C₂₂H₁₂N₄O)(C₃H₇NO)₂(H₂O)]ClO₄·H₂O, has been synthesized and characterized. A cyclic hydrogen‐bonded water–perchlorate anionic cluster, i.e. [(ClO₄)₂(H₂O)₂]²⁻, has been identified within the structure. Each cyclic anionic cluster unit is interconnected by hydrogen bonding to the cation. The cations join into an infinite hydrogen‐bonded chain running in the [010] direction. Furthermore, interaction of the complex with calf‐thymus DNA (CT‐DNA) and cellular localization within the cells was explored. Spectroscopic studies indicate that the compound has a good affinity for DNA and stains the nucleus of the cells.     

希土冠醚配合物的研究——Ⅶ.轻希土高氯酸盐与2, 3, 11, 12-四苯基-1, 4, 7, 10, 13, 16-六氧-2, 11-十八环二烯配合物的合成和性质

合成了五种轻希土高氯酸盐与标题不饱和冠醚的新固体配合物,并进行了元素分析、溶解度、摩尔电导、UV、IR和~1HNMR等性质研究。     

高浓度LiClO4/丙酮溶液中离子-溶剂和离子-离子的相互作用

利用红外和拉曼光谱技术研究了不同浓度LiClO₄/丙酮溶液中离子-溶剂和离子-离子的相互作用. 红外和拉曼光谱的分析表明, Li^＋与丙酮分子发生了强烈的相互作用, 导致丙酮C—C伸缩振动谱带、C＝O伸缩振动谱带等发生了分裂. Li^＋的溶剂化数随溶液浓度的增加逐渐降低, 在所研究的LiClO₄浓度范围(0.31～3.98 mol•kg^－1)内由3.4减小到1.9. 此外, 根据的谱带变化确定了溶液中存在的多种离子对的形式, 计算了缔合平衡常数, 并与电导实验结果进行了比较, 解释了这两种方法测定的离子缔合常数存在差异的主要原因.     

LITHIUM ION CONDUCTING POLYMER ELECTROLYTES BASED ON ALTERNATING MALEIC ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE CHAINS

A comb polymer with oligo-oxyethylene side chains of the type -(CH_2CH_2O)_(12)CH_3was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethyleneglycol) methyl ether. The polymer can dissolve LiClO_4 salt to form homogeneous amor-phous polymer electrolyte. The ac ion conduction was measured using the complex impedancemethod, and conductivities were investigated as functions of temperatures and salt con-centration. The complexes were first found to have two classes of glass transition whichincrease with increasing salt content. The optimum conductivity attained at 25℃ is inthe order of 5.50×10~(-6)Scm~(-1). IR spectroscopy was used to study the cation-polymerinteraction.     

高氯酸锂-乙酰胺新型二元熔盐电解质的谱学研究

高氯酸锂与乙酰胺在适宜摩尔配比范围内可形成热稳定性良好、电化学性能优良的室温熔盐.从分析LiClO4与乙酰胺形成熔盐的作用机制出发,通过红外、拉曼光谱的谱学分析并应用非局部密度泛函理论方法进行量化计算对二者的相互作用进行了讨论.发现乙酰胺通过Li－O键与LiClO4中的Li＋配位而破坏了LiClO4的离子键,形成很大的配位阳离子,削弱了阴阳离子间的库伦作用力;同时Li－O也导致乙酰胺分子间的氢键断裂,因而体系的共熔温度较之纯物质熔点显著降低,部分样品室温下以液体状态稳定存在.     

Effect of lithium perchlorate on the spontaneous copolymerization of 4‐vinylpyridine with various electron‐rich vinyl monomers

The spontaneous copolymerization of 4‐vinylpyridine (4‐VP) activated with lithium perchlorate (LiClO₄) with various electron rich monomers (p‐methoxystyrene, MeOSt; p‐methylstyrene, MeSt; styrene, St) was investigated in various solvent systems at 75°C. Increasing the LiClO₄ concentration and the nucleophilicity of the electron rich monomer increased the copolymer yields. Both ¹H‐NMR and elemental analysis confirmed the almost 1:1 copolymer structure for VP/MeOSt system which possessed high molecular weight and narrow polydispersity (PDI). Compared to 4‐VP activated with zinc chloride, LiClO₄ systems showed slightly lower yields and much narrower PDI. We also investigated the spontaneous copolymerization of 4‐VP activated with various protic acids in the reaction with various electron rich comonomers. However, generally protic salt forms showed less solubility in organic solvents and showed low molecular weight polymer products with low yields. The proposed initiation mechanism exhibits the formation of a σ‐bond between the β‐carbons of the two donor‐acceptor monomers, creating the 1,4‐tetramethylene biradical intermediate initiating the copolymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1709–1716, 1999     

［Cd(CHZ)3］(ClO4)2的制备和分子结构研究

本文报道了高氯酸三碳酰肼合镉(Ⅱ)的制备方法和分子结构。该配合物结构式为［Cd(CHZ)₃］(ClO₄)₂。晶体属单斜晶系,P2₁/n空间群。晶体学参数为：a=1.0281(1) nm, b=0.8617(1) nm, c=2.1360(1) nm,β=100.53°, V=1.8604(3) nm³; Z=4, Dc=2.076 g·cm^-3, μ(Mo, K_α)=15.43 cm^-1。经全矩最小二乘法对非氢原子坐标和温度因子进行修正。最终偏离因子R=0.0296。在该配合物中,碳酰肼(CHZ)分子作为双齿配体,由羰基氧原子和1位氮原子与Cd配位,形成五员平面螯合环,配合物分子中共有三个这样的螯合环,中心离子为六配位八面体构型;配合物的外界是两个高氯酸根离子,通过库仑力与内界结合在一起。     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

CuO nanoparticles supported on three‐dimensional nitrogen‐doped graphene as a promising catalyst for thermal decomposition of ammonium perchlorate

In the present work, CuO nanoparticles grown on three‐dimensional nitrogen‐doped graphene‐based frameworks (CuO@3D‐(N)GFs) were synthesized using a two‐step method. After the synthesis of three‐dimensional nitrogen‐doped graphene, CuO nanoparticles were deposited on it, by adding cupric acetate followed by thermal treatment. Different analysis methods were used to characterize the products. The as‐prepared nanocomposite was used as a promising catalyst for thermal decomposition of ammonium perchlorate (AP) as one of the most common oxidizer in composite propellants. Differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) techniques were used to investigate the thermal decomposition of ammonium perchlorate. According to the DSC/TGA, high temperature decomposition of AP decreased to 111 °C in the presence of 4% CuO@3D‐(N)GFs and the total heat release (ΔH) from decomposition of AP increased to 1893 J g^?1 which is much more than 590 J g^?1 for pure AP.     

分散微固相萃取/超高效液相色谱-高分辨质谱法测定茶叶中高氯酸盐

基于分散微固相萃取(DMSPE)技术,采用超高效液相色谱-高分辨质谱(UHPLC-HRMS)建立了茶叶中高氯酸盐的检测方法.样品采用乙腈提取,以PSA 和PCX 为吸附填料进行DMSPE 净化,采用Poroshell 120 PFP 色谱柱(50 mm×2.1 mm,1.9 μm)为分析柱,甲醇-1.0％乙酸水溶液作为...