CO oxidation over ceria supported Au22 nanoclusters: Shape effect of the support

CO oxidation over ceria-supported Au₂₂ nanoclusters shows strong dependence on the support shape: the lattice oxygen in CeO₂ rods is more reactive than in the cubes and thus make rods a superior support for Au nanoclusters in catalyzing low temperature CO oxidation.     

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

The self‐assembled structures of atomically precise, ligand‐protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding‐directed self‐assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p‐mercaptobenzoic acid (pMBA)‐protected atomically precise silver nanocluster, Na₄[Ag₄₄(pMBA)₃₀], and pMBA‐functionalized GNRs were used. High‐resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H‐bonding, leading to octahedral symmetry. The use of water‐dispersible gold nanoclusters, Au_≈250(pMBA)_n and Au₁₀₂(pMBA)₄₄, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities.     

The Origin of the Photoluminescence Enhancement of Gold‐Doped Silver Nanoclusters: The Importance of Relativistic Effects and Heteronuclear Gold–Silver Bonds

The weak photoluminescence of silver nanoclusters prevents their broad application as luminescent nanomaterials. Recent experiments, however, have shown that gold doping can significantly enhance the photoluminescence intensity of Ag₂₉ nanoclusters but the molecular and physical origins of this effect remain unknown. Therefore, we have computationally explored the geometric and electronic structures of Ag₂₉ and gold‐doped Ag_29?xAu_x (x=1–5) nanoclusters in the S₀ and S₁ states. We found that 1) relativistic effects that are mainly due to the Au atoms play an important role in enhancing the fluorescence intensity, especially for highly doped Ag₂₆Au₃, Ag₂₅Au₄, and Ag₂₄Au₅, and that 2) heteronuclear Au?Ag bonds can increase the stability and regulate the fluorescence intensity of isomers of these gold‐doped nanoclusters. These novel findings could help design doped silver nanoclusters with excellent luminescence properties.     

聚胸腺嘧啶单链DNA-CuNCs荧光增强法用于汞离子的高灵敏检测

基于Hg~(2+)与DNA中胸腺嘧啶(T)结合的高度特异性和DNA铜纳米簇的荧光增强性质,构建了一种简便、灵敏检测汞离子的新方法.当Hg~(2+)存在时,聚T单链DNA(P1)通过T-Hg~(2+)-T特异性结合形成双链DNA,Cu~(2+)经抗坏血酸钠还原后生成的中间体Cu+与双链DNA螺旋结构间的氢键部分有强的结合力,促使Cu0附着聚集在双链DNA上形成铜纳米簇,导致体系荧光增强,从而实现对汞离子的高灵敏检测.体系荧光强度与Hg~(2+)浓度的对数值成正比,对Hg~(2+)检测的线性范围为1.0 nmol/L~10μmol/L,检出限达0.4 nmol/L,对湖水样品中Hg~(2+)检测的回收率达到97.2%~106.6%.与传统方法相比,该方法具有无需标记、检出限低及选择性好等优点,可用于环境水体中汞离子的测定.     

Bimetallic Au2Cu6 Nanoclusters: Strong Luminescence Induced by the Aggregation of Copper(I) Complexes with Gold(0) Species

The concept of aggregation‐induced emission (AIE) has been exploited to render non‐luminescent Cu^ISR complexes strongly luminescent. The Cu^ISR complexes underwent controlled aggregation with Au⁰. Unlike previous AIE methods, our strategy does not require insoluble solutions or cations. X‐ray crystallography validated the structure of this highly fluorescent nanocluster: Six thiolated Cu atoms are aggregated by two Au atoms (Au₂Cu₆ nanoclusters). The quantum yield of this nanocluster is 11.7 %. DFT calculations imply that the fluorescence originates from ligand (aryl groups on the phosphine) to metal (Cu^I) charge transfer (LMCT). Furthermore, the aggregation is affected by the restriction of intramolecular rotation (RIR), and the high rigidity of the outer ligands enhances the fluorescence of the Au₂Cu₆ nanoclusters. This study thus presents a novel strategy for enhancing the luminescence of metal nanoclusters (by the aggregation of active metal complexes with inert metal atoms), and also provides fundamental insights into the controllable synthesis of highly luminescent metal nanoclusters.     

D-Proline capped gold nanoclusters for turn-on detection of serum Raltitrexed

Using D-proline (D-Pro) as the reducing agent and capper, D-Pro@AuNCs was rapidly constructed. Its fluorescence could be quenched by AuNPs. Due to the electrostatic interaction between anticancer drug Raltitrexed (RTX) and AuNPs induced fluorescence "turn-on" principle, the resultant fluorescent probe exhibited good selectivity and sensitivity for detecting RTX in rat serums.     

Density functional theory analysis of reactivity of PtxPdy alloy clusters

We investigate the reactivity of various Pt_xPd_y combinations (with x + y = 10 and various x:y ratios) towards the adsorption of specific intermediates of the oxygen reduction, using the B3PW91 hybrid density functional theory. The reactivity is shown to be not only sensitive to the composition of the cluster, but also to the atomic distribution. The calculations indicate that two different ensembles: one ordered and one randomly mixed, with overall composition Pt₃Pd₇ are thermodynamically more favorable than pure Pt₁₀ for the oxygen reduction reaction. The reasons for this behavior are clearly explained in terms of the atomic and electronic distribution, which makes the Pd atoms to act as electron donors both to Pt atoms and to the adsorbates, thus the reactivity of the Pd atoms in such environment becomes intermediate between Pt and Pd. Moreover, it is found that in a mixed Pt₃Pd₇ state the electronic distribution makes the average atom more similar to Pt than to Pd, whereas in an ordered Pt₃Pd₇ cluster, the average atom is more similar to Pd than to Pt.     

Interaction of humic and fulvic acids with nanoclusters of aluminum hydroxo cations on the surface of kaolinite according to IR spectroscopy data

We chemically modified the surface of kaolinite with nanoclusters of aluminum hydroxo cations. We have determined their composition and sizes. We have used IR spectroscopy to establish the interaction between the carbonyl and -diketone groups of fulvic and humic acids with the Lewis acid sites: coordination unsaturated Al³⁺ cations of the Al₁₃ nanoclusters. We have obtained spectral evidence for hydrogen bond formation between the carboxyl groups of fulvic acid and the hydroxyl groups of the aluminum hydroxo cations.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 45–49, January–February, 2005.