离子液体辅助水热法合成六方WO3纳米棒束

提出了利用简单的离子液体1-甲基-3-乙基-咪唑溴辅助水热法合成六方WO₃纳米棒束的方法,对其结构进行了表征,并讨论其形成机理。TEM照片表明：WO₃纳米棒束由长200~300 nm、直径25~30 nm的纳米棒组装而成。离子液体1-甲基-3-乙基-咪唑溴在纳米棒的形成过程中起到了结构导向剂的作用。     

A Tray‐Shaped,PdII‐Clipped Au3 Complex as a Scaffold for the Modular Assembly of [3×n] Au Ion Clusters

A tray‐shaped Pd^II₃Au^I₃ complex ( 1 ) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with Au^I followed by Pd^II clipping. Tray 1 is an efficient scaffold for the modular assembly of [3×n] Au^I clusters. Treatment of 1 with the Au^I₃ tricyclic guest 2 in H₂O/CH₃CN (7:3) or H₂O results in the selective formation of a [3×2] cluster ( 1 ⋅ 2 ) or a [3×3] cluster ( 1 ⋅ 2 ⋅ 1 ), respectively. Upon subsequent addition of Ag^I ions, these complexes are converted to an unprecedented Au₃–Au₃–Ag–Au₃–Au₃ metal ion cluster.     

Surface and Structural Properties of Gold Nanoparticles and Their Biofunctionalized Derivatives in Aqueous Electrolytes Solution

Gold nanoparticles reduced by sodium citrate (d ～ 10 nm) and purchased gold colloid particles (d ～ 500 nm) were examined and compared. The properties of both gold particles and their biofunctionalized derivatives with L-cysteine and L-glutathione were studied in the presence of sodium nitrate. The structural investigations indicated an aggregated inner structure.

The isoelectric points of pure gold, citrate reduced gold, and functionalized gold were measured and compared. The low isoelectric point of pure gold/water interface was explained by considering the distribution and accumulation of H⁺ and OH^? ions within the interfacial water layer, being more pronounced for OH^? ions.      

Flame atomic absorption spectrometry determination of trace amount of gold after separation and preconcentration onto ion-exchange polyethylenimine coated on Al2O3

The object of this work is to develop a simple and selective method for efficient extraction of Au(III) ions in aqueous solution using a new solid-phase extraction sorbent. Polyethylenimine (PEI) ion-exchange polymer was coated on alumina in the presence of NaNO₃. The method is based on sorption of Au³⁺ ions on 50 mg PEI/Al₂O₃. A solution of 0.5 M thiourea, then 1.0 M HCl effectively eluted the gold ion and then aspirated into flame atomic absorption spectroscopy (FAAS). The influence of flow rate of sample solution and eluent, the pH effect, eluent type and sorption capacity was investigated. The effects of various diverse ions for preconcentration and separation of the gold ion were investigated. Relative standard deviation of 4.0 μg mL⁻¹ of gold was 1.46% (n = 10). The detection limit was 26.2 ng L⁻¹ in original solution. The method has been applied successfully for the recovery of trace amount of Au(III) ions from water samples.     

Theoretical investigation of inclusion complex formation of Gold (III) – Dimethyldithiocarbamate anticancer agents with cucurbit[n = 5,6]urils

Gold (III)-N,N-dimethyldithiocarbamate [DMDT(Au)X₂] complexes have recently gained increasing attention as potential anticancer agents because of their strong tumor cell growth–inhibitory effects, generally achieved by exploiting non-cisplatin-like mechanisms of action. The goal of our research work is to encapsulate the gold(III) dimethyldithiocarbamate complexes as anticancer with cucurbit[n]urils (CB[n = 5, 6]) by accurate calculations, to predict the inclusion complex formation of gold(III) species with cucurbiturils (CB[n = 5, 6]). The calculations were carried out just for the 1:1 stoichiometric complexes. Upon encapsulation, binding energy, thermodynamic parameters, structural parameters and electronic structures of complexes are investigated. The results of the thermodynamic calculations and the binding energy show that the inclusion process is exothermic and the CB[6]/[DMDT(Au)Br₂] complex is more stable than other complexes. The final geometry of CB[n]/drugs indicates that the drugs were expelled from the cavity of CB[n]. NBO calculations reveal that the hydrogen bonding between CB[n] and drugs and electrostatic interactions are the major factors contributing to the overall stabilities of the complexes.     

紫外光辐照下CH3NH3PbI3基钙钛矿太阳能电池失效机制

随着光伏产业的不断发展,有机无机杂化钙钛矿太阳能电池的研发成为科学与工业界广泛关注的焦点。到目前为止,其光电转换效率已经提高到了25.2%,成为替代硅基太阳能电池的核心方案之一。然而,钙钛矿太阳能电池的稳定性较差,容易受到环境中氧气、水分、温度甚至光照的影响,这严重制约了其大规模推广与应用。大量科学研究表明,如何避免紫外辐照下有机无机杂化钙钛矿太阳能电池的性能衰减,对于提高钙钛矿太阳能电池的光照稳定性至关重要。然而到目前为止,仍然没有系统的工作来对紫外辐照下钙钛矿太阳能电池性能以及微结构演化过程进行详细的表征与分析。本文中,我们利用聚焦离子束-扫描电子显微分析(FIB-SEM)以及球差校正透射电子显微分析(TEM)等技术,全面地研究了紫外辐照过程中有机无机杂化钙钛矿太阳能电池性能变化规律以及电池微结构演化特征。实验结果表明,紫外辐照过程中太阳能电池内部会形成0.5–0.6 V的内建电场,钙钛矿中的I^-离子在电场的驱动下向金属Au电极和空穴传输层2, 2’, 7, 7’-四[N, N-二(4-甲氧基苯基)氨基]-9, 9'-螺二芴(Spiro-OMeTAD)一侧迁移;随后,空穴传输层与金电极的界面处,碘离子与光生空穴一起与金电极发生反应,将金属态Au氧化成离子态Au⁺。而Au⁺离子则在内建电场的驱动下反向迁移穿过钙钛矿MAPbI₃层,直接被SnO₂和MAPbI₃界面处的电子还原形成金属Au纳米团簇。除此之外,紫外辐照过程中钙钛矿太阳能电池性能降低的同时,往往伴随着Spiro-OMeTAD与钙钛矿界面处物质迁移、钙钛矿薄膜内晶界展宽以及Au纳米颗粒周围MAPbI₃物相分解等现象。以上各种因素的协同作用,共同导致了紫外光照下有机无机杂化钙钛矿太阳能电池光电转换性能(PCE)、开路电压(V_oc)以及短路电流(J_sc)等性能参数的急剧下降。     

Pressure-responsive AuNPs/Polyacrylamide Nanocomposite Hydrogel with Highly Stable and Tunable Electrochemiluminescence Performances

Synergistically taking the advantage of distinctive porous matrix, luminophore and functional nanoparticles, we prepared functional nanocomposite hydrogel combining the hydrophilic three-dimensional network of hydrogels as matrix for the adsorption of luminophore, Ru(bpy)₃²⁺, and in situ grown gold nanoparticles (AuNPs) as the conductive. Interestingly, the designed nanocomposite hydrogel shows external pressure resposnsive properties, which precisely tune the distance between the AuNPs becomes shorter, resulting in a remarkable amplification of electrochemiluminescence (ECL) signals. Additionally, differing from the poor stability of conventional ECL, uniform dispersion of the Ru(bpy)₃²⁺ over nanocomposite hydrogel significantly enhanced the long term stability of ECL.     

Block Copolymer Supported Gold Nanoparticles Assemblies with Exposed Gold Surface

Polymer-involved nanoparticles or nanoparticle assemblies are now facing a crossroad, where the exposure of nanoparticle and multiple nanoparticles cannot be obtained at the same time. Therefore, a new series of nanoparticle clusters is synthesized, where multiple gold nanoparticles assemble with amphiphilic block copolymers supporting inside. The exposure of gold nanoparticles of the structure is confirmed and increases the reduction rate of 4-nitrophenol by 60%. The assemblies can also be used as surface enhanced Raman scattering(SERS) probes with an enhancement factor(EF) as high as 3×10³.     

Gold-Catalyzed One-Pot Synthesis of Polyfluoroalkylated Oxazoles from N-Propargylamides Under Visible-Light Irradiation

A gold-catalyzed synthesis of polyfluoroalkylated oxazoles from N-propargylamides under visible-light irradiation has been developed. These reactions display excellent compatibility of radicals and gold catalysts under visible-light irradiation. Mechanistic experiments indicate that polyfluoroalkyl iodides play a dual role in enhanced compatibility of radicals and gold catalysts through assisted protodeauration of vinyl gold and reactivated the gold catalyst. In addition, PPh₃AuNTf₂ not only activates N-propargylamide to generate vinyl gold intermediate, but also greatly promotes homolysis of polyfluoroalkyl iodides under blue light irradiation.     

Biogenic synthesis of gold and silver nanoparticles used in environmental applications: A review

Due to their physical, chemical, optical, and mechanical properties, metallic nanoparticles (MNPs) are increasingly being used, with an emphasis on silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs). In recent years, green synthesis has gained prominence for exploring the use of naturally available biological sources for the obtention of metallic nanoparticles. Among these, algae and plants stand out due to the presence of polysaccharides, proteins, polyphenols, and vitamins (among others) in their composition, which can act in the reduction and stabilisation of MNPs, and these biogenic materials have been characterised mainly by spectrometric and microscopic techniques. In addition, due to the numerous advantages of nanoparticles (NPs) synthetize from biogenic source, such as their simplicity and cost benefits, they have been used in the development of sensors applied in the determination of contaminants present in environmental samples and in the catalytic reduction of organic and inorganic contaminants. Therefore, this review describes the synthesis, mechanisms, characterization, and environmental analytical applications of NPs obtained by biogenic synthesis as well as the perspectives and challenges of these NPs.