Cu(Ⅱ)、Zn(Ⅱ)Schiff碱配合物的合成及其光热性质

用5-硝基水杨醛与色氨酸缩合制备了一种Schiff碱配体,将其与过渡金属Cu(Ⅱ)、Zn(Ⅱ)进行作用合成出两种新型的配合物.采用元素分析、差热-热重、IR、UV、摩尔电导率等对配体和配合物进行了表征,并测定了化合物的荧光性质和对超氧离子的催化歧化作用.     

新型BrΦnsted-Lewis酸性离子液体的合成及其在松香二聚反应中的应用(英文)

合成、表征了新型 Brφnsted-Lewis 酸性离子液体 1-（3-磺酸）-丙基-3-甲基咪唑氯锌酸盐 （[HO3S-（CH2）3-mim]Cl-ZnCl2）, 并将其用于催化松香二聚反应. 结果表明, [HO3S-（CH2）3-mim]Cl-ZnCl2 （ZnCl2摩尔分数x 〉 0.5）为 Brφnsted 和 Lewis 双酸性, 且以 [HO3S-（CH2）3-mim]Cl-ZnCl2 （x = 0.64） 的催化性能较佳. 在松香 5.0 g, 甲苯15 g, 离子液体质量分数 5%, 反应温度 110℃ 和反应时间 4 h 的较佳实验条件下, 所得产物聚合松香的软化点为 118 ℃. 此外, 该催化剂的使用有利于产物的分离且分离的离子液体催化剂具有良好的重复使用性能.     

粉末压片X射线荧光光谱法与红外吸收光谱法联合测定萤石中各组分

采用粉末直接压片法,用X-射线荧光光谱法[1]测得萤石中Ca总量,Fe2O3,P,SiO2,K2O的含量,再用红外吸收光谱法测得样品中碳含量,换算得到CaCO3中的钙含量,进一步求得萤石中CaF2含量。此方法简便、准确。用9个标准物质制定了工作曲线,并进行了自测,另用该系列中5号样品(GBW07254)进行准确度和精密度测试,结果令人满意。     

无碱条件下Au/ZnO选择性催化氧化1,3-丙二醇合成3-羟基丙酸甲酯

采用溶胶-沉积法合成了高选择性的Au/ZnO催化剂,用于1,3-丙二醇选择性氧化酯化为3-羟基丙酸甲酯的反应.研究了保护剂PVA用量、金溶胶合成温度、金负载量及催化剂循环利用对反应的影响,且优化了反应温度和反应压力,并对催化剂进行了XRD和TEM表征.结果表明,PVA∶Au(m/m)=1∶4、金溶胶合成温度25℃、金负载量1%的Au/ZnO对目标反应的催化活性最好,在100℃和Po2=2MPa的条件下1,3-丙二醇的转化率达82.8%,产物3-羟基丙酸甲酯的选择性达95.4%.Au纳米粒子的粒径影响催化性能,在Au平均粒径为2.8~6.1nm的范围内,产物选择性随Au纳米粒子的粒径的减小而增大,平均粒径在2.8~4.8nm的范围内时,催化剂具有较好的产物选择性(大于90%);Au/ZnO催化剂循环利用4次后催化性能(转化率和选择性)无明显下降;并推测了无碱条件下Au/ZnO选择性催化氧化1,3-丙二醇合成3-羟基丙酸甲酯的反应机制.     

高效液相色谱法测定润肤霜和洗发露中的银杏黄酮类物质

建立了测定润肤霜和洗发露中3种银杏黄酮类物质(槲皮素、山萘素和异鼠李素)的高效液相色谱分析方法。样品经甲醇提取、离心后,提取液以Fortis Phenyl色谱柱(4.6×250 mm,5μm)分离,体积分数0.5%H3PO4-甲醇流动相体系等度洗脱,在波长367 nm下用二极管阵列检测器检测,以保留时间结合紫外光谱定性,外标法定量。结果表明:3种目标分析物分离度好;在0.25~50.0 mg/L范围内线性关系良好,相关系数为0.9992~0.999 9;槲皮素、山萘素和异鼠李素的方法检出限(S/N=3)分别为0.8,1.0和1.0 mg/kg;添加水平为5~500 mg/kg时,回收率为83.5%~102.8%,相对标准偏差(RSD,n=6)为1.6%~6.5%。方法适用于护肤类和洗护发类化妆品中槲皮素、山萘素和异鼠李素的测定。     

Validation study on 660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry

A new method using gel permeation chromatography (GPC) cleanup followed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) has been established for quantitative determination of 437 pesticide residues in animal tissues such as beef, mutton, pork, chicken, and rabbit. Based on an appraisal of the characteristics of both GC-MS and LC-MS-MS, validation experiments were conducted for 660 pesticides. In the method, 10 g animal samples were mixed with 20 g sodium sulfate and extracted with 35 mL of cyclohexane+ethyl acetate (1+1) twice by blender homogenization, centrifugation, and filtration. Evaporation was conducted and an equivalent of 5 g sample was injected into a 400 mm x 25 mm S-X3 GPC column, with cyclohexane+ethyl acetate (1+1) as the mobile phase at a flow rate of 5 mL/min. The 22-40 min fraction was collected for subsequent analysis. For the 368 pesticides determined by GC-MS, the portions collected from GPC were concentrated to 0.5 mL and exchanged with 5 mL hexane twice. For the 69 pesticides by LC-MS-MS, the portions collected from GPC were dissolved with acetonitrile+water (60+40) after taking the extract to dryness with nitrogen gas. In the linear range of each pesticide, the correlation coefficient was r > or = 0.98, exceptions being dinobuton, linuron, and fenamiphos sulfoxide. At the low, medium and high three fortification levels of 0.2-4800 microg/kg, recoveries fell within 40-120%, among which 417 pesticides recoveries between 60% and 120%, accounting for 95%, 20 analytes between 40% and 60%, accounting for 5%. The relative standard deviation was below 28% for all 437 pesticides. The limits of detection for the method were 0.2-600 microg/kg, depending on each pesticide.     

萘咪唑类稀土配合物的晶体结构和荧光性质

通过2-（2''-羟基-3''-甲氧基）萘咪唑（HL）和Ln（NO）₃·6H₂O反应,合成了4种单核稀土配合物[Ln（HL）₂（NO₃）₃]·CH₂Cl₂（Ln=Sm（1）,Eu（2）,Tb（3））和[Ln（HL）₂（NO₃）₂（CH₃OH）]NO₃·CH₃OH（Ln=Yb（4））。X射线单晶衍射分析表明配合物1~4均通过配体萘环间的π-π作用呈现蝴蝶状结构。荧光性质表明仅有配合物4显示Yb³⁺稀土离子的特征发光,固态和在乙腈溶液中的荧光寿命分别为8.27 μs和4.40 μs。     

氧化程度对微细鳞片可膨胀石墨结构及膨胀性的影响

以平均粒径为19.71μm的天然微细鳞片石墨为原料,通过化学氧化法制备了具有不同氧化程度的可膨胀石墨,采用XRD、FTIR、Raman、SEM等对可膨胀石墨的结构与膨胀性进行了表征。结果表明：当氧化程度较低时制得的微细鳞片可膨胀石墨由石墨、石墨层间化合物和氧化石墨三相组成;随着氧化程度的增加,氧化石墨相含量与可膨胀石墨结构无序程度逐渐增高,石墨层间化合物相含量先增加后减少,石墨相含量则逐渐降低;氧化促使HSO₄^-或SO₄^2-插入石墨层间,插入层间的HSO₄^-或SO₄^2-量是决定可膨胀石墨膨胀容积的关键因素,制备的微细鳞片膨胀石墨的膨胀容积可达65.9mL·g^-1。     

Prenylated isoflavones with potential antiproliferative activities from Mappianthus iodoides

Abstract

A phytochemical investigation on the stems of Mappianthus iodoides led to the isolation of a new naturally occurring prenylated isoflavone, mappianthone A (1), together with seven known analogues (2?8). The structure of 1 was elucidated by extensive spectroscopic methods and the known compounds were identified by comparison with data reported in the literature. All isolated compounds were evaluated for their antiproliferative activities against five human cancer cell lines: HL-60, SMMC-7721, A-549, MCF-7 and SW480 in vitro. Compounds 1?8 showed significant antiproliferative effects against several human cancer cell lines with IC₅₀ values ranging from 0.16 to 12.68?μM.

     

α-取代氨基氟代苯基膦酸酯衍生物的合成、晶体结构与抗癌活性

利用席夫碱与亚磷酸酯反应, 合成了新型O,O'-二烷基-α-(6-甲氧苯并噻唑-2-基氨基)-4-氟苯基膦酸酯化合物, 结构经元素分析, IR, ¹H NMR, ¹³C NMR和X单晶衍射确认. X单晶衍射测试结果表明: 化合物3d分子属于四面体晶系, 空间群I4(1)/a, a＝2.1055(3) nm, b＝2.1055(3) nm, c＝2.0521(5) nm, α＝90.00°, β＝90.00°, γ＝90.00°, V＝0.9098(3) nm³, Z＝16, D_c＝1.321 mg/m³, ＝0.250 mm^－1, F(000)＝3808. 化合物还存在着1个分子内氢键[N(2)—H(2)…O(1)]. 生物测定表明化合物3f在20 g/mL浓度下对PC3细胞的抑制率为84.3%.