Supramolecules‐Guided Synthesis of Brightly Near‐Infrared Au22 Nanoclusters with Aggregation‐Induced Emission for Bioimaging

Protein‐protected gold nanoclusters with emission in the near‐infrared wavelength range have been widely considered for applications in biomedical fields. However, their quantum yield (QY) remains low, thus limiting their practical applications. Herein, a novel strategy to synthesize bovine serum albumin–encapsulated gold nanoclusters (BSA‐AuNCs) with QY of 23% is developed. Assembled coordination polymers (supramolecules) of Au(I)‐BSA complexes are initially formed because of the intermolecular forces between BSA ligands. The forces are easily controlled by pH level during the reaction, leading to significant change in the photoluminescence of BSA‐AuNCs. By regulating the pH and reaction temperature, Au(0)@Au(I) core‐shell structured BSA‐AuNCs are fabricated in 2 h. Importantly, such AuNCs are in a rigidified state with high Au(I) content in the shell, offering an explanation for their high luminescence character. Further increasing QY to 29% is achieved by confining BSA‐AuNCs into a cationic polymer, poly(allylamine) hydrochloride (AuNCs@PAH). Enhanced cellular uptake and improved sensitivity of AuNCs@PAH to glutathione compared to BSA‐AuNCs is demonstrated. These findings may give insights into the synergistic effect of pH level and reaction temperature on the properties of protein‐encapsulated AuNCs and provide a possible way for up‐scaled fabrication of brighter AuNCs protected by other protein templates.     

Synthesis and characterization of binaphthalene-2,2′-diamine-functionalized gold nanoparticles

Gold nanoparticles 1.7 and 54 nm in diameters have been synthesized and functionalized successfully with their surfaces engineered using two atropisomeric capping ligands, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) and 1,1′-binaphthalene-2,2′-diamine (DABN), respectively. A systematic study to compare the two different gold nanoparticles is presented using multiple material characterization techniques. It was found that the two systems show different capping mechanism and hence differ in their intrinsic core and surface properties. The compound BINAP plays only surface capping agent and stabilizes the gold nanoparticles, resulting in small particle size and suppressed surface plasmon resonance absorption at 520 nm. The DABN capping ligand is different from BINAP and acts as both reducing and capping agent, causing the reduction of Au (III) to Au (0). The nucleation growth of the gold core occurs in accordance with the polymerization-passivation process by DABN, resulting in a big particle size of 20 nm. A strong surface plasmon resonance band shows a maximum peak at 564 nm, consistent with the Au core size. The simultaneous oxidative polymerization of DABN and the induced metal reduction process lead to the formation of gold nanoparticles encapsulated by a mixture of DABN oligomers or polymers.

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Laser-assisted generation of gold nanoparticles and nanostructures in liquid and their plasmonic luminescence

Nanoparticles (NPs) and surface nanostructures (NS) are produced via laser ablation of a bulk gold target in liquid using second harmonics of 10 ps Nd:YAG laser (532 nm) with repetition rate of 50 kHz. The morphology and plasmon photoluminescence (PL) properties of obtained nanoscale objects are described. Transmission electron microscopy and field emission scanning electron microscopy are used for morphology characterization of NPs and NS, respectively. Plasmon PL of both gold NPs and NS is experimentally studied using the third harmonics of the Nd:YAG picosecond laser (355 nm) as a pump. The wavelength of intensity maximum of PL of Au NPs colloidal solution virtually coincides with the position of Au NPs plasmon absorption peak. Real-time excitation of both plasmon PL and Raman scattering of surrounding liquid by picosecond laser pulses in aqueous colloidal solution is also investigated. The efficient cross section of plasmon PL of Au NPs colloid is evaluated using Raman scattering of water as a comparative parameter. The results are in good agreement with values obtained in previous works. Plasmon PL from self-organized NS on the Au surface produced via laser ablation is observed for the first time. Its spectrum is compared to PL spectra of both aqueous colloidal solutions of NPs and of NPs deposited on a Si wafer. The obtained experimental data are discussed with reference to the band structure of bulk Au.     

Preparation of Gold/triblock Copolymer Composite Nanoparticles

A kind of novel gold (Au)/hydroxylated poly (styrene-b-butadiene-b-styrene) triblock copolymer (HO-SBS) composite nanoparticles was synthesized by reduction of tetrachloroaurate ions in HO-SBS micelle. The Au–HO-SBS composite nanoparticles are composed by gold core about 35 nm in diameter and polymer shell about 7 nm in thickness. Formation of the Au/HO-SBS nanoparticles is indentified by infrared (IR) and UV-visible absorption spectroscopies. Transmission electron microscopy (TEM) result shows that the composite nanoparticles tend to aggregate into an ordered hexagonal array on carbon-coated grid.     

Gold Nanoparticles Stabilized by Single Tripodal Ligands

In order to coat the entire surface of gold nanoparticles (AuNPs) by a single ligand, tripodal macromolecules comprising benzylic thioethers coordinating to the AuNP surface are synthesized and their abilities to stabilize AuNPs are investigated. Out of the five studied ligands 1 – 5 , the tetraphenylmethane‐based oligomers 4 and 5 display excellent AuNP coating features. Both ligand structures are able to control the dimensions of the AuNPs by stabilizing particles of narrow size distributions during their syntheses (1.05 ± 0.28 nm for Au‐4 , and 1.15 ± 0.34 nm for Au‐5 ). Closer inspection of these AuNPs by transmission electron microscopy and thermogravimetric analyses suggests that single ligands 4 and 5 are able to stabilize entire AuNPs. These particles Au‐4 and Au‐5 are obtained in good yields and display promising thermal stabilities (110 °C for Au‐4 , and 95 °C for Au‐5 ), making them interesting nanoscale inorganic–organic building blocks for further functionalization/processing by wet chemistry.     

Composition distributions in FePt(Au) nanoparticles

Ternary alloy FePt(Au) nanoparticles were prepared by the co-reduction of platinum(II) acetylacetonate and gold(III) acetate and the thermal decomposition of iron pentacarbonyl in hot phenyl ether in the presence of oleic acid and oleylamine ligands. This gave spherical particles with an average diameter of 4.4 nm with a range of diameters from approximately 1.6–9 nm. The as-synthesized particles had a solid solution, face-centered-cubic structure. Though the average composition of the particles was Fe₄₄Pt₄₅Au₁₁, individual particle analysis by Scanning Transmission Electron Microscopy–X-ray Energy Dispersive Spectroscopy showed a broad distribution in composition. In general, smaller-sized particles tended to have a lower amount of Au as compared to larger-sized particles. As the Au content increased, the ratio of Fe/Pt widened.     

PEGylated Luminescent Gold Nanoclusters: Synthesis,Characterization, Bioconjugation,and Application to One‐ and Two‐Photon Cellular Imaging

Biocompatible, near‐infrared luminescent gold nanoclusters (AuNCs) are synthesized directly in water using poly(ethylene glycol)‐dithiolane ligands terminating in either a carboxyl, amine, azide, or methoxy group. The ≈1.5 nm diameter AuNCs fluoresce at ≈820 nm with quantum yields that range from 4–8%, depending on the terminal functional group present, and display average luminescence lifetimes approaching 1.5 μs. The two‐photon absorption (TPA) cross‐section and two‐photon excited fluorescence (TPEF) properties are also measured. Long‐term testing shows the poly(ethylene glycol) stabilized AuNCs maintain colloidal stability in a variety of media ranging from saline to tissue culture growth medium along with tolerating storage of up to 2 years. DNA and dye‐conjugation reactions confirm that the carboxyl, amine, and azide groups can be utilized on the AuNCs for carbodiimide, succinimidyl ester, and Cu^I‐assisted cycloaddition chemistry, respectively. High signal‐to‐noise one‐ and two‐photon cellular imaging is demonstrated. The AuNCs exhibit outstanding photophysical stability during continuous‐extended imaging. Concomitant cellular viability testing shows that the AuNCs also elicit minimal cytotoxicity. Further biological applications for these luminescent nanoclustered materials are discussed.     

Size-controlled growth of gold nanoparticle-doped carbon foams as sensitive electrochemical sensors for the determination of Pb(II)

A sensitive and selective electrochemical Pb²⁺ sensor consisting of a gold-carbon foam/chitosan/gold (Au-CFs/Chit/Au)-modified electrode was prepared. The electrode was synthesized via an oil-in-water emulsion polymerization and carbonization approach. Phenolic resins were used as a carbon source. HAuCl₄ was used as a gold source and as an acidic catalyst. Melamine was used as a coordination and coupling agent to control the size of the Au nanoparticles (AuNPs). The morphologies and microstructures of the Au-CFs were characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results revealed that the carbon foams contained interconnected macropores with diameters of nearly 5.0 μm and AuNPs with mean diameters of approximately 20.0, 9.0, and 7.0 nm. Brunauer–Emmett–Teller analysis revealed that the biggest surface area is 653.82 m²/g for Au/CFs-7. The electrochemical properties of modified electrodes and their responses to Pb²⁺ were characterized using cyclic voltammetry and differential pulse anodic stripping voltammetry. The influence of the test conditions were studied to optimize operational parameters such as the choice of supporting electrolyte, pH, deposition potential, and deposition time. Under optimal conditions, typical Au/CFs-7-modified gold electrodes exhibited an excellent electrochemical response for Pb²⁺ with a wide linear response range from 0.01 to 1.2 μM, a correlation coefficient of 0.995, and a lower limit of detection of 0.63 nM with deposition time of 180 s (S/N?=?3).     

Studies on multivalent interactions of quantum dots–protein self-assemble using fluorescence coupled capillary electrophoresis

A method is presented for using a single laser pulse to transform polymorphic polycrystalline gold nanoparticles (Au NPs) into crystalline nanospheres. Transmission electron microscope analysis of the nominally 60-nm-diameter Au NP starting material and the product suspension confirms the production of slightly smaller particles that exhibit greater crystallinity and feature reduced caliper diameter aspect ratios and anisotropy. Centrifugation followed by ultrasonic resuspension into citrate solution separates the nanospheres from the <15 nm ablation fragments, providing a route to monodisperse spherical crystalline Au NPs.     

Deposition of colloidal gold nanoparticles by fully pulsed-voltage-controlled electrohydrodynamic atomisation

Pulsed electrohydrodynamic atomisation (EHDA) of aqueous 10 nm gold colloid in a full voltage-controlled form was investigated. By using 4 µm and 20 μm nozzles, electrified fluid jet was emitted and Au nanoparticles in the jet were deposited onto a silicon substrate. Scanning electron microscopy (SEM) revealed that different morphology of the artifact was formed by using different voltages pulses. Particularly, island-liked artifact down to 10 μm can be produced regularly in the case of cone-jet mode by low voltage pulse. Our results demonstrate pulsed EHDA is a promising approach in creating micro-patterns of colloid-based nanomaterials.     

Green Chemical Synthesis of N-Cholyl-L-Cysteine Encapsulated Gold Nanoclusters for Fluorometric Detection of Mercury Ions

Herein we report a simple, single-step, cost-effective, environmentally friendly, and biocompatible approach using sodium salt of N-cholyl-L-cysteine (NaCysC) capped gold nanoclusters (AuNCs) with green emission properties at above the CMC in aqueous medium under UV-light irradiation. The primary and secondary CMC of NaCysC was found to be 4.6 and 10.7 mM respectively using pyrene as fluorescent probe. The synthesized AuNCs exhibit strong emission maxima at 520 nm upon excitation at 375 nm with a large Stokes shift of 145 nm. The surface functionality and morphology of NCs are studied by fourier transform infrared spectroscopy, dymanic light scattering studies and transmission electron microscopy. The formation of AuNCs was completed within 5 h and exhibit high stability for more than 6 months. The NaCysC templated AuNCs selectively quenches the Hg²⁺ ions with higher sensitivity in aqueous solution over the other metal ions. The fluorescence analysis of Hg²⁺ showed a wide linear range from 15 to 120 µM and a detection limit was found to be 15 nM.

     

Silver,gold and the corresponding core shell nanoparticles: synthesis and characterization

Simple strategies for producing silver and gold nanoparticles (AgNP and AuNP) along with the corresponding core shell nanoparticles (Au–Ag and Ag–Au) by reduction of the metal salts AgBF₄ and HAuCl₄ by NaBH₄ in water will be presented. The morphologies of the obtained nanoparticles are determined by the order of addition of reactants. The obtained NPs, with sizes in the range 3–40 nm, are characterized by transmission electronic microscopy (TEM) and UV–Vis absorption spectroscopy, so as to evaluate their qualities. Moreover, a direct electrochemical detection protocol based on a cyclic voltammetry in water solution that involves the use of glassy carbon electrode is also applied to characterize the prepared NPs. The developed NPs and the related electroanalytical method seem to be with interest for future sensing and biosensing applications including DNA sensors and immunosensors.     

Multifunctional Plasmonic Co‐Doped Fe2O3@polydopamine‐Au for Adsorption,Photocatalysis, and SERS‐based Sensing

A new type of multifunctional plasmonic nanoparticles, cobalt‐doped Fe₂O₃@polydopamine‐Au (Co‐Fe₂O₃@PDA‐Au), is fabricated via coating PDA through self‐polymerization onto Co‐Fe₂O₃ and further loading gold nanoparticles by in situ reduction onto the surface of PDA shell. Benefiting from the universal adhesive ability of PDA and negative zeta potetntial of the composite, the Co‐Fe₂O₃@PDA‐Au shows strong adsorptivity for cationic dyes. The presence of gold nanoparticle with the diameter of 15 nm in the Co‐Fe₂O₃@PDA‐Au system promotes surface‐enhanced Raman scattering (SERS) activity with an impressive detection limit of 1 × 10^?6 m . Thanks to the synergistic effect of the light harvesting of PDA, the surface plasmon resonance of Au, and the electron conductibility of PDA and Au, the Co‐Fe₂O₃@PDA‐Au exhibits an enhanced photocatalytic activity comparing with unmodified Co‐Fe₂O₃. All the above‐mentioned functions enable Co‐Fe₂O₃@PDA‐Au to be a multifunctional material system for various applications toward environmental pollutants.     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

水溶性金单层包覆团簇的制备与光学性能分析

 采用硼氢化钠在水溶液中还原氯金酸,并以水溶性硫醇巯基丁二酸在生成的金核表面包覆单分子层的方法,制备了单层包覆金团簇（MPC）。傅里叶变换红外光谱仪结果表明,巯基丁二酸与金形成了Au－S键,并得到了Auz^x(SR)^y形式的MPC。TEM照片显示,当Au和S的物质的量的比为1∶3时,金MPC的核尺寸约为2 nm。探讨了制得的金MPC的紫外-可见吸收特性及荧光特性,发现金MPC水溶液在520 nm附近无紫外吸收现象,而在451及480 nm波长紫外光激发下,可在796 nm附近观察到明显的荧光现象。反映表面等离子基元共振的520 nm附近吸收峰的消失是量子尺寸效应作用的结果。荧光现象与金MPC表面全充满的5d10和6(sp)1导带间的带间跃迁有关。     

基于聚腺嘌呤单链DNA-金纳米簇的荧光法高灵敏快速检测汞离子

聚腺嘌呤-金纳米簇（聚A-AuNCs）制备简单,快速,且具有优良的荧光性能和光学稳定性。基于聚A单链DNA为模板合成的金纳米簇,构建了一种灵敏、简单、快速的新传感方法用于检测汞离子。以柠檬酸钠为还原剂,通过水浴加热法合成金纳米簇。用荧光光谱仪和透射电镜对金纳米簇的荧光性能和微观形貌进行了表征。结果表明：合成的金纳米簇为球形,分散性良好,平均粒径约为7 nm。金纳米簇在280 nm紫外光激发下,于471 nm处发射出强烈的蓝色荧光,且金纳米簇的光学稳定性良好。溶液在4 ℃下避光保存1个月,金纳米簇的荧光强度变化很小。当汞离子存在时,汞离子与纳米金之间的高亲和力,可以有效地猝灭金纳米簇的荧光。文中讨论了反应体系中缓冲溶液pH值和反应时间对传感器性能的影响,发现缓冲溶液pH值对该方法的影响不大。汞离子对金纳米簇的荧光猝灭反应非常迅速,1 min之内就可以完成,所以后续反应仅需简单的混合即可进行荧光的测定。在最优化实验条件下,对一系列汞离子浓度进行了检测,线性方程为：y=-335.57x+541.35,检测线性范围在0.01~1 μmol·L-1之间,相关系数为0.992 6。根据空白的三倍标准偏差原则确定检测下限为3 nmol·L-1。该方法选择性好,通过9种金属离子的加入对金纳米簇的荧光信号并无明显影响,验证了金纳米簇对汞离子检测的特异性。用该方法检测了环境水样中的汞离子,加标回收率在95.33％~103.8％之间,相对标准偏差（RSD）不大于4%,可用于实际样品中Hg2+的检测。该法仅需将溶液简单混合即可实现对汞离子的检测,具有操作简便、快速、灵敏度高和选择性好等优点。     

A Correlative Analysis of Gold Nanoparticles Internalized by A549 Cells

Fluorescently labeled nanoparticles are widely used to investigate nanoparticle cell interactions by fluorescence microscopy. Owing to limited lateral and axial resolution, nanostructures (<100 nm) cannot be resolved by conventional light micro­scopy techniques. Especially after uptake into cells, a common fate of the fluorescence label and the particle core cannot be taken for granted. In this study, a correlative approach is presented to image fluorescently labeled gold nanoparticles inside whole cells by correlative light and electron microscopy (CLEM). This approach allows for detection of the fluorescently labeled particle shell as well as for the gold core in one sample. In this setup, A549 cells are exposed to 8 nm Atto 647N‐labeled gold nanoparticles (3.3 × 10⁹ particles mL^?1, 0.02 μg Au mL^?1) for 5 h and are subsequently imaged by confocal laser scanning microscopy (CLSM) and transmission electron microscopy (TEM). Eight fluorescence signals located at different intracellular positions are further analyzed by TEM. Five of the eight fluorescence spots are correlated with isolated or agglomerated gold nanoparticles. Three fluorescence signals could not be related to the presence of gold, indicating a loss of the particle shell.     

Generation of MoS<Subscript>2</Subscript> quantum dots by laser ablation of MoS<Subscript>2</Subscript> particles in suspension and their photocatalytic activity for H<Subscript>2</Subscript> generation

MoS₂ quantum dots (QDs) have been obtained in colloidal suspensions by 532 nm laser ablation (7 ns fwhp/pulse, 50 mJ/pulse) of commercial MoS₂ particles in acetonitrile. High-resolution transmission electron microscopy images show a lateral size distribution from 5 to 20 nm, but a more homogeneous particle size of 20 nm can be obtained by silica gel chromatography purification in acetonitrile. MoS₂ QDs obtained by laser ablation are constituted by 3–6 MoS₂ layers (1.8–4 nm thickness) and exhibit photoluminescence whose λ_PL varies from 430 to 530 nm depending on the excitation wavelength. As predicted by theory, the confinement effect and the larger periphery in MoS₂ QDs increasing the bandgap and having catalytically active edges are reflected in an enhancement of the photocatalytic activity for H₂ generation upon UV–Vis irradiation using CH₃OH as sacrificial electron donor due to the increase in the reduction potential of conduction band electrons and the electron transfer kinetics.     

Nitrogen-doped and gold-loaded TiO2 photocatalysts synthesized by sequential reactive pulsed laser deposition

Nitrogen-doped titanium oxide thin films covered by gold metal nanoparticles were grown on (001) SiO₂ quartz substrates by pulsed laser deposition. A KrF* excimer laser source (λ = 248 nm, τ _FWHM ≤ 25 ns, ν = 10 Hz) was used for the irradiation of TiO₂ and gold metal targets. The experiments were performed in controlled reactive oxygen or nitrogen atmosphere. The layers were grown for photocatalytic applications. Evaluation of photocatalytic activity was performed by photodegradation of methyl orange under near-UV light irradiation. Our results show that nitrogen doping and addition of gold nanoparticles have complementary effects, photoactivity being significantly improved as compared to that of pure titanium oxide.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.