Water-soluble Au25(Capt)18 nanoclusters: synthesis, thermal stability, and optical properties

This work was motivated by the unsatisfactory stability of Au(25)(SG)(18) in solution under thermal conditions (e.g. 70-90 °C for DNA melting). Thus, we searched for a better, water-soluble thiol ligand. Herein, we report a one-pot synthesis and investigation of the stability and optical properties of captopril (abbreviated Capt)-protected Au(25)(Capt)(18) nanoclusters. The Au(25)(Capt)(18) (anionic, counterion: Na(+)) nanoclusters were formed via size focusing under ambient conditions. Significantly, Au(25)(Capt)(18) nanoclusters exhibit largely improved thermal stability compared to the glutathione (HSG) capped Au(25)(SG)(18). Both Au(25)(Capt)(18) and Au(25)(SG)(18) nanoclusters show fluorescence centered at ～700 nm. The chiral ligands (Capt, SG, as well as chirally modified phenylethanethiol (PET*)) give rise to distinct chiroptical features. The high thermal stability and distinct optical properties of Au(25)(Capt)(18) nanoclusters render this material quite promising for biological applications.     

N,N-Dimethylformamide-stabilized gold nanoclusters as a catalyst for the reduction of 4-nitrophenol

In this study, we investigated the catalytic properties of N,N-dimethylformamide (DMF)-stabilized gold nanoclusters (AuNCs) in the reduction of 4-nitrophenol (PNP) to 4-aminophenol by NaBH(4), a well known model reaction to be catalyzed by metal surfaces. The DMF-stabilized AuNCs were prepared in DMF by a surfactant-free method. The DMF-stabilized AuNCs showed high catalytic activity even when used in small quantities (～10(-7) g). The pseudo-first-order rate constant (k(app)) and activation energy were estimated to be 3 × 10(-3) s(-1) and 31 kJ mol(-1), respectively, with 1.0 μM of the gold catalyst at 298 K. The catalytic activity of the DMF-stabilized AuNCs was strongly influenced by the layer of adsorbed DMF on the Au NCs. This layer of adsorbed DMF prohibited the reactants from penetrating to the surface of the AuNCs via the diffusion at the beginning of the reaction, resulting in an induction time (t(0)) before PNP reduction began. Restructuring of the DMF layer (essentially a form of activation) was the key to achieving high catalytic activity. In addition, atomically monodisperse Au(25)(SG)(18)NCs (SG: glutathione) showed higher catalytic activity in the PNP reduction (k(app) = 8 × 10(-3) s(-1)) even with a low catalyst concentration (1.0 μM), and there was no induction time (t(0)) in spite of the strongly binding ligand glutathione. This suggested that the catalytically active surface sites of the Au(25)(SG)(18)NCs were not sterically hindered, possibly because of the unique core-shell-like structure of the NCs. Retaining these open sites on AuNCs may be the key to making the NCs effective catalysts.     

Unexpected reactivity of Au25(SCH2CH2Ph)18 nanoclusters with salts

We report some interesting results of the chemical reactivity of thiolate-protected [Au(25)(SCH(2)CH(2)Ph)(18)](0) nanoclusters with two types of salts, including tetraoctylammonium halide (TOAX) and NaX. At the early stage of the reaction, [Au(25)(SCH(2)CH(2)Ph)(18)](0) was found to spontaneously convert to its anionic form ([Au(25)(SCH(2)CH(2)Ph)(18)](-)) in the presence of either type of salt. However, a large difference was observed in the second stage of the reaction. With NaX, we observed decomposition of anionic clusters, while with TOAX, the clusters show excellent stability. We have gained some insight into the reaction mechanism. The X(-) ions seem to attack [Au(25)(SCH(2)CH(2)Ph)(18)](q) surface and displace some thiolates, evidenced by the observation of halide-bound clusters such as Au(25)(SCH(2)CH(2)Ph)(18-x)Br(x) in mass spectrometry analysis. These halide-bound clusters show a reduced stability, and their decomposition into Au(I) complexes leads to the release of gold valence electrons of the clusters; concurrently, the non-halide-bound [Au(25)(SCH(2)CH(2)Ph)(18)](0) clusters are reduced into [Au(25)(SCH(2)CH(2)Ph)(18)](-). For the second stage of reaction with organic salts such as TOA-Br, after [Au(25)(SCH(2)CH(2)Ph)(18)](0) clusters are converted to [Au(25)(SCH(2)CH(2)Ph)(18)](-)) the TOA(+) counterions surprisingly protect the anionic clusters from further attack by halide ions, hence, TOA(+) cations can stabilize [Au(25)(SCH(2)CH(2)Ph)(18)](-) clusters. In contrast, with NaX salts the Na(+) ions do not provide any steric stabilization of the [Au(25)(SCH(2)CH(2)Ph)(18)](-) clusters, hence, degradation occurs when being further attacked by halide ions, especially Br(-) and I(-).     

Ligand-exchange synthesis of selenophenolate-capped Au25 nanoclusters

We report the synthesis and characterization of selenophenolate-capped 25-gold-atom nanoclusters via a ligand-exchange approach. In this method, phenylethanethiolate (PhCH(2)CH(2)S) capped Au(25) nanoclusters are utilized as the starting material, which is subject to ligand-exchange with selenophenol (PhSeH). The as-obtained cluster product is confirmed to be selenophenolate-protected Au(25) nanoclusters through characterization by electrospray ionization (ESI) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), thermogravimetric analysis (TGA), elemental analysis (EA), UV-Vis and (1)H/(13)C NMR spectroscopies. The ligand-exchange synthesis of [Au(25)(SePh)(18)](-)[(C(8)H(17))(4)N](+) nanoclusters demonstrates that the core size of gold nanoclusters is retained in the thiolate-to-selenolate exchange process and that the 18 surface thiolate ligands can be completely exchanged by selenophenolate, rather than giving rise to a mixed ligand shell on the cluster. The two types of Au(25)L(18) (L = thiolate or selenolate) nanoclusters also show some differences in stability and optical properties.     

Ligand effects on the stability of thiol-stabilized gold nanoclusters: Au25(SR)18(-), Au38(SR)24, and Au102(SR)44

We have studied the electrochemical and thermodynamic stability of Au(25)(SR)(18)(-), Au(38)(SR)(24), and Au(102)(SR)(44), R = CH(3), C(6)H(13), CH(2)CH(2)Ph, Ph, PhF, and PhCOOH, in order to examine ligand effects on the stability of thiol-stabilized gold nanoclusters, Au(m)(SR)(n). Aliphatic thiols, in general, have higher electrochemical and thermodynamic stability than aromatic thiols, and the -SCH(2)CH(2)Ph thiol is particularly appealing because of its high electrochemical and thermodynamic stability. The stabilization of Au(m) by nSR for Au(m)(SR)(n) can be rationalized by the stabilization of an Au atom by an SR for the simple molecule AuSR, regardless of interligand interaction and system size and shape. Thiol moieties play a strong role in the electron oxidation and reduction of Au(m)(SR)(n). Accounting for the characteristics of thiol ligands is essential for understanding the electronic and thermodynamic stability of thiol-stabilized gold nanoclusters.     

The halogen analogs of thiolated gold nanoclusters

Is it possible to replace all the thiolates in a thiolated gold nanocluster with halogens while still maintaining the geometry and the electronic structure? In this work, we show from density functional theory that such halogen analogs of thiolated gold nanoclusters are highly likely. Using Au(25)X(18)(-) as an example, where X = F, Cl, Br, or I replaces -SR, we find that Au(25)Cl(18)(-) demonstrates a high similarity to Au(25)(SR)(18)(-) by showing Au-Cl distances, Cl-Au-Cl angles, band gap, and frontier orbitals similar to those in Au(25)(SR)(18)(-). DFT-based global minimization also indicates the energetic preference of staple formation for the Au(25)Cl(18)(-) cluster. The similarity between Au(m)(SR)(n) and Au(m)X(n) could be exploited to make viable Au(m)X(n) clusters and to predict structures for Au(m)(SR)(n).     

Different coordination modes of a tripod phosphine in gold(i) and silver(i) complexes

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au(3)(tripod)X(3) [X = Cl(1), Br(2), I(3)]; [Au(3)(tripod)(2)Cl(2)]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag(3)(tripod) (NO(3))(4) (7), Ag(tripod)NO(3) (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), (31)P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes 2 and 3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex 3 has a Au***Au intramolecular distance of 3.326 A degrees , while complex 2 had a short Au***Au intermolecular interaction of 3.048 A degrees . Complexes 4-6 were found by (31)P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au(3)(tripod|)(2)Cl(2)]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au(3) (tripod)Cl(3)] (1) with tripod led successfully to the formation of [Au(3)(tripod|)(2)Cl(2)](+) and [Au(3)(tripod)(2)Cl(3)](+) and [Au(3)(tripod|)(3)Cl](2+). The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively.     

Investigating the structural evolution of thiolate protected gold clusters from first-principles

Unlike bulk materials, the physicochemical properties of nano-sized metal clusters can be strongly dependent on their atomic structure and size. Over the past two decades, major progress has been made in both the synthesis and characterization of a special class of ligated metal nanoclusters, namely, the thiolate-protected gold clusters with size less than 2 nm. Nevertheless, the determination of the precise atomic structure of thiolate-protected gold clusters is still a grand challenge to both experimentalists and theorists. The lack of atomic structures for many thiolate-protected gold clusters has hampered our in-depth understanding of their physicochemical properties and size-dependent structural evolution. Recent breakthroughs in the determination of the atomic structure of two clusters, [Au(25)(SCH(2)CH(2)Ph)(18)](q) (q = -1, 0) and Au(102)(p-MBA)(44), from X-ray crystallography have uncovered many new characteristics regarding the gold-sulfur bonding as well as the atomic packing structure in gold thiolate nanoclusters. Knowledge obtained from the atomic structures of both thiolate-protected gold clusters allows researchers to examine a more general "inherent structure rule" underlying this special class of ligated gold nanoclusters. That is, a highly stable thiolate-protected gold cluster can be viewed as a combination of a highly symmetric Au core and several protecting gold-thiolate "staple motifs", as illustrated by a general structural formula [Au](a+a')[Au(SR)(2)](b)[Au(2)(SR)(3)](c)[Au(3)(SR)(4)](d)[Au(4)(SR)(5)](e) where a, a', b, c, d and e are integers that satisfy certain constraints. In this review article, we highlight recent progress in the theoretical exploration and prediction of the atomic structures of various thiolate-protected gold clusters based on the "divide-and-protect" concept in general and the "inherent structure rule" in particular. As two demonstration examples, we show that the theoretically predicted lowest-energy structures of Au(25)(SR)(8)(-) and Au(38)(SR)(24) (-R is the alkylthiolate group) have been fully confirmed by later experiments, lending credence to the "inherent structure rule".     

A photoresponsive Au25 nanocluster protected by azobenzene derivative thiolates

An Au(25) cluster protected by azobenzene derivative thiolates (S-Az) ([Au(25)(S-Az)(18)](-)) was synthesized with the aim of producing a photoresponsive Au(25) cluster. The matrix-assisted laser desorption/ionization mass spectrum of the product revealed that [Au(25)(S-Az)(18)](-) was synthesized in high purity. Optical absorption spectra of [Au(25)(S-Az)(18)](-) obtained before and after photoirradiation suggest that the azobenzenes in the ligands of Au(25)(S-Az)(18) isomerize with an efficiency of nearly 100%, both from the trans to cis conformation and from the cis to trans conformation. Furthermore, the redox potential and optical absorption of Au(25)(S-Az)(18) were found to change reversibly due to photoisomerization of azobenzenes.     

Electron transfer catalysis with monolayer protected Au(25) clusters

Au(25)L(18) (L = S(CH(2))(2)Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au(25)L(18)(+) quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au(25)L(18)(+) was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au(25)L(18)/Au(25)L(18)(-) and the Au(25)L(18)(+)/Au(25)L(18) redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (k(ET)) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log k(ET)vs.ΔG°) relationship. Comparison with the k(ET) obtained using a ferrocene-type donor with a formal potential similar to that of Au(25)L(18)/Au(25)L(18)(-) showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.     

Electronic and steric effects in gold(i) phosphine thiolate complexes

The unusual yellow color of Au(2)(dppm)(SR)(2) (R = 4-tolyl; dppm = diphenylphosphinomethane) is attributed to a red-shift in the S-->Au charge transfer caused by destabilization of the sulfur highest occupied molecular orbital (HOMO). Variable temperature experiments show two broad bands at -80 degrees C in the (31)P{(1)H} NMR spectrum of Au(2)(dppm)(SR)(2) and the activation energy for interconversion is 10 kcal/mol. Only one sharp band is observed down to -80 degrees C in the spectrum of the white complex, Au(2)(dppe)(SR)(2) (dppe = diphenylphosphinoethane). Molecular mechanics calculations on Au(2)(dppm)(SR)(2) and Au(2)(dppe)(SR)(2) reveal that, for Au(2)(dppe)(SR)(2), a series of maxima and minima, separated by 2.5 kcal/mol, occur every 120 degrees which is consistent with rotation around an unhindered carbon-phosphorus single bond. The Au atoms are not within bonding distance in any conformation. Computational results for Au(2)(dppm)(SR)(2) indicate one minimum energy structure in which the Au-P bonds are anti. There is a high energy conformation (9 kcal/mol above the global minimum) where overlap between golds is maximized. The implications of gold-gold bonding in this complex are discussed. The steric influence of the thiolate ligand has been examined by synthesizing a series of dinuclear gold(I) complexes in which the steric properties of the thiolate are varied: Au(2)(dppm)(SR)(2) (R = 2,6-dichlorophenyl; 2,6-dimethylphenyl; 3,5-dimethylphenyl). The 2,6-disubstituted complexes are white, while the 3,5-dimethyl complex is yellow. These results, along with VT-NMR experiments, are consistent with the conclusion that the more sterically-bulky thiolates hinder the close approach of the golds in the dinuclear complexes.     

Redox Chemistry and [Au(CN)(2)] in the Formation of Gold Metabolites

The role of hypochlorite ion, which can be generated by the enzyme myleoperoxidase, in the biochemistry of gold(I) anti-arthritic drugs was investigated. Sodium hypochlorite (OCl(-)) directly and rapidly oxidizes AuSTm, Au(CN)(2) (-), AuSTg (gold thioglucose) and auranofin (Et(3)PAuSATg). The resulting gold(III) species were detected by an Ion Chromotography Ion-Pairing technique that was developed to distinguish gold(I) and gold(III). Formation of Au(III) was also demonstrated spectrophotometrically after the conversion to AuCl(4) (-). The reactions of AuSTm, AuSTg, and auranofin are complex and gold(III) appears only after the initial oxidation of the thiolate (and phosphine) ligands.The enzymatic reaction, using MPO with H(2)O(2) and Cl(-) as substrates, leads to slow oxidation of Au(CN)(2) (-), AuSTm or AuSTg. The extent and rate of reaction depend on the concentrations of MPO, H(2)O(2), and Au(I). The continued presence of Au(I) during the initial stages of reaction (oxidation of the thiolates in AuSTm and AuSTg) and the conversion to Au(III) in the latter stages of the reaction were demonstrated. Au(CN)(2) (-), a gold metabolite, binds tightly to serum albumin. Unlike other gold(I) complexes, aurocyanide reacts almost negligibly at Cys-34 via ligand exchange. Instead, there is a strong association (K(1) = 5.5 x 10(4) and K(2) = 7.0 x 10(3); n(1) = 0.8 and n(2) = 3) of intact Au(CN)(2) (-). The full extent of binding is revealed only by equilibrium methods such as NMR or ultrafiltration; the bound gold dissociates extensively on conventional gel-exclusion columns and partially on Penefesky spun columns.The immunological and pharmacological significance of these results are discussed.     

Microwave-assisted rapid synthesis of luminescent gold nanoclusters for sensing Hg2+ in living cells using fluorescence imaging

A microwave-assisted strategy for synthesizing dihydrolipoic acid (DHLA) capped fluorescent gold nanoclusters (AuNCs) has been developed. Irradiation with microwaves during synthesis enhanced the fluorescence quantum yield (QY) of AuNCs by about five-fold and shortened the reaction time from hours to several minutes. The as-synthesized DHLA-AuNCs possessed bright near-infrared fluorescence (QY: 2.9%), ultrasmall hydrodynamic diameter (3.3 nm), good colloidal stability over the physiologically relevant pH range of 5-10 as well as low cytotoxicity toward HeLa cells. Moreover, these DHLA-AuNCs were capable of sensing Hg(2+) through the specific interaction between Hg(2+) and Au(+) on the surface of AuNCs; the limit of detection (LOD) was 0.5 nM. A potential application in imaging intracellular Hg(2+) in HeLa cells was demonstrated by using spinning disc confocal microscopy.     

Fabrication of sensor for reactive oxygen species using gold electrodes modified with electropolymerized porphyrins and application for detection of stress of plants

Reactive Oxygen Spiecies (ROS) such as superoxide anion radical (.O(2)(-)) act as signals for the activation of stress-response and defense pathways. However, excess ROS generated by perturbing .O(2)(-) homeostasis stimulated many environmental stress, including intense light, drought, temperature stress, herbicides, induce high radical toxicity. Consequently, quantitative analysis of .O(2)(-) is a subject of intense research, since most of ROS are derived from .O(2)(-). Iron meso-tetrakis(3-thienyl)porphyrin complexes were electropolymerized onto a Au wire electrode. The modified Au electrode were applied to .O(2)(-) sensor to detect catalytic oxidation current of .O(2)(-) which was generated as an intermediate during the oxidation of xanthine by catalystic XOD. It was revealed that the sensor was quantitative to measure .O(2)(-). The modified Au electrode were applied to measure oxidation current of .O(2)(-) in mung beans under environmental stress condition. Plants were grown in atmosphere, 25 degrees C and in black darkness. The other plants were exposed to oxygen excess. The oxidation current of .O(2)(-) were increased plants were grown by high-oxygen environment compared to plants were grown at atmosphere. This experiment was indicated that environmental stress such as hyperoxia induced excess .O(2)(-) and Au wire sensor using iron porphyrin complexes is capable of .O(2)(-) detection in plants under environmental stresses.     

卤化物在合成亚硫酸金盐溶金过程中的作用

用离子交换膜电解法研究了金在Na2SO3溶液中加入Cl-、Br-后的阳极溶解机理.结果表明,在Na2 SO3溶液中加入Cl-和Br-后,由于竞争配位作用可以加快金的溶解速率.Br-在阳极表面被氧化生成初生态Br2,Br2可以快速氧化阳极金从而更有效地抑制SO32-氧化,有利于获得高纯度Na3 Au(SO3)2溶液.     

含咔唑基聚合物的合成、发光性能及应用

采用封管聚合法合成了3种含咔唑基聚合物——聚乙烯基咔唑(PVK)、聚2-(9-咔唑基)乙基甲基丙烯酸酯(PCEM)和聚N-〔3-(9-乙基咔唑基)〕甲基丙烯酰胺(PECMA),考察了其紫外光谱和荧光光谱,探讨了取代基对咔唑基团发光性能的影响。结果表明,单体CEM和ECMA表现出明显的结构自猝灭效应(SSQE),而相应的聚合物未见SSQE。单体乙烯基咔唑(NVK)、CEM的荧光最大发射波长分别为440、435 nm,相对于咔唑(418nm)有明显的红移,ECMA则蓝移(410 nm),而相应的聚合物红移或蓝移都不明显。将聚合物作为空穴传输材料,通过共聚引入8-羟基喹啉铝高分子后,8-羟基喹啉铝高分子发光材料的电致发光起亮电压由14 V下降至9V,发光效率提高了3~4倍。     

Relaxation dynamics of Au25L18 nanoclusters studied by femtosecond time-resolved near infrared transient absorption spectroscopy

The relaxation dynamics of electronically excited [Au(25)(SR)(18)](q), where q = 0 or -1 and SR = S(CH(2))(2)Ph, were studied using femtosecond time-resolved transient absorption spectroscopy. Nanoclusters excited by 400 nm light were probed using temporally delayed broad-bandwidth continuum probe pulses. Continuum pulses were generated in both the visible and near infrared (NIR) spectral regions, providing access to a wide range of transient spectral features. The use of NIR probe pulses allowed the relaxation dynamics of the excited states located near the HOMO-LUMO energy gap to be monitored in the probe step via the sp ← LUMO and sp ← LUMO+1 transitions. These NIR measurements yielded excited state absorption (ESA) data that were much less congested than the typical visible transient spectrum. For the neutral nanocluster, the time-domain data were composed of three components: (1) a few-picosecond decay, (2) a slower decay taking a few hundred picoseconds and (3) a non-decaying plateau function. Component 1 reflected energy relaxation to semi-ring ligand states; component 2 was attributed to relaxation via a manifold of states located near the HOMO-LUMO energy gap. Component 3 arose from slow radiative recombination. The dynamics of the anion depended upon the identity of the excited state from which the particle was relaxing. The LUMO+1 state of the anion exhibited relaxation dynamics that were similar to those observed for the neutral nanocluster. By comparison, the time-domain data observed for the LUMO state contained only two components: (1) a 3.3 ± 0.2 ps decay and (2) a 5 ± 1 ns decay. The amplitude coefficients of each component were also analyzed. Taken together, the amplitude coefficients and lifetimes were indicative of an activation barrier located approximately 100 meV above the HOMO-LUMO energy gap, which mediated a previously unobserved excited state decay process for [Au(25)(SR)(18)](0). These data suggested that NIR ESA measurements will be instrumental in describing the relaxation processes of quantum-confined nanoclusters.     

乙醇-硫酸铵-碘化钾体系萃取分离Bi(Ⅲ)的新方法

研究了乙醇-硫酸铵-碘化钾体系分离铋的行为及其与常见离子分离的条件。实验表明,在碘化钾存在下,B i(Ⅲ)以B iI63-形式与质子化乙醇(C2H5OH2+)形成离子缔合物B iI63-(C2H5OH2+)3,可被乙醇相萃取,固定B i(Ⅲ)用量为50μg,乙醇用量为3.0 mL,当(NH4)2SO4用量为3.5 g,K I(0.1 mol/L)用量为1.25 mL时,B i(Ⅲ)能被完全浮选,控制pH 2.0,B i(Ⅲ)能与常见离子Mn(Ⅱ)、Fe(Ⅲ)、N i(Ⅱ)、Zn(Ⅱ)分离。     

Formation of first gold(III) complex of an N(4)-disubstituted thiosemicarbazone derived from 2-benzoylpyridine: structural and spectral studies

The reaction between gold(III) chloride(AuCl₃) and 2-benzoylpyridine N(4), N(4)-(butane-1,4-diyl) thiosemicarbazone (HBpypTsc) leads to an unexpected formation of a first gold(III) complex from an N(4)-disubstituted thiosemicarbazone derived from 2-benzoylpyridine. The crystal structure, spectroscopic characterization, and preliminary biological activity of [Au(III)(Cl)(BpypTsc)][Au(I)Cl₂] complex are discussed herein.