环境化学开放性实验设计:重金属污染土壤的化学淋洗*

介绍了一个开放性环境化学实验。该实验以被重金属污染的土壤为研究对象,分别使用稀盐酸、乙二胺四乙酸、氯化钙为淋洗剂,对其进行化学淋洗修复。通过电感耦合等离子体光谱仪分析比较修复前后土壤中铅、镉的含量,用以帮助学生加深理解配合/螯合作用、酸-碱反应、离子交换反应、胶体的性质、土壤重金属形态、土壤性质与组成等相关环境化学知识。实验所用的土壤样品由学生自选,不同类型土壤的理化性质影响淋洗效果,从而增加了实验结果的不确定性。本实验贴近学科前沿且联系工程实际,可激发学生独立思考和探索精神,提高学生的科研能力与解决复杂问题的能力。     

Hexanuclear Fe(III)2Co(III)2M(II)2 (M = Cu, Ni, Mn) clusters based on Kläui's tripodal ligand and tricyanometalates: syntheses, structures and magnetic properties

With the use of Kl?ui's tripodal ligand, [(Cp)Co(P(O)(OEt)(2))(3)](-) (L(CoEt), Cp = cyclopentadiene) as the auxiliary ligand to react with different metal salts and tricyanometalate building blocks, five neutral trimetallic hexanuclear complexes: [(Tp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·6H(2)O (1, Tp = hydridotris(pyrazolyl)borate), [(Tp*)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·2H(2)O (2, Tp* = hydridotris(3,5-dimethyl-pyrazolyl)borate), [(pzTp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·H(2)O·3MeOH (3, pzTp = tetra(pyrazolyl)borate), [(Tp)(2)Fe(2)(CN)(6)Ni(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN·2H(2)O (4) and [(Tp)(2)Fe(2)(CN)(6)Mn(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN (5), have been obtained and structurally characterized. Magnetic measurements confirm that there are ferromagnetic couplings between the cyano-bridged Fe and Cu/or Ni ions and antiferromagnetic interaction between the cyano-bridged Fe and Mn ions. Slow relaxation of the magnetization is observed in complexes 1 and 4, while complex 3 exhibits metamagnetic behavior with a critical field of 17.5 kOe.     

实现粒子布居高效转移的两种激光脉冲时序方案的理论研究

基于最近实验工作的结果(2010 Nat.Phys.6 265)即Danzl等在五能级M型级联系统中分别利用连续型和四光子型受激拉曼绝热通道(stimulated Raman adiabatic passage,STIRAP)实现了将Feshbach态上弱束缚的Cs2有效转移到其振转基态,本文理论研究了两种STIRAP方案实施的基本条件,解析推导系统的准暗态、绝热参数的具体形式并分析其存在的必要性,详细讨论布居转移效率对相关参量的依赖关系.通过比较激光脉冲的时序、中间能级的失谐量和自发辐射率、光场脉冲的幅值等诸多参量的不同影响,讨论方案各自的优缺点,找到了参量优化的方法以实现最高效的粒子布居数转移.与前人的实验结果相比,本文研究表明,实验观测值(约0.60)均低于理论预估最佳值(约0.97)的主要原因是受限于激发态能级的自发辐射率过大.该理论方案还可用于制备量子纠缠态,在量子逻辑门操控、量子信息传输等领域都有潜在的应用.     

Effect of Structural Relaxation on Deformation Behaviour of Zr-Based Metallic Glass

Structural relaxation through isothermal annealing at temperature below glass transition is conducted on Zr46.75 Ti8.25 CU7.5Ni11Be27.5 （Vitreloy-4） bulk metallic glass. Defect concentration is correlated with the annealing time t according to differential scanning calorimetry thermalgrams. The effects of structural relaxation on mechanical properties and deformation behaviour are investigated by using instrumented nanoindentation. It is found that the as-cast alloy exhibits pronounced serration flow during the loading process of nanoindentation, and the size and number of the serrations decrease with the annealing time. The change of the deformation behaviour with structural relaxation is explained using a free volume model.     

Hydrogencyanamido bridged multinuclear copper(II) complexes: from strong antiferromagnetic couplings to weak ferromagnetic couplings

In the presence of ammonia, the reactions of cyanamide and Cu(II) ions with different organic blocking ligands afford three hydrogencyanamido bridged dinuclear complexes: [(dmbpy)(4)Cu(2)(HNCN)](ClO(4))(3)·H(2)O (1, dmbpy = 4,4'-dimethyl-2,2'-bipyridine), [(phen)(4)Cu(2)(HNCN)](ClO(4))(3)·2H(2)O (2, phen = 1,10-phenanthroline) and [(bpy)(2)Cu(2)(HNCN)(2)(ClO(4))(2)] (3, bpy = 2,2'-bipyridine), respectively. However, using the di(2-pyridyl)ketone (dpk) ligand in similar experimental conditions, an interesting reaction between the hydrogencyanamido anion and dpk is observed. Using Cu(ClO(4))·6H(2)O or Co(ClO(4))·6H(2)O as the metal source, it gives the mixed bridged hexanuclear complex [(dpk·OMe)(4)(dpk·NCN)(2)Cu(6)(H(2)O)(2)](ClO(4))(4) (4), or the mononuclear complex [(dpk·OMe)(dpk·HNCN)Co](ClO(4))·2H(2)O (5), respectively. Their structures are characterized by single crystal X-ray diffraction analyses. Magnetic measurements reveal moderate antiferromagnetic interaction between the Cu(II) ions in complex 1, weak ferromagnetic coupling in complex 2, and strong antiferromagnetic interactions for complexes 3 and 4. The magnetostructural correlations of these complexes are discussed.     

Selective trace enrichment of acidic pharmaceuticals in real water and sediment samples based on solid-phase extraction using multi-templates molecularly imprinted polymers

A novel multi-templates molecularly imprinted polymer (MIP), using acidic pharmaceuticals mixture (ibuprofen (IBP), naproxen (NPX), ketoprofen (KEP), diclofenac (DFC), and clofibric acid (CA)) as the template, was prepared as solid-phase extraction (SPE) material for the quantitative enrichment of acidic pharmaceuticals in environmental samples and off-line coupled with liquid chromatography–mass spectrometry (LC/MS/MS). Washing solvent was optimized in terms of kind and volume for removing the matrix constituents nonspecifically adsorbed on the MIP. When 1 L of water sample spiked at 1 μg/L was loaded onto the cartridge, the binding capacity of the MIP cartridge were 48.7 μg/g for KEP, 60.7 μg/g for NPX, 52 μg/g for CA, 61.3 μg/g for DFC and 60.7 μg/g for IBP, respectively, which are higher than those of the commercial single template MIP in organic medium (e.g. toluene) reported in the literature. Recoveries of the five acidic pharmaceuticals extracted from 1 L of real water samples such as lake water and wastewater spiked at 1 μg/L were more than 95%. The recoveries of acidic pharmaceuticals extracted from 10-g sediment sample spiked at the 10 ng/g level were in the range of 77.4–90.6%. To demonstrate the potential of the MIP obtained, a comparison with commercial C18 SPE cartridge was performed. Molecularly imprinted solid-phase extraction (MISPE) cartridge showed higher recoveries than commercial C18 SPE cartridge for acidic pharmaceuticals. These results showed the suitability of the MISPE method for the selective extraction of a group of structurally related compounds such as acidic pharmaceuticals.     

New europium coordination polymers with efficient energy transfer from conjugated tetracarboxylate ligands to Eu3+ ion: syntheses, structures, luminescence and magnetic properties

Two novel lanthanide coordination polymers, [Eu(2)(EBTC)(DMF)(5)(NO(3))(2)]·DMF (1) and [Eu(2)(BBTC)(1.5)(CH(3)OH)(2)(H(2)O)(2)]·7DMF·HNO(3) (2) (EBTC(4-) = 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; BBTC(4-) = 1,1'-butadiynebenzene-3,3',5,5'-tetracarboxylate), were successfully synthesized from conjugated ligands of EBTC(4-) and BBTC(4-). Although the two tetracarboxylate ligands have similar structures, their different rigidity/flexibility results in quite different networks upon complexation. Complex 1 has a two-dimensional (2-D) layered structure with two crystallographically independent Eu(3+) ions, one in a distorted monocapped square-antiprism and the other in a distorted square-antiprism coordination geometry. Complex 2 exhibits a three-dimensional (3-D) porous framework, with one type of Eu(3+) in a distorted square-antiprism and the other in a trigondodecahedron environment. Both 1 and 2 emit the intensely red characteristic luminescence of Eu(3+) ion at room temperature, with a long lifetime of up to 1.3 and 0.7 ms, respectively, during which the ligand emission of EBTC(4-)/BBTC(4-) was quenched by the Eu(3+) ion, indicating the existence of efficient energy transfer between the conjugated ligand of EBTC(4-)/BBTC(4-) and the Eu(3+) ion. Thus, both EBTC(4-) and BBTC(4-) are ideal ligands with an "antenna" effect for the Eu(3+) ion. The two complexes show the single-ion magnetic behaviors of Eu(3+) with strong spin-orbit coupling interactions even if there are shorter distances (5.714 ? for 1 versus 4.275 and 5.360 ? for 2) between the neighboring Eu(3+) ions connected by oxygen atoms of the tetracarboxylates.     

Structures and physical properties of oligomeric and polymeric metal complexes based on bis(pyridyl)-substituted TTF ligands and an inorganic analogue

The bis(pyridyl)-substituted TTF derivative, 2,6(7)-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (TTF(py)(2)), and an inorganic analogue, [Ni(4-pedt)(2)] (4-pedt = 1-(pyridin-4-yl)ethylene-1,2-dithiolate), were used as bridging ligands to construct two multinuclear complexes {Co(II)(2)(Tp(Ph2))(2)(OAc)(2)[TTF(py)(2)]} (1, Tp(Ph2) = hydridotri(3,5-diphenylpyrazol-1-yl)borate) and {Co(II)(2)(Tp(Ph2))(2)(OAc)(2)[Ni(4-pedt)(2)]} (2), and two 1D zigzag chain complexes, {[M(II)(tta)(2)][TTF(py)(2)]}(n) (M = Cu for 3, and Mn for 4; tta = thenoyltrifluoroacetonate). X-Ray structural studies indicate that complexes 1 and 2 are very similar as a result of the isolobal analogy between TTF(py)(2) and [Ni(4-pedt)(2)], whereas complexes 3 and 4 are isostructural. The absorption spectra, electrochemical and magnetic properties for these new complexes have been studied. The results show that the interactions between the paramagnetic ions are weak owing to the large separation of the bridging ligands of TTFs and the inorganic analogue.