卡尔曼滤波伏安分析法同时测定钴(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)

卡尔曼滤波（ＫＹ）用于解析互相干扰离子的Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｚｎ（Ⅱ）的伏安重叠峰。用该法对钢铁试样中的这些离子进行了测试，效果良好。设计了ＢＡＳＩＣ程序，将有关数据输入后，直接给出结果。为保证结果准确度，程序中设置了两个监控出口。     

Simple,Selective,and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel(Ⅱ),Copper(Ⅱ), Cobalt(Ⅱ),and Iron(Ⅲ)with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone(2-PYAINH)was synthesized and studied for the spectrophotometric determination of nickel,copper,cobalt,and iron in detail.At a pH value of 7.0,9.0,9.0,and 8.0,respectively,which greatly increased the selectivity;nickel,copper,cobalt, and iron reacted with 2-PYAINH to form a 1:2 yellow-orange,1:2 yellow-green,1:2 yellow and 1:1 yellow complexes,with absorption peaks at 363,352,346,and 359 nm,respectively.Under the optimal conditions,Beer's law was obeyed over the ranges of 0.01-1.4,0.01-1.5,0.01-2.7,and 0.01-5.4 mg/L,respectively.The apparent molar absorptivity and Sandell's sensitivities were 8.4×104,5.2x104,7.1×104,and 3.9×104L·mol-1.cm-1,respectively,and 0.00069,0.0012,0.00078,and 0.0014 μ g·cm-2,respectively.The detection limits were found to be 0.001,O.002,0.003,and 0.01 mg/L,respectively.The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

含酚氧桥的新型Cu(Ⅱ)-Mn(Ⅱ)和Cu(Ⅱ)-Co(Ⅱ)配合物的合成和磁性

合成了3种新型配合物[Cu(samen)Mn(NO_(2-)Phen)_2](1)、[Cu(sampn)Mn(NO_(2-)Phen)_2](2)和[Cu(samen)CO(terp)](3)(samen~(4-)、sampn~(4-)、NO_(2-)Phen和terp分别表示N,N′-乙二水杨酰胺根阴离子、N,N′-1,2-丙二水杨酰胺根阴离子、5-硝基-1,10-菲绕啉和联三吡啶),测得配合物的变温磁化率,求出交换积分,J分别为-63cm~(-1)(1)、—65cm~(-1)(2)和—7.68cm~(-1)(3),表明金属离子间有反铁磁超交换作用。     

锰(Ⅱ)、钴(Ⅱ)、铜(Ⅱ)和镉(Ⅱ)与吡哆醇配合物的结构研究

本文合成了吡哆醇与锰(Ⅱ)、钴(Ⅱ)、铜(Ⅱ)和镉(Ⅱ)的配合物。通过元素分析确定了配合物的组成。通达摩尔电导、比移值,紫外光谱、红外光谱和核磁共振谱的测定和分析,推断了配合物的结构。     

双安息香缩乙二胺的合成及其配位性质

合成了双安息香缩乙二胺及其与 Ni( )、Pd( )、Pt( )、Zn( )、Cd( )和 Hg( )的配合物 ,并经质谱、红外光谱、元素分析和电子光谱等方法所表征 ;测定了溶液中配合物的稳定常数 ,并就该配体的特殊配位性质进行了讨论。     

甲醛-苯氧乙酸树脂对金属离子的交换性能研究

研究了甲醛-苯氧乙酸树脂对重金属离子铅、镉、汞的交换性能,并考察了温度、pH值、浓度等因素对交换性能的影响。结果表明,树脂对3种重金属离子的等温交换过程均符合Langmuir交换等温式,交换受液膜扩散控制;其交换容量可分别达1.85mmol/g、1.73mmol/g、1.13mmol/g。     

人工神经网络分光光度法同时测定铜（Ⅱ）、镉（Ⅱ）、镍（Ⅱ）和锌（Ⅱ）

在pH 9.80的硼砂-氢氧化钠缓冲溶液、十六烷基三甲基溴化铵（CTMAB）存在下,铜（Ⅱ）、镉（Ⅱ）、镍（Ⅱ）和锌（Ⅱ）与二甲酚橙（XO）发生灵敏的显色反应,所形成的络合物吸收光谱严重重叠,各组分间相互干扰。采用人工神经网络结合分光光度法,设计不经分离同时测定铜（Ⅱ）、镉（Ⅱ）、镍（Ⅱ）和锌（Ⅱ）含量的方法。结果表明...     

Preparation, Properties and Mechanism of Inhomogeneous Calcium Alginate Ion Cross-linking Gel Microspheres

Inhomogeneous calcium alginate ion cross-linking gel microspheres,a novel ion absorbent,were prepared by dropping a sodium alginate solution to a calcium chloride solutioin via an electronic droplet generator.Calcium alginate microspheres have uniform particle sizes.a smooth surface and a microporous structure.The electrode probe reveals the inhomogeneous distribution of calcium ions with the highest concentration on the surface,and the lowest concentration in the cores of the spheres.As a novel ion adsorbent,calcium alginate gel microspheres have a lower limiting adsorption mass concentration,a higher enrichment capacity and a higher adsorption capacity for Pb^2 than usual ion exchange resins.The highest percentage of the adsorption is 99.79%.The limiting adsorption mass concentration is 0.0426mg/L.The adsorption capacity for Pb^2 is 644mg/g,Calcium alginate gel microspheres have a much faster ion exchange velocity than D418 chelating resin and D113 polyacrylate resin.The moving boundary model was employed to interpret the ion exchange kinetics process,which indicates that the ion exchange process is controlled by intraparticle diffusion of adsorbable ions.So the formation of inhomogeneous gel microspheres reduces the diffusion distance of adsorbable ions within the spheres and enhances the ion exchange velocity.Alginate has a higher selectivity for pb^2 than for Ca^2 and the selectivity coefficient KCa^Pb is 316. As an ion cross-linking gel,calcium alginate inhomogeneous microspheres can effectively adsorb heavy metal Pb^2 at a higher selectivity and a higher adsorption velocity.It is a novel and good ion adsorbent.     

Synthesis and Characterization of Nickel(Ⅱ) and Copper(Ⅱ) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes,Ni(salen) (salen=(1R,2R)-(-)-diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene) 1 and Cu(salen) 2,have been synthesized and characterized by IR,microanalysis,TGA,powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P2_12_12 with Z=4. For 1,α= 12.082(2),b = 15.447(3),c = 18.784(4)(A),V= 3505.7(12) (A)~3,M_r = 731.50,D_c = 1.386 g/cm~3,μ= 0.606 mm~(-1),F(000)=1544,the final GOOF=1.043,R=0.0496 and wR=0.1248 for 4791 observed reflections with Ⅰ> 2σ(Ⅰ). For 2,α=12.181(2),b=15.501(3),c=18.877(4)(A),V= 3564.3(12)(A)~3,M_r=736.33,Dc = 1.372 g/cm~3,μ=0.665 mm~(-1),F(000)=1548,the final GOOF= 1.062,R=0.0575 and wR=0.1508 for 4562 observed reflections with Ⅰ> 20(Ⅰ). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.     

酚氧桥联的不对称双铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成和磁性

本文合成了一组新的不对称双核配合物「Cu(samen)Cu(terp)」和「Cu(samen)Zn(terp)」,samen~4和terp分别表示N N’-乙二水杨酰胺胺根阴离子和2.2′:6′2″-联三吡啶。配合物「Cu(samen)Cu(terp)」的变温磁化率已测,其数值用最小二乘法与Bleancy-Bowers方程拟合,求得交换积分J=-0.538cm~(-1),表明配合物中铜离子间有极弱的反铁磁自旋交换作用。     

大环配体过渡金属配合物的研究(Ⅳ)——Schiff碱型四呋喃[26]-N_4O_4大环配体及其过渡金属配合物的合成与性质研究

Schiff碱型大环配体能与周期表中的大多数金属离子形成稳定的配合物,是配位化学的一个重要研究方向.对其多核配合物的研究,不仅有助于认识生物体中多金属中心配合物,还有助于对这类化合物的键合、多电子还原、磁交换性质等方面的研究.为此,我们合成了未见文献报道的Schiff碱型四呋喃[26]-N_4O_4大环配体(L)及其过渡金属(Cu(Ⅱ)、Co(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ))配合物(2MCl_2·L·2H_2O),并对它们的性质作了初步的研究.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Synthesis and Crystal Structure of a Ternary Complex: [Ni(phen)2(pmal)]·8H2O

A new ternary complex [Ni(phen)(pmal)]·8H2O (phen = 1,10-phenanthroline,pmal2- = phenethyl malonic acid) has been synthesized by the reaction of nickel acetate, phen and phenethyl malonic acid. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: triclinic system, space group P1, a = 10.387(5), b = 13.112(6), c = 14.229(6) (A), α = 76.176(7), β =83.778(8), y = 71.770(6)°, C35H42N4O12Ni, Mr= 769.44, Z = 2, F(000) = 808, V = 1786.1 (A)3, Dc =1.431 g/cm3, μ = 0.612 mm-1, the final R = 0.0653 and wR = 0.1033 for 9379 (Rint = 0.0244)independent reflections and 4730 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the coordination geometry of Ni(Ⅱ) is a distorted octahedron. A novel two-dimensional structure is constructed from (H2O)4 and (H2O)12 water clusters, and the complex forms a 3-D network supramolecular structure by hydrogen bonds and π-π stacking of neighboring phens.     

Determination of Ultratrace Amounts of Copper(Ⅱ) in Water Samples by Electrothermal Atomic Absorption Spectrometry After Cloud Point Extraction

A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry (ETAAS) after cloud point extraction (CPE). 1-( 2-Pyridylazo)-2-naphthol was used as the chelating reagent and Triton X-114 as the micellar-forming surfactant. CPE was conducted in a pH 8.0 medium at 40 ℃ for 10 min. After the separation of the phases by centrifugation, the surfactant-rich phase was diluted with 1 mL of a methanol solution of 0. 1 mol/L HNO3. Then 20 μL of the diluted surfactant-rich phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng/L was obtained after preconcentration. The linear dynamic range of the copper mass concentration was found to be 0-2.0ng/mL, and the relative standard deviation was found to be less than 3.1% for a sample containing 1.0 ng/mL Cu(Ⅱ). This developed method was successfully applied to the determination of ultratrace amounts of Cu in drinking water, tap water, and seawater samples.     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

具有非正规自旋态结构的新型Mn(Ⅱ)-Cu(Ⅱ)-Mn(Ⅱ)三核配合物的合成和磁性

合成和表征了四种新的异三核配合物,{[Mn(L)_2]_2[Cu(Pba)]}(ClO_4)_2,其中Pba表示为亚丙基-1,3-双(草胺酸根);L表示1,10-菲咯啉(phen)、5-硝基-1,10-菲咯琳(NO_2-phen)、2,2’-联吡啶(bpy)、4,4′-二甲基-2,2’-联吡啶(Me_2bpy).基于{[Mn(phen)_2]_2[Cu(pba)]}(ClO_4)_2·H_2O的变温磁化率测量(4.2～300K),求出交换积分J=-41.5cm(-1),表明Mn(Ⅱ)和Cu(Ⅱ)离子间为反铁磁耦合.在 X_MT-T图上,X_MT在175K附近呈现出一极小值,这是具有非正规自旋态结构的多金属耦合体系的典型特征.