The Au25(pMBA)17Diglyme Cluster

A modification of Au₂₅(pMBA)₁₈ that incorporates one diglyme ligand as a direct synthetic product is reported. Notably the expected statistical production of clusters containing other ligand stoichiometries is not observed. This Au₂₅(pMBA)₁₇diglyme product is characterized by electrospray ionization mass spectrometry (ESI-MS) and optical spectroscopy. Thiolate for thiolate ligand exchange proceeds on this cluster, whereas thiolate for diglyme ligand exchange does not.     

Recombination rate constant of free electrons and holes in thin CdSe films

The decay kinetics of electrons generated in thin CdSe films by laser pulse (wavelength 337 nm, pulse duration 8 ns) at 295 K was studied by the microwave photoconductivity method (36 GHz). Based on analysis of the photoresponse decay kinetics and the reactions of free and trapped electrons, holes, and ions, a model for the processes was proposed and the recombination rate constant of free electrons and holes in cadmium selenide was determined, being (4–6)· 10–11 cm³ s⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 740–743, May, 2006. The samples were kindly presented by Yu. V. Meteleva.     

Theoretical study of the stability and properties of magic numbers (m = 5, n = 2) and (m = 6, n = 3) of bimetallic bismuth‐copper nanoclusters; Bim Cun

Inspired by the experimental discovery of magic numbers we present a first study using density functional theory for the structure and properties of neutral and cationic Bi₆Cu₃ and Bi₅Cu₂ clusters. Our results confirm predictions based on Wade's rules. The closed electron shells, characteristic of cationic clusters help impose enhanced stability, while also complying with Wade's rules. Charge distribution analysis, as well as electrostatic potential maps show that in almost all cases, Bi atoms donate charges to Cu atoms. According to the analysis of condensed Fukui indices, Cu atoms inside both clusters are not reactive. Contrastingly, Bi atoms are reactive and may be targeted by different types of attack. This study of the electronic properties may thus help to determine experimental strategies with the capacity to enhance the synthesis of catalysts.     

Template Controlled Synthesis (TCS) of size-controlled metal nanoclusters: preparation of nanostructured metals supported by inorganic supports

Strictly size-controlled metal nanoclusters of palladium(0) and gold(0) can be easily formed in the organic component of an organic-inorganic composite between a gel-type resin (DV44) and silica. To this purpose, silica is impregnated at incipient wetness with a solution of the required co-monomers (N,N-dimethylacrylamide, 4-vinylpyridine and N,N′-methylene-bis-acrylamide), which are co-polymerized to give the composite. The silica-supported polymeric framework is then loaded with palladium(II) or gold(III) precursors. Their chemical reduction with aqueous solutions of sodium boronhydride yields the metal nanoclusters. Their size is controlled by the nanomorphology of the polymeric framework, which acts as a template during the nanocluster growth (Template Controlled Synthesis). Upon thermal decomposition of the polymeric template at 600°C under nitrogen, the nanostructured metals are deposited onto the silica surface. In the case of palladium the final step occurs with retention of the original size of the nanoclusters.     

Manipulation of the morphology of semiconductor-based nanostructures from core-shell nanoparticles to nanocables: the case of CdSe/SiO(2)

The morphology of CdSe/SiO(2) was manipulated from core-shell-structured nanoparticles to nanocables by using a chemical vapor deposition (CVD) process. The growth of nanocables, with cores no more than 20 nm in diameter, is initiated by the formation of core-shell nanoparticles with SiO(2) as matrix and CdSe clusters dispersed inside. After the subsequent vaporization of the SiO(2) matrix, the follow-up CdSe vapor crystallizes with the remaining CdSe clusters as nuclei to form CdSe nanowires as the furnace was cooled to 1200 degrees C. During the controlled cooling of the furnace, the SiO vapor re-deposits to sheathe the nanowires. The thickness of the shell and the diameter of core were successfully controlled. The photoluminescence measurements show that the CdSe/SiO(2) nanocables have strong visible-light emission bands located at 590 and 688 nm, which are attributed to the defects induced by SiO(2) sheaths nanowires and the quantum confinement effect of the CdSe, respectively. The UV/Vis absorption spectra of the naked CdSe nanowires further validate the above-mentioned quantum confinement effect. The deterministic growth of these nanocables is very important for the design of the nanodevices based on them.     

Tuning the Accessibility and Activity of Au25(SR)18 Nanocluster Catalysts through Ligand Engineering

In this work, the effects of thiolate ligands (‐SR, e.g., chain length and functional moiety) on the accessibility and catalytic activity of thiolate‐protected gold nanoclusters (e.g., Au₂₅(SR)₁₈) for 4‐nitrophenol hydrogenation is reported. The data suggest that Au₂₅(SR)₁₈ bearing a shorter alkyl chain shows a better accessibility to the substrates (shown by shorter induction time, t₀) and a higher catalytic activity (shown by higher apparent reaction rate constant, k_app). The functional moiety of the ligands is another determinant factor, which clearly suggests that ligand engineering of Au₂₅(SR)₁₈ would be an efficient platform for fine‐tuning its catalytic properties.     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

Synthesis and Crystal Structure of a Three-dimensional Coordination Polymer {[Cd(cda)_2]·2CH_3OH}_n Generated from Cadmium(II) and Carbamyldicyanomethanide Anion Bridging Ligand

1 INTRODUCTION The polynitrile-ligands, such as TCNE, TCNB, TCNQ, TCNP, tcm, dca and so on, are of ideal multi-functional bridging ligands. Many complexes with poly-nitriles as bridging ligands and uncoor- dinated ligand (electron acceptors) display dist…     

Kinetics of the thermal decomposition of cadmium carbonate (CdCO3)

Cadmium carbonate used in the study was prepared from cadmium chloride, ammonium carbonate and ammonia. The X-ray powder diffraction, infrared spectral and chemical analysis conducted on the product show that the sample is of analytically acceptable purity. The thermal decomposition kinetics of cadmium carbonate was then studied by using the isothermal thermogravimetric method under a flow of dry nitrogen gas. The decomposition kinetics is best described by a two-dimensional phase boundary reaction mechanism (R ₂). An activation energy (E _a) of 135.006 kJ·mol^?1 and natural logarithm of the frequency factor (lnZ) of 16.754 were obtained in the range of 9 temperatures (400, 390, 380, 370, 360, 350, 340, 330 and 320°C).     

A Quantitative Analysis of the Reduction Kinetics Involved in the Synthesis of Au@Pd Concave Nanocubes

Surface capping has been shown to play a pivotal role in controlling the evolution of metal nanocrystals into different shapes or morphologies. With the synthesis of Au@Pd concave nanocubes as an example, here we demonstrate that the capping agent can also impact the reduction kinetics of a precursor, and thereby its reduction pathway, for the formation of metal nanocrystals with distinct morphologies. A typical synthesis involves the reduction of a Pd^II precursor by ascorbic acid at room temperature in the presence of Au nanospheres as seeds, together with the use of hexadecyltrimethylammonium chloride (CTAC) or hexadecyltrimethylammonium bromide (CTAB) as the capping agent. In the case of CTAC, the Pd^II precursor prevails as PdCl₄²⁻, leading to the formation of Au@Pd concave nanocubes with a rough surface because of the fast reduction kinetics and thus the dominance of solution reduction pathway. When switched to CTAB, the Pd^II precursor changes to PdBr₄²⁻ that features slow reduction kinetics and surface reduction pathway. Accordingly, the Au@Pd concave nanocubes take a smooth surface. This work demonstrates that both reduction kinetics and surface capping play important roles in controlling the morphology of metal nanocrystals and these two roles are often coupled to each other.     

胍基稀土配合物[(CH2)5NC(NiPr)2]3Yb的合成及晶体结构

胍基可以通过改变氮上的取代基来调控配合物的空间及电荷效应,它们作为辅助配体用于稀土金属配合物的合成得到了人们的广泛关注。本文通过胍基锂盐和无水YbCl3以3：1的摩尔比进行复分解反应,合成了均配型稀土化合物[(CH2)5NC(N^iPr)2]3Yb,测得它为正交品系,     

Facile preparation of glutathione-stabilized gold nanoclusters for selective determination of chromium (III) and chromium (VI) in environmental water samples

A novel method for selective determination of Cr(III) and Cr(VI) in environmental water samples was developed based on target-induced fluorescence quenching of glutathione-stabilized gold nanoclusters (GSH-Au NCs). Fluorescent GSH-Au NCs were synthesized by a one-step approach employing GSH as reducing/protecting reagent. It was found that Cr(III) and Cr(VI) showed pH-dependent fluorescence quenching capabilities for GSH-Au NCs, and thus selective determination of Cr(III) and Cr(VI) could be achieved at different pHs. Addition of EDTA was able to effectively eliminate the interferences from other metal ions, leading to a good selectivity for this method. Under optimized conditions, Cr(III) showed a linear range of 25–3800 μg L⁻¹ and a limit of detection (LOD) of 2.5 μg L⁻¹. The Cr(VI) ion demonstrated a linear range of 5–500 μg L⁻¹ and LOD of 0.5 μg L⁻¹. The run-to-run relative standard deviations (n = 5) for Cr(III) and Cr(VI) were 3.9% and 2.8%, respectively. The recoveries of Cr(III) and Cr(VI) in environmental water samples were also satisfactory (76.3–116%). This method, with its simplicity, low cost, high selectivity and sensitivity, could be used as a promising tool for chromium analysis in environmental water samples.     

Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction

A structural study of ligand exchange on chalcogen‐passivated copper nanoclusters is far less developed. Herein, we report the synthesis of polyhydrido copper nanoclusters [Cu₂₀H₁₁{Se₂P(O ⁱBu)₂}₉] ( 2 ) passivated by Se‐donor ligands via ligand replacement reaction on [Cu₂₀H₁₁{S₂P(O ⁱPr)₂}₉] ( 1 ) with NH₄[Se₂P(O ⁱBu)₂]. In parallel to the synthesis of 2 , cluster [Cu₂₀H₁₁{S₂P(CH₂CH₂Ph)₂}₉] ( 4 ) was produced by the ligand exchange reaction on a new derivative of 1 , that is [Cu₂₀H₁₁{S₂P(O ⁿPr)₂}₉] ( 3 ). Solid state structures of both clusters 2 and 4 were unequivocally established by single‐crystal X‐ray diffraction studies and cluster 4 epitomizes exceptional case to preserve both the shape and size of the nanocluster during the course of ligand exchange. Structurally precise cluster 2 is the second example where the copper hydride nanocluster is stabilized by Se‐donor ligands. The anatomy of 2 can be visualized as a twisted cuboctahedral Cu₁₃ core, two triangular faces of which are capped by a Cu₆ cupola and a single Cu atom along the C₃ rotational axis.     

Cyanex272功能化的橘子皮对Cd(Ⅱ)的吸附动力学和热力学

本文采用橘皮(OP)吸附剂从水介质中去除Cd(Ⅱ).用萃取剂Cyanex272对生物质进行预处理活化,找到了去除Cd(Ⅱ)的最佳操作条件.通过用几种模型拟合实验数据后,发现最佳拟合模型为Langmuir模型和准二级动力学模型.不同吸附剂对Cd(Ⅱ)的吸附量顺序依次为272SCO>SCO>272CO>272OP>CO>OP.272SCO的最大吸附量为0.8663mol·g^-1,Cd(Ⅱ)的吸附量严格依赖于pH,所有吸附剂的最适合pH范围为5.5~6.0.对于吸附剂的再生,以0.1mol·L^-1 HCl为最佳解吸剂,解吸率接近100%.萃取剂Cyanex 272预处理后的橘皮可作为一种高效、低成本的吸附剂,用于去除水溶液中的镉.     

Syntheses, Structures, and Nonlinear Optical Properties of Two Crown-like Heteroselenometallic Compounds [Et4N]4[(μ5-WSe4)(CuX)5(μ-X)2] (X = Cl, Br)

Two isostructural crown-like heteroselenometallic cluster compounds, [Et₄N]₄[(μ₅-WSe₄)(CuX)₅(μ-X)₂] (X = Cl 1, Br 2), were prepared from the reactions of [Et₄N]₂[WSe₄] with CuX and [Et₄N]X· xH₂O in the presence of 2-picoline and characterized by single-crystal diffraction analysis. The [(μ₅-WSe₄)(Cu-X)₅(μ-X)₂]⁴⁻ anions in the cluster compounds consists of five CuX fragments coordinated to the five edges of the tetrahedral [WSe₄]²⁻ moiety along with two bridging halides connected to each of the two pairs of the symmetric copper atoms, exhibiting a novel crown-like core structure. The nonlinear optical absorption and refraction of cluster compound 2 were determined to be α₂ = 6.15 × 10⁻¹⁰ m/W and n ₂ = 4.18 × 10⁻¹¹ esu, respectively.     

Label-free colorimetric sensor for mercury(II) and DNA on the basis of mercury(II) switched-on the oxidase-mimicking activity of silver nanoclusters

In this paper, a novel colorimetric biosensor for Hg²⁺ and DNA molecules is presented based on Hg²⁺ stimulated oxidase-like activity of bovine serum albumin protected silver clusters (BSA-Ag NCs). Under mild conditions, Hg²⁺ activated BSA-Ag NCs to show high catalytic activity toward the oxidation of 3,3′,5, 5′-tetramethylbenzidine (TMB) using ambient dissolved oxygen as an oxidant. The oxidase-like activity of BSA-Ag NCs was “switched-on” selectively in the presence of Hg²⁺, which permitted a novel and facile colorimetric sensor for Hg²⁺. As low as 25 nmol L⁻¹ Hg²⁺ could be detected with a linear range from 80 nmol L⁻¹ to 50 mmol L⁻¹. In addition, the sensing strategy was also employed to detect DNA molecules. Hg²⁺ is known to bind very strongly and specifically with two DNA thymine bases (T) to form thymine–Hg²⁺–thymine (T–Hg²⁺–T) base pairs. The hairpin-structure was disrupted and Hg²⁺ ions were released after hybridization with the DNA target. By coupling the Hg²⁺ switched-on the oxidase-mimicking activity of BSA-Ag NCs, we developed a novel label-free strategy for facile and fast colorimetric detection of DNA molecules. More important, target DNA can be detected as low as 10 nmol L⁻¹ with a linear range from 30 to 225 nmol L⁻¹. Compared with other methods, this method presents several advantages such as the independence of hydrogen peroxide, high sensitivity and good selectivity, avoiding any modification or immobilization of DNA, which holds a great potential of metal NCs for clinical application in biosensing and biotechnology.     

Colorimetric detection of hepatitis B virus (HBV) DNA based on DNA-templated copper nanoclusters

DNA detection plays an important role in early diagnosis of genetic disease. The conventional detection methods of DNA are based on expensive equipment, which do not meet the demands of developing countries. Thus, we developed a colorimetric method, which could be observed with naked eye and used copper nanoclusters for cost-effective. Moreover, the target of this method is the DNA in Hepatitis B virus that is one of the most popular chronic viral infections in developing countries over the past years. Our method was sensitive and the limit of detection was 12 × 10⁹ molecules. Three-base-pair mismatches target DNA was detected easily. These results revealed the favorable sensitivity and selectivity of this approach. Most importantly, our method may have potential applications in correct diagnosis of genetic disease and monitoring of gene therapy in the poverty-stricken areas.     

Theoretical determination of the differential polarizability and anisotropy of alkaline earth oxide nanoclusters (BeO)n [n = 2–9]: The basis set and electron correlation effects

As an important lineage of metal oxides, alkaline earth oxides have attracted significant interest due to their unique properties and potential applications in material science and industry. In this article, we present the first ab initio (HF, MP2, and CCSD(T)) and density functional theory (TPSSh functional) investigation on the optical properties such as polarizabilities per atom (PPA), differential polarizability per unit (DPPU), and anisotropies of (BeO)_n [n = 2–9] nanoclusters as an illustrative example of alkaline earth oxides nanostructures. Basis set augmentation effects on the studied properties of BeO nanoclusters have been explored by using basis sets of triple‐zeta quality starting from 6‐311G with increasing completeness of the diffuse and polarization functions to the 6‐311+G(3df) basis. Checking carefully the basis set effects, it is shown that the 6‐311+G(3d) basis set provides the best compromise between the accuracy and computational cost. We found a decreasing trend for PPA values of BeO nanoclusters using all considered methods, indicating the strong electron delocalization with increasing cluster size. Moreover, in accordance with the energetic analysis of stability of BeO nanoclusters, the values of PPA show that the (BeO)₄ and (BeO)₆ clusters are the most stable magic numbers compared to the neighbors, satisfying the minimum polarizability principle. The computed values of DPPU demonstrate a strong binding effect in BeO nanoclusters. Taking into account the electron correlation correction (ECC), it is observed that the variations of ECC on dipole polarizabilities are almost smooth for clusters under study. © 2013 Wiley Periodicals, Inc.