氮杂冠醚取代单Schiff碱过渡金属配合物催化氧化对二甲苯研究

本文将苯并-10-氮杂-15-冠-5或吗啉基取代的单Schiff碱过渡配合物作为催化剂,在常压和120℃条件下,以空气为氧源,研究了对二甲苯催化氧化反应。实验探讨了Schiff碱配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基和反应时间等对对二甲苯催化氧化反应的影响。实验结果表明:Schiff碱配合物中氮杂冠醚的存在能显著缩短反应诱导期,提高催化反应活性和产物选择性;Schiff碱Mn(III)配合物比Schiff碱Co(II)具有更高的催化反应活性;氮杂冠醚Schiff碱Mn(III)配合物对于二甲苯的催化氧化反应转化率大于60%,对甲苯甲酸产物的选择性均高于70%。     

气相色谱-质谱法测定水体中5种典型有机紫外防晒剂

建立了水体中5种典型有机紫外防晒剂甲氧基肉桂酸乙基己酯（ethylhexyl methoxycinnamate,EHMC）、二苯酮-3（benzophenone-3,BP-3）、4-甲基苄亚基樟脑（4-methylbenzylidene camphor,4-MBC）、奥克立林（octocrylene,OC）和胡莫柳酯（homosalate,HMS）的气相色谱-质谱检测方法。对HMS、BP-3衍生化条件进行了系统的优化。以100 μL双（三甲基硅烷基）三氟乙酰胺（N,O-bis（trimethylsilyl） trifluoroacetamide,BSTFA）为衍生化试剂,在100 ℃下反应100 min。水样固相萃取选用Oasis HLB萃取柱（0.5 g）,洗脱溶剂为乙酸乙酯-二氯甲烷（1：1,v/v）,水样pH 3~5。该方法对5种化合物的检出限范围为0.5~1.2 ng/L,定量限范围为1.4~4.0 ng/L。最佳实验条件下,加标水样回收率为87.85%~102.34%,相对标准偏差（n=3）均小于5%。该方法成功地应用于昆明市第一污水厂进出口水样中目标物质的分析。     

席夫碱-铝化合物催化己内酯的开环聚合

设计合成了一系列不对称席夫碱-铝化合物1a~3a,考察了化合物在己内酯(CL)开环聚合反应中的催化性能,研究发现,配合物对CL聚合具有较高的反应活性,并具有活性聚合的特点,聚合反应均符合一级动力学反应特征.在其它条件相同时,吸电子取代的配合物的催化速率约为无吸电子的配合物的4倍,表明席夫碱配体上吸电子基团的存在可以提高配合物催化聚合的活性.     

NEWS

高效液相色谱的应用范围十分广泛,约有80％的有机物均可使用高效液相色谱进行分析。近年来其发展颇为迅猛,功能不断完善。2006年获得匹兹堡金奖产品的赛默飞UltiMate 3000 DGLC双三元液相色谱,便是杰出的代表。其采用独特的双泵设计,每个泵作为一个单独的体系,有各自独立的比例阀和流动相体系,同时单独控制三种不同的流动相,在Chromeleon变色龙软件的支持下,结合独特的阀切换技术,通过灵活的流路连接设计,一套系统即可以轻松实现在线固相萃取、中心切割及全二维液相色谱分离、流动相在线除盐、柱后衍生和反梯度补偿、并联/串联色谱等高级应用。本刊中有多篇文章利用UltiMate 3000 DGLC双三元液相色谱的在线固相萃取( online SPE)技术和二维及全二维液相色谱分离技术,解决了他们遇到的复杂难题。     

磺酰化修饰聚苯乙烯的合成及芳香烃萃取性能

利用自由基聚合反应合成了低分子量聚苯乙烯, 经过端基氧化和磺酰化反应, 制备出一系列极性砜基修饰的低分子量聚苯乙烯. 通过红外光谱(FTIR)、 核磁共振谱(NMR)、 差示扫描量热分析(DSC)以及热重分析(TGA)等手段对聚合物的结构和性能进行了表征, 并通过混合烃萃取分离实验对其芳香烃选择性进行了测试. 结果表明, 随着磺化比例的增加, 甲苯的选择系数和分布系数均显著提高, 表明极性修饰聚苯乙烯对多种芳香烃/链烷烃混合物均具有明显的芳香烃选择性.     

基于配位聚合物的纳米材料的可控合成研究进展

本文围绕近年来基于配位聚合物的纳米材料,包括配合物纳米材料和以其为前体制备的各种氧化物、硫化物等半导体材料和磁性材料的可控合成研究工作,总结了配合物纳米材料的制备方法,主要有液相法、微乳法、扩散法、界面反应法、水热/溶剂热法、高温裂解法等,以及应用方面的研究进展,并展望了配合物纳米材料今后可能的发展方向。     

Syntheses,Characterizations, and Crystal Structures of Two Binuclear Silver Complexes Based on O,O'-Dialkyldithiophosphate and 1,10-Phenanthroline

Two binuclear silver complexes, [Ag2{μ-S2P(OCH2Ph)2}2(phen)2](1) and [Ag2{μ-S2P(OCH2CH2Ph)2}2(phen)2](2), were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetric analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in the triclinic system, space group P1 with a = 9.7881(4), b = 10.7726(4), c = 13.1952(6) , a= 103.686(4), γ = 99.477(3), γ = 107.494(4)°, V = 1246.88(9) 3, Dc = 1.591 g·m-3 and Z = 1; Complex 2 is of monoclinic system, space group P21/n with a = 10.6014(8), b = 24.3969(15), c = 11.5353(10) , β = 14.125(10)°, V = 2722.9(4) 3, Dc = 1.526 g·m-3 and Z = 2. In the molecules of 1 and 2, O,O'-dialkyldithiophosphate anions,(PhCH2O)PS2- and(PhCH2CH2O)PS2- act as bridging ligands and connect two Ag(I) centers into a binuclear unit with Ag2S4P2 eight-membered rings in "chair" conformations. In both crystal structures, face-to-face π-π stacking interactions between the adjacent paralleling aromatic rings of 1,10-phenanthroline play a prominent role in the crystal packing and result in a 1D chain. And such 1D chains are further linked into 3D networks by weak intermolecular C–H···π interactions for 1.     

含肽键芳酰腙镧(Ⅲ)配合物的合成、表征及对四种作物病害的抑制作用

合成了未见文献报道的镧(Ⅲ)与含肽键芳酰腙配体(2-羰基丙酸水杨酰腙)的配合物,经化学分析、元素分析及摩尔电导率等表征推测其组成为:La(H2L)(HL)·H2O(H3L为2-羰基丙酸水杨酰腙C10H10N2O4)。通过红外、紫外及荧光的研究表明配体以羧基氧、羰基氧和亚氨基氮与La3+三齿配位,形成了两个共边五元环的稳定结构。盆栽活体试验表明该配合物对四种作物病害都有不同程度的抑制作用,其中对小麦条锈病的防治效果最好,防治效果达80.8%。     

Synthesis,Crystal Structure and Luminescent Property of an Eu~(3+) Complex

A new Eu(Ⅲ) complex, {[Eu(tta)2(C2H5OH)(NO3)]2(bmp)}·bmp(tta = 2-thenoyltrifluoro- acetonate, bmp = 2,2'-bipyrimidine), has been synthesized and characterized by elemental analysis, IR, luminescence and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/n space group, with a = 11.894(6), b = 14.235(8), c = 19.078(10) , β = 103.423(9)o, V = 3142(3) 3, Z = 2, Mr = 1721.10, Dc = 1.819 g/cm3, F(000) = 1696, the final R = 0.0452 and wR = 0.1398 for 5375 observed reflections with I 2σ(I). In the complex, each Eu(Ⅲ) ion is coordinated with four oxygen atoms from two tta ligands and two nitrogen atoms from a bmp ligand, three oxygen atoms from one NO3- anion and one ethanol molecule, forming a distorted tricapped trigonal prism geometry. Luminescence measurement indicates that the europium complex is a strong red emitter in the solid state at room temperature.     

A New Porous Cadmium(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative and Dicarboxylate:Syntheses,Structure, Thermal Behavior and Luminescence

A new porous Cd(Ⅱ) coordination compound, namely, [Cd(bpdc)(L)2]·3H2O(1, L = 11-fluoro-dipyrido[3,2-a:2,3-c]phenazine and bpdc = 1,1-biphenyl-2,2-dicarboxylate) was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffraction. It crystallizes in tetragonal, space group P4122 with a = 9.8486(4), b = 9.8486(4), c = 45.925(4)A, V = 4454.5(5) 3, Z = 4, C50H29 Cd F2N8O7, Mr = 1004.21, Dc = 1.497 g/cm3, F(000) = 2028, μ(Mo Ka) = 0.562 mm-1, R = 0.0566 and w R = 0.1585. Each Cd(Ⅱ) atom is coordinated by one bpdc anion and two L ligands to give a discrete molecule. Neighboring discrete molecules are stacked by π-π interactions among L ligands, resulting in an interesting 1D supramolecular chain. Moreover, the 1D supramolecular chains are packed with each other to give a porous structure, in which an infinite channel is filled with water molecules. In addition, the thermal behavior and luminescent property of 1 have also been studied.