香豆素类荧光增强型Cu2+荧光分子探针

设计合成了含酰肼和亚胺结构的双香豆素类Cu2+荧光分子探针CCu,其结构用1HNMR、IR、HRMS和元素分析进行了表征,并考察了其光谱性能。CCu在常见碱金属离子(K+,Na+)、碱土金属离子(Ca2+,Mg2+)、过渡金属及重金属离子(Cd2+,Ag+,Fe3+,Pb2+,Hg2+,Cr3+,Co2+,Ni2+,Cu2+,Zn2+)中能够专一性地识别Cu2+。滴加Cu2+后引起吸收光谱蓝移38 nm,荧光光谱蓝移17 nm,荧光增强8.2倍,溶液荧光由无色变为蓝色。CCu对pH不敏感具有较低的pKa值(3.32±0.07),可在近中性和弱碱性范围内对Cu2+进行检测。     

二氨基硫脲异双核席夫碱化合物的合成与表征

以3-羧基水杨醛与二氨基硫脲为原料,在酸性条件下,以甲醇为溶剂,合成了3-羧基水杨醛双缩二氨基硫脲席夫碱(H2L)及其单核配合物NiL和异双核配合物NiML(M=Mn3+,Fe3+,Co2+,Cu2+,Zn2+)。考察了反应时间、温度、原料配比对该合成的影响。结果表明,反应的最佳条件为:3-羧基水杨醛∶二氨基硫脲=2.4∶1(摩尔比),在70~80℃条件下反应3 h,产率可达78%。通过元素分析、1HNMR、IR、UV-vis、摩尔电导等手段对合成得到的席夫碱化合物的组成和结构进行表征。     

一个镉配位聚合物对Fe3+的识别

以一个镉配位聚合物{[Cd(L1)(1,3-bdc)(H2O)2][Cd(1,3-bdc)(H2O)3]·2H2O}(1)(L1=4-(4-甲基苯基)-4H-1,2,4-三唑,1,3-bdc=间苯二甲酸根)为荧光探针,对14种金属离子识别。结果表明配合物1能够选择性识别Fe3+,除Cu2+外几乎不受他金属离子(Ag+、Zn2+、Pb2+、Ni2+、K+、Hg2+、Mg2+、Co2+、Cd2+、Ca2+、Ba2+和Al3+)干扰。探针配合物1的荧光强度与Fe3+的浓度(1. 0×10-5～10. 0×10-5mol/L)呈良好的线性关系,R2=0. 9938。     

罗丹明荧光探针对铜离子的识别性能研究

根据罗丹明母体结构的闭环(无荧光)与开环(强荧光)的相互转化的机理,设计并合成了2个用于检测铜离子的新型Schiff-base缩合的罗丹明荧光探针RH-2和RH-3。在生理环境下(20 mmol/L PBS缓冲溶液,p H值7.4),当加入Mg2+,Ca2+,Ag+,Cd2+,Co2+,Fe2+,Fe3+,Mn2+,Ni2+,Pb2+,Zn2+,Cr3+,Hg2+和Al3+等金属离子后,探针荧光强度迅速增强,而只有加入铜离子后荧光增强比较小,证明探针对铜离子具有很好的选择性。这种高选择性的荧光探针对于研究生理活动、环境中Cu(II)离子的存在和含量具有潜在应用价值。     

DIPYRRIN和BODIPY衍生物的合成及其对金属离子识别性能的研究

本文设计了一类基于DIPYRRIN和BODIPY衍生物的荧光传感器2a和2b,在PBS缓冲溶液中对Pb2+具有良好的选择性和灵敏度。2a的荧光增强作用是其他离子(Na+,Li+,K+,Ag+,Mg2+,Ca2+,Cu2+,Ba2+,Fe3+,Y3+,Al3+,Co2+,Ni2+,Pb2+和Zn2+)的5倍,2b为2倍。试验证明2a和2b与Cu2+是以1∶3的方式结合。     

SOFC阴极材料PrBa0.85Ca0.15CoMO5+δ的制备与性能研究

采用溶胶-凝胶法分别制备出PrBa_(0.85)Ca_(0.15)CoMO_(5+δ)(M=Co,Fe,Mn,Ni,Cu)阴极材料,通过X射线衍射(XRD)、扫描电镜(SEM)、直流四探针法、热膨胀系数(TEC)测试的手段对样品进行了表征。结果表明:溶胶-凝胶法制备的PBCCM(M=Co,Fe,Mn,Ni,Cu)均为双钙钛矿结构,阴极粉体颗粒小而且分布均匀。在温度400—800℃的测试条件下,PBCCM(M=Co,Cu,Fe)的电导率随着温度的升高而减小,表现出类金属导电机理。掺杂Cu的阴极材料的电导率在400℃最大达到451 S/cm。Mn,Ni,Cu元素的掺杂都能明显地降低PBCCM系阴极材料的热膨胀系数。     

金属酞菁光复合催化剂的制备及光催化性能研究

采用固相熔融法制备了不同中心金属的酞菁配合物MPc(M=Mn2+、Co2+、Ni2+)光复合催化剂,研究MPc对亚甲基蓝的催化降解效果。结果表明,可见光照射下,MPc对亚甲基蓝的降解效率Ni Pc> MnPc> Co Pc,最佳反应条件为:空气通入量120 m L/min,催化剂Ni Pc的加入量1. 0 g/L,反应150 min时,10 mg/L亚甲基蓝的降解率达97. 5%。降解反应符合一级动力学议程。     

金属酞菁光复合催化剂的制备及光催化性能研究

采用固相熔融法制备了不同中心金属的酞菁配合物MPc(M=Mn2+、Co2+、Ni2+)光复合催化剂,研究MPc对亚甲基蓝的催化降解效果。结果表明,可见光照射下,MPc对亚甲基蓝的降解效率Ni Pc MnPc Co Pc,最佳反应条件为:空气通入量120 m L/min,催化剂Ni Pc的加入量1. 0 g/L,反应150 min时,10 mg/L亚甲基蓝的降解率达97. 5%。降解反应符合一级动力学议程。     

以香豆素为母体的荧光探针的合成、离子识别及拟合计算研究

设计合成了含噻唑和腙结构的香豆素类钴离子荧光探针分子CCo,其结构用1HNMR和13CNMR进行了表征,考察了其光谱性能和电化学性能,并对其结构进行了拟合计算研究。CCo在常见金属离子(Cd2+、Co2+、Na+、Mn2+、Fe3+、Pb2+、Hg2+、Cu2+、Zn2+、Cu+、K+、Mg2+、Ag+、Ni2+、Cr3+)中能够选择性地识别Co2+。滴加Co2+后探针吸收光谱红移60 nm,荧光光谱蓝移75 nm。探针分子溶液在三电极系统及四丁基高氯酸胺作电解质下能用于Hg2+的检测。通过拟合计算进一步验证了探针吸收光谱峰值与实验值一致。     

由电镀废液制备Ni-Zn-Cu合金或Ni-Zn合金镀液

Ni- Zn- Cu或 Ni- Zn合金镀液的制备可以由电镀废液和含 Ni或 Zn的金属屑酸浸出液相混合。具体做法如下 :1 )选择两种以上的电镀废液 ,测定其中的Ni2 +、Cu2 +、Zn2 +、Fe2 +、Fe3+、Cr3+和 Pb2 +等离子的浓度。2 )测定含 Ni和 Zn的金属屑酸浸出液中 Ni2 +和 Zn2 +离子的浓度。3)将已测定浓度的两种溶液混合并适当加水 ,使所得混合液中各种离子的浓度分别为 Ni2 +1 5～ 58g/L;Zn2 +2 8～ 4 4g/L;Cu2 +0～ 1 .4 3g/L;( Fe2 ++ Fe3+) 0～ 5.0 g/L;Cr3+0～ 1 .0 g/L 和Pb2 +0 .0 5g/L。当 Cu2 +的浓度低于 0 .5g/L时 ,得到适合电…     

二连接芳香酰胺配体桥联稀土一维配位聚合物的合成与表征

制备了二连接酰胺配体L{L=1,4-双[(2′-苄胺甲酰基苯氧基)-甲基]苯}的稀土Pr3+、Eu3+和Tb3+的配合物,测定了Pr3+配合物的单晶结构,同时还对Eu3+和Tb3+配合物的荧光性质进行研究。X-射线单晶衍射测定结果表明,荧光配体采用双-单齿桥联配位特征与稀土Pr3+离子形成环链相间的一维聚合物{[Pr(NO3)3]2.L3}n。配合物属三斜晶系,PI空间群,稀土离子与来自三个配体的羰基氧和三个双齿硝酸根配位,总配位数为9,形成变形的三帽三角棱柱构型的配位多面体。荧光测试结果表明,芳香羧酸经酰胺化后依然能保持对稀土Eu3+、Tb3+离子的敏化发光性能,而配合物的溶解性与水杨酸配合物相比则得到明显改善。     

Metal ion-binding properties of the diphosphate ester analogue, methylphosphonylphosphate, in aqueous solution

The stability constants of the 1:1 complexes formed between methylphosphonylphosphate (MePP(3-)), CH(3)P(O)(-) (2)-O-PO3(2-), and Mg(2+), Ca(2+), Sr(2+), Ba(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), or Cd(2+) (M(2+)) were determined by potentiometric pH titration in aqueous solution (25 degrees C; l = 0.1 M, NaNO(3)). Monoprotonated M(H;MePP) complexes play only a minor role. Based on previously established correlations for M(2+)-diphosphate monoester complex-stabilities and diphosphate monoester beta-group. basicities, it is shown that the M(Mepp)(-) complexes for Mg(2+) and the ions of the second half of the 3d series, including Zn(2+) and Cd(2+), are on average by about 0.15 log unit more stable than is expected based on the basicity of the terminal phosphate group in MePP(3-). In contrast, Ba(Mepp)(-) and Sr(Mepp)(-) are slightly less stable, whereas the stability for Ca(Mepp)(-) is as expected, based on the mentioned correlation. The indicated increased stabilities are explained by an increased basicity of the phosphonyl group compared to that of a phosphoryl one. For the complexes of the alkaline earth ions, especially for Ba(2+), it is suggested that outersphere complexation occurs to some extent. However, overall the M(Mepp)(-) complexes behave rather as expected for a diphosphate monoester ligand.     

聚硅酸硫酸铝铁(PSAFS)的制备

以硫酸铝、硫酸铁、硅酸钠为原料,采用水热法制备了高效复合絮凝剂聚硅酸硫酸铝铁(PSAFS),研究了铁铝比、pH、反应时间、反应温度、铁硅比对PSAFS去浊性能的影响,获得了制备PSAFS的优化工艺条件为:N(Fe~(3+)):N(Al~(3+))=1:1、pH为1.5、反应时间为5h、反应温度为50℃、N(Fe~(3+)):N(Si O_2)=10:1。最后对优化工艺条件下的产物进行了物相分析。     

氨荒酸盐的合成及配位性能

以CS2、NaOH和仲胺为原料,在无水乙醇中制得了3种N,N-二烃基氨荒酸盐R2NCS2Na.H2O[R2N=i-Pr2N、O(CH2CH2)2N、MeN(CH2CH2)2N],用元素分析、XRD、FTIR等对产物进行了表征,并探索了合成工艺条件,利用紫外分光光度法测定了氨荒酸盐与As3+、Sb3+、Bi3+的配位性能。结果表明,氨荒酸盐与金属离子能形成稳定的配合物,其配位能力的强弱顺序为BiI3.(i-Pr)2NCS2Na.H2OSbI3.(i-Pr)2NCS2Na.H2OAsI3.(i-Pr)2NCS2Na.H2O。实验确定的合成工艺条件为:n(仲胺)∶n(NaOH)∶n(CS2)=1.0∶1.5∶1.8,反应时间2h,产率分别为89.7%、91.2%和93.2%。     

β-二酮包覆发光粉制备PVC发光塑料的研究

以β-二酮为原料,利用有机配位体(β-二酮)与SrAl_2O_4发光粉中的Eu~(2+),Dy~(3+)金属离子形成配位键,制备出表面包覆有β-二酮的(SrAl_2O_4:Eu~(2+),Dy~(3+))复合发光粉体,将包覆的发光粉与聚氯乙烯(PVC)共混制成发光塑料.荧光光谱测试结果表明:包覆后的发光粉加到PVC中的发光强度几乎不受影响.     

A metal-coordinating DNA hairpin mimic

A self-complementary oligodeoxynucleotide containing a 6,6"-substituted terpyridine was found to adopt a highly stable, hairpin-like structure. In addition to serving as a hairpin-loop mimic, the terpyridine can act as a coordination site for metals. Thus, the binding of several divalent transition metals (Zn(2+), Co(2+), Ni(2+), Cu(2+) and Pd(2+)) to the terpyridine hairpin mimic was investigated. The terpyridine-modified hairpin mimic forms a stable secondary structure in the presence of these metals. The stability of the metal-coordinated hairpin mimic was found to be lower than in the absence of metal. Furthermore, the T(m) of the metallohairpin is strongly influenced by the type of the bound metal, with T(m)'s increasing in the order Co(2+) approximately Ni(2+) < Zn(2+) < Cu(2+) < Pd(2+). Model considerations suggest that a conformational change of the terpyridine ligand is required to allow coordination of the metal.     

分子筛固载西佛碱和四氢西佛碱铜配合物的合成和表征

合成了三种西佛碱H₂L(H₂L₁=双水杨醛缩丙二胺,H₂L2=双水杨醛缩环己二胺,H₂L₃=双水杨醛缩乙二胺)及相应的四氢西佛碱配体H₂［H₄］L,并与醋酸铜反应合成其铜配合物。采用自由配体法将金属铜配合物封装在Y型分子筛的超笼里,同时利用红外手段对其进行了表征。证明在环己烷氧化反应中Cu［H₄］-Y比CuL-Y具有更高的反应活性。     

Cation ordering and superstructures in natural layered double hydroxides

Layered double hydroxides (LDHs) constitute an important group of materials with many applications ranging from catalysis and absorption to carriers for drug delivery, DNA intercalation and carbon dioxide sequestration. The structures of LDHs are based upon double brucite-like hydroxide layers [M(2+)(n)M(3+)(m)(OH)(2(m+n)](m+), where M(2+) = Mg(2+), Fe(2+), Mn(2+), Zn(2+), etc.; M(3+) = Al(3+), Fe(3+), Cr(3+), Mn(3+), etc. Structural features of LDHs such as cation ordering, charge distribution and polytypism have an immediate influence upon their properties. However, all the structural studies on synthetic LDHs deal with powder samples that prevent elucidation of such fine details of structure architecture as formation of superstructures due to cation ordering. In contrast to synthetic materials, natural LDHs are known to form single crystals accessible to single-crystal X-ray diffraction analysis, which provides a unique possibility to investigate 3D cation ordering in LDHs that results in formation of complex superstructures, where 2D cation order is combined with a specific order of layer stacking (polytypism). Therefore LDH minerals provide an indispensable source of structural information for modeling of structures and processes happening in LDHs at the molecular and nanoscale levels.     

氧化铝负载铜催化剂的制备及其对富氧条件下丙烯选择还原NO的催化性能研究

采用拟薄水铝石制备-γA l2O3,经SO42-改性和添加助剂La,再负载上Cu2+,制备了用于富氧条件下丙烯选择还原NO的金属氧化物催化剂。实验结果表明,经SO42-改性后,催化剂活性有了大幅度的提高,能使NO的转化率提高约30%,达到79.9%;助剂La的引入进一步提高了催化剂的活性和热稳定性;在SO42-用量w(SO42-)为30%、采用分步浸渍法引入w(La)=2%、负载上w(Cu2+)=3%的条件下,制得的催化剂的活性最好,在300℃时能使NO的转化率高达83.7%,在500℃还能使NO的转化率为30.9%。     

Fe_3O_4/丙烯酸系磁性微球的制备及对Hg~(2+)、Cu~(2+)、Ni~(2+)的吸附

以二乙烯苯为交联剂,采用悬浮聚合法制备了Fe3O4/丙烯酸系磁性吸附剂。聚合条件为:n(丙烯酸甲酯)∶n(二乙烯苯)=17∶1、w(引发剂)=1%、反应温度75~80℃、反应时间6 h。采用X射线衍射(XRD)、红外(IR)、热重分析(TGA)等对其进行了表征,并考察了它对金属离子的吸附性能。结果表明,制备的磁性吸附剂粒径35~55μm,w(Fe3O4)≈18%。吸附容量随pH升高而增加。饱和吸附容量qm(mmol/g)为:Hg2+2.3,Cu2+2.2,N i2+1.1。采用Lagergrent方程计算的吸附速率常数kad(m in-1)分别为:Hg2+0.023,Cu2+0.034,N i2+0.036。吸附剂可用c(H2SO4)=1 mol/L或c(HNO3)=0.5 mol/L再生。