Gold nanoparticles protected with pH and temperature-sensitive diblock copolymers

Aqueous dispersions of gold nanoparticles protected with a stimuli-sensitive diblock copolymer were studied as a function of pH and temperature. Poly(methacrylic acid)-block-poly(N-isopropylacrylamide), PMAA-b-PNIPAM, copolymer was synthesized using the RAFT technique. A one-pot method utilizing the dithiobenzoate functionalized polymer was used to prepare gold nanoparticles protected with PMAA-b-PNIPAM. The gold nanoparticles coated with block copolymers, with the PNIPAM block bound to the particle surface and PMAA as an outer block form stimuli-sensitive aggregates in water. The changes in the absorption maxima of the surface plasmon resonance, SPR, of the gold particles and in the size of the aggregates were investigated as a function of pH and temperature. pH was observed to affect the size of the aggregates, whereas the effect of temperature was moderate. However, a blue shift in the SPR was observed both with decreasing pH and increasing temperature. Whereas the PMAA blocks control the colloidal stability of the particles and their aggregates, the thermo-sensitive PNIPAM blocks have a noticeable effect on the polarity of the immediate surroundings of the particles.     

Formation of gold nanoparticles catalyzed by platinum nanoparticles: assessment of the catalytic mechanism

The understanding of how the formation of metal nanoparticles in aqueous solutions is influenced by the presence of presynthesized nanoparticles is important for precise control over size, shape, and composition of nanoparticles. New insights into the catalytic mechanism of Pt nanoparticles are gained by studying the formation of gold nanoparticles from the reduction of AuCl(4)(-) in aqueous solution in the presence of presynthesized Pt nanoparticles as a model system. The measurement of changes of the surface plasmon resonance band of gold nanoparticles, along with TEM analysis of particle size and morphology, provided an important means for assessing the reaction kinetics. The reductive mediation of Pt-H species on the Pt nanocrystal surface is believed to play an important role in the Pt-catalyzed formation of gold nanoparticles. This important physical insight is evidenced by comparison of the rates of the Pt-catalyzed formation of gold nanoparticles in the presence and in the absence of hydrogen (H(2)), which adsorb dissociatively on a Pt nanocrystal surface forming Pt-H species. Pt-H effectively mediates the reduction of AuCl(4)(-) toward the formation of gold nanoparticles. Implications of the findings to the controllability over size, composition, and morphology of metal nanoparticles in the aqueous synthesis environment are also discussed.     

Preparation of Gold Nanorods by Electrolysis:Electrochemical Reduction or Chemical Reduction?

In the synthesis of nanosized materials, to control the particle shape is as important as to control its size, because the properties of the nanoparticles strongly depend on both size and shape. The properties of Au nanorods are different from its spherical counterparts in some ways due to the geometric anisotropy. For example, there are two surface plasmon resonance (SP) peaks in the UV-Vis region for Au nanorods, namely, the transverse (SP_t) peak and the longitudinal (SP₁) peak, respectively, while only one for spherical nanoparticles. Recently, Wang et al.^[1,2] proposed an electrolysis-based method to produce Au nanorods with high throughput for the first time, and it was successfully adopted by El-Sayed et al.^[3,4] in their studies on the optical properties and the thermal/laser induced shape transition of gold nanorods. However, the detailed growth mechanism of Au nanorods in such an approach remains untouched at present stage. To this point, only an ambiguous statement is available in Wang's paper^[1,2] as that "the gold nanorods were converted from the bulk anode most likely at the interfacial region of the cathodic surface and within the electrolytic solution",it is still unclear whether the gold nanorods are formed electrochemically or chemically.     

Electromagnetic interactions in plasmonic nanoparticle arrays

Single two-dimensional planar silver arrays and one-dimensional linear gold chains of nanoparticles were investigated by dark-field surface plasmon spectroscopy and studied as a function of interparticle distance, particle size, and number of particles. In agreement with recent theoretical predictions, a red shift of the surface plasmon resonance occurring in two-dimensional arrays was found for lattice spacings below 200 nm. This red shift is associated with a significant broadening of the resonance and is attributed to the onset of near-field interactions. We found that the relative contributions of the long-range and short-range interactions in two-dimensional arrays of particles are fundamentally different to those occurring in individual linear chains.     

Estimation of dielectric function of biotin-capped gold nanoparticles via signal enhancement on surface plasmon resonance

Biotin-capped gold nanoparticles assembled on flat gold with volume fraction f are studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM) in order to estimate the dielectric function of the gold nanoparticles based on the Maxwell-Garnett (MG) theory. The complex dielectric function (epsilon',epsilon') of the spherical nanoparticles at three representative wavelengths in the vis-near-IR region, i.e., lambda = 543, 632.8, and 1152 nm, is estimated for a surface homogeneously covered with nanoparticles in order to discuss the wavelength dependence of the dielectric function. The SPR response of a surface covered with particles in 2D aggregates is also analyzed. The experimental SPR curve of the particle aggregates deviates from the theoretical predictions, suggesting dipole interactions between particles.     

Characterization of Labeled Gold Nanoparticles for Surface-Enhanced Raman Scattering

Noble metal nanoparticles (NP) such as gold (AuNPs) and silver nanoparticles (AgNPs) can produce ultrasensitive surface-enhanced Raman scattering (SERS) signals owing to their plasmonic properties. AuNPs have been widely investigated for their biocompatibility and potential to be used in clinical diagnostics and therapeutics or combined for theranostics. In this work, labeled AuNPs in suspension were characterized in terms of size dependency of their localized surface plasmon resonance (LSPR), dynamic light scattering (DLS), and SERS activity. The study was conducted using a set of four Raman labels or reporters, i.e., small molecules with large scattering cross-section and a thiol moiety for chemisorption on the AuNP, namely 4-mercaptobenzoic acid (4-MBA), 2-naphthalenethiol (2-NT), 4-acetamidothiophenol (4-AATP), and biphenyl-4-thiol (BPT), to investigate their viability for SERS tagging of spherical AuNPs of different size in the range 5 nm to 100 nm. The results showed that, when using 785 nm laser excitation, the SERS signal increases with the increasing size of AuNP up to 60 or 80 nm. The signal is highest for BPT labelled 80 nm AuNPs followed by 4-AATP labeled 60 nm AuNPs, making BPT and 4-AATP the preferred candidates for Raman labelling of spherical gold within the range of 5 nm to 100 nm in diameter.     

Assembly process of CuHCF/MPA multilayers on gold nanoparticles modified electrode and characterization by electrochemical SPR

Gold nanoparticles were deposited onto 2-mercaptoethylamine (MEA)-assembled planar gold thin film to construct gold nanoparticles modified electrode by virtue of a solution-based self-assembly strategy. Subsequently, 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers were constructed on the as-prepared gold nanoparticles modified electrode. The resulted multilayer nanostructures were investigated by electrochemical surface plasmon resonance (EC-SPR) and atomic force microscopy (AFM) with primary emphasis upon the effect of the gold nanoparticles on the MPA/CuHCF multilayers growth and their surface morphology. Compared with the multilayer system on a planar gold electrode, the different electrochemical and optical properties might result from higher curvature effect and extraordinary surface-to-volume ratio characteristic of gold nanoparticles and the nanoparticle-selective growth of CuHCF. A dendrimer-like assembly process was proposed to explain the experiment results. This new motif of multilayer on the gold nanoparticles modified electrode was different from that of on a planar gold electrode, indicating a potential application of EC-SPR technique in the study of nanocomposite materials.     

Effect of Laser Pulse Energy on the Characteristics of Cu Nanoparticles Produced by Laser Ablation Method in Acetone

The effect of laser fluence on the characteristics of Cu nanoparticles, prepared by laser ablation method, is investigated experimentally. 1–6 nm Cu nanoparticles were synthesized by the pulsed laser ablation of a high purity copper bulk in acetone. Effect of laser fluence on the size, morphology and structure of produced nanoparticles has been studied. Pulses of a Q-switched Nd:YAG laser of 1,064 nm wavelengths at 7 ns pulse width at different fluences was employed to irradiate the Cu target in acetone. The UV–Vis–NIR absorption spectra of nanoparticles exhibit surface plasmon resonance absorption peak in the visible region. TEM and SEM micrographs indicate that with increasing the laser fluence the average size of spherical Cu nanoparticles is decreased and only the sample which is produced with the highest fluence shows exceptional behavior. It is found that Cu nanoparticles exhibit photoluminescence emission with single peak due to its interband transition.     

Fabrication of Xanthan stabilized green gold nanoparticles based tolbutamide delivery system for enhanced insulin secretion in mice pancreatic islets

Abstract

Tolbutamide is an oral anti-diabetic agent for the treatment of type 2 diabetic patients. Its lower absorption results in its inferior therapeutic efficacy. Nano-carrier systems have the subject of greater interests for enhancing efficacy of such drugs. Current study was designed to improve the tolbutamide therapeutic efficacy through its delivery in Gum Xanthan (GX) stabilized green gold nanoparticles (AuNPs). GX stabilized AuNPs were characterized for surface plasmon resonance (SPR), morphology, size, polydisoersity index (PDI) and zeta potential through UV spectrophotometer, atomic force microscope (AFM) and zetasizer respectively. They were used for loading tolbutamide and loaded nanoparticles were investigated for morphology, size, PDI, zeta potential and drug loading efficiency. FT-IR analysis was used for conforming GX functional groups involvement in AuNPs stabilization and drug-excepients interactions. Tolbutamide loaded in the synthesized nanoparticles was investigated for its insulin secretion potentials in isolated mice islets. Synthesized AuNPs were found in nano-size range with spherical morphology, increased surface negativity and loaded increased concentration of drug without changing its chemical nature. They markedly enhanced the tolbutamide insulin secretion potentials as compared to simple drug solution. Results confirm that the developed nano-carrier system is highly efficient in achieving higher therapeutic efficacy of drugs like tolbutamide.     

Sensitivity of metal nanoparticle surface plasmon resonance to the dielectric environment

Electrodynamic simulations of gold nanoparticle spectra were used to investigate the sensitivity of localized surface plasmon band position to the refractive index, n, of the medium for nanoparticles of various shapes and nanoshells of various structures. Among single-component nanoparticles less than 130 nm in size, sensitivities of dipole resonance positions to bulk refractive index are found to depend only upon the wavelength of the resonance and the dielectric properties of the metal and the medium. Among particle plasmons that peak in the frequency range where the real part of the metal dielectric function varies linearly with wavelength and the imaginary part is small and slowly varying, the sensitivity of the peak wavelength, lambda, to refractive index, n, is found to be a linearly increasing function of lambda, regardless of the structural features of the particle that determine lambda. Quasistatic theory is used to derive an analytical expression for the refractive index sensitivity of small particle plasmon peaks. Through this analysis, the dependence of sensitivity on band position is found to be determined by the wavelength dependence of the real part, epsilon', of the particle dielectric function, and the sensitivity results are found to extend to all particles with resonance conditions of the form, epsilon' = -2chin(2), where chi is a function of geometric parameters and other constants. The sensitivity results observed using accurate computational methods for dipolar plasmon bands of gold nanodisks, nanorods, and hollow nanoshells extend, therefore, to particles of other shapes (such as hexagonal and chopped tetrahedral), composed of other metals, and to higher-order modes. The bulk refractive index sensitivity yielded by the theory serves as an upper bound to sensitivities of nanoparticles on dielectric substrates and sensitivities of nanoparticles to local refractive index changes, such as those associated with biomolecule sensing.     

Simple reductant concentration-dependent shape control of polyhedral gold nanoparticles and their plasmonic properties

We report a facile seed-mediated method for the synthesis of monodisperse polyhedral gold nanoparticles, with systematic shape evolution from octahedral to trisoctahedral structures. The control over the particle growth process was achieved simply by changing the concentration of the reductant in the growth solution, in the presence of small spherical seed nanoparticles. By progressively increasing the concentration of the reductant used in the growth solution (ascorbic acid), while keeping the amount and type of added surfactant constant, the morphology of the gold nanoparticles was varied from octahedral to truncated octahedral, cuboctahedral, truncated cubic, cubic, and finally trisoctahedral structures. These nanoparticles were monodisperse in size, possessed similar volumes, and were naturally oriented so that their larger crystal planes were face down on quartz substrates when deposited from the solution. By adjusting the volume of gold seed nanoparticle solution added to a growth solution, the size of the simplest gold nanoparticles (with a highly symmetric cubic morphology) could be tuned from 50 ± 2.1 to 112 ± 11 nm. When other seed nanoparticles were used, the size of the cubic Au nanoparticles reached 169 ± 7.0 nm. The nanoparticle growth mechanism and the plasmonic properties of the resulting polyhedral nanoparticles are discussed in this paper.     

Collective and individual plasmon resonances in nanoparticle films obtained by spin-assisted layer-by-layer assembly

Nanoscale uniform films containing gold nanoparticle and polyelectrolyte multilayer structures were fabricated by the using spin-assembly or spin-assisted layer-by-layer (SA-LbL) deposition technique. These SA-LbL films with a general formula [Au/(PAH-PSS)nPAH]m possessed a well-organized microstructure with uniform surface morphology and high surface quality at a large scale (tens of micrometers across). Plasmon resonance peaks from isolated nanoparticles and interparticle interactions were revealed in the UV-visible extinction spectra of the SA-LbL films. All films showed the strong extinction peak in the region of 510-550 nm, which is due to the plasmon resonance of the individual gold nanoparticles redshifted because of a local dielectric environment. For films with sufficient density of gold nanoparticles within the layers, the second strong peak was consistently observed between 620 and 660 nm, which is the collective plasmon resonance from intralayer interparticle coupling. Finally, we suggested that, for certain film designs, interlayer interparticle resonance might be revealed as an independent contribution at 800 nm in UV-visible spectra. The observation of independent and concurrent individual, intralayer, and interlayer plasmon resonances can be critical for sensing applications, which involve monitoring of optomechanical properties of ultrathin optically active compliant membranes.     

Synthesis and plasmonic properties of silver and gold nanoshells on polystyrene cores of different size and of gold–silver core–shell nanostructures

Simple methods of preparing silver and gold nanoshells on the surfaces of monodispersed polystyrene microspheres of different sizes as well as of silver nanoshells on free-standing gold nanoparticles are presented. The plasmon resonance absorption spectra of these materials are presented and compared to predictions of extended Mie scattering theory. Both silver and gold nanoshells were grown on polystyrene microspheres with diameters ranging from 188 to 543 nm. The commercially available, initially carboxylate-terminated polystyrene spheres were reacted with 2-aminoethanethiol hydrochloride (AET) to yield thiol-terminated microspheres to which gold nanoparticles were then attached. Reduction of silver nitrate or gold hydroxide onto these gold-decorated microspheres resulted in increasing coverage of silver or gold on the polystyrene core. The nanoshells were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV–vis spectroscopy. By varying the core size of the polystyrene particles and the amount of metal (silver or gold) reduced onto them, the surface plasmon resonance of the nanoshell could be tuned across the visible and the near-infrared regions of the electromagnetic spectrum. Necklace-like chain aggregate structures of gold core–silver shell nanoparticles were formed by reducing silver nitrate onto free citrate-gold nanoparticles. The plasmon resonance absorption of these nanoparticles could also be systematically tuned across the visible spectrum.     

Preparation, characterization, and optical properties of gold, silver, and gold-silver alloy nanoshells having silica cores

This report describes the structural and optical properties of a series of spherical shell/core nanoparticles in which the shell is comprised of a thin layer of gold, silver, or gold-silver alloy, and the core is comprised of a monodispersed silica nanoparticle. The silica core particles were prepared using the St?ber method, functionalized with terminal amine groups, and then seeded with small gold nanoparticles (approximately 2 nm in diameter). The gold-seeded silica particles were coated with a layer of gold, silver, or gold-silver alloy via solution-phase reduction of an appropriate metal ion or mixture of metal ions. The size, morphology, and elemental composition of the composite nanoparticles were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The optical properties of the nanoparticles were analyzed by UV-vis spectroscopy, which showed strong absorptions ranging from 400 nm into the near-IR region, where the position of the plasmon band reflected not only the thickness of the metal shell, but also the nature of the metal comprising the shell. Importantly, the results demonstrate a new strategy for tuning the position of the plasmon resonance without having to vary the core diameter or the shell thickness.     

AuNPs/PNIPAM复合颗粒的制备及其温敏性质

将金纳米颗粒(AuNPs)组装到聚N-异丙基丙烯酰胺(PNIPAM)水凝胶微球表面制备出AuNPs/PNIPAM复合颗粒. 将PNIPAM 凝胶的温敏特性与AuNPs的光学性质结合, 通过改变温度调节AuNPs的局部表面等离子共振(LSPR)吸收峰位置. 研究结果表明, 温度升高使AuNPs的LSPR吸收峰发生红移, 并且这种效应是可逆的. 同时发现, AuNPs的光学性质还可以作为表征PNIPAM水凝胶微球温敏行为的一种手段. 利用透射电镜、紫外-可见光谱仪及动态光散射仪对AuNPs/PNIPAM复合颗粒的形貌、光学性质、粒径变化等进行了分析.     

Gold and silver nanoparticles: a class of chromophores with colors tunable in the range from 400 to 750 nm

This paper presents several solution-phase methods for the large-scale synthesis of metal nanoparticles with controllable compositions (e.g., spherical nanoparticles of gold/silver alloys), morphologies (e.g., nanospheres, triangular nanoplates, circular nanodisks, and nanocubes of silver), and structures (e.g., solid vs. hollow colloids). Spectral measurements indicated that the positions of surface plasmon resonance (SPR) bands for these nanoparticles could be tuned by varying all these parameters. The number of SPR peaks was found to increase as the symmetry of the nanoparticles decreased. In addition to their use as chromophores with strong extinction coefficients, these nanoparticles could serve as a platform to probe binding events of chemical and biochemical species on their surfaces. Gold nanoshells with hollow interiors were, in particular, shown to exhibit a much higher sensitivity to environmental changes than gold solid colloids with roughly the same size.     

金纳米线阵列制备及其光谱特性

利用电化学沉积方法在重离子径迹模板中制备出直径从45 nm到200 nm, 长径比达700的金纳米线阵列, 利用扫描电子显微镜(SEM)和X射线衍射(XRD)对所制备金纳米线的形貌及晶体结构进行分析, 结果表明, 在1.5 V(无参比电极)沉积电压下所制备出的直径为200 nm金纳米线沿[100]晶向具有较好择优取向. 利用紫外-可见光谱(UV-Vis)对镶嵌在透明模板中平行排列的金纳米线阵列光学特性进行研究, 发现金纳米线直径为45 nm时, 其紫外可见光谱在539 nm处有强烈吸收峰, 随着金纳米线直径增加, 吸收峰红移, 当金纳米线直径达到200 nm时, 其吸收峰峰位移至700 nm. 结合金纳米颗粒相关表面等离子体共振吸收效应对实验结果进行了讨论.     

纳米金汞核-壳粒子的电化学制备及其光谱性质

在聚乙烯吡啶修饰导电玻璃电极表面进行了金纳米粒子的二维单层结构组装,通过电沉积方法在金粒子表面制备了纳米汞壳层.研究结果表明,汞壳层的形成导致了内部金粒子表面等离子体共振的谱峰红移和强度衰减.吸附于汞壳表面的结晶紫分子因可承受被金核增强的电磁场,而使其拉曼散射得到极大的增强.     

Spectroscopic characterizations of molecularly linked gold nanoparticle assemblies upon thermal treatment

The understanding of surface properties of core-shell type nanoparticles is important for exploiting the unique nanostructured catalytic properties. We report herein findings of a spectroscopic investigation of the thermal treatment of such nanoparticle assemblies. We have studied assemblies of gold nanocrystals of approximately 2 nm core sizes that are capped by alkanethiolate shells and are assembled by covalent or hydrogen-bonding linkages on a substrate as a model system. The structural evolution of the nanoparticle assemblies treated at different temperatures was probed by several spectroscopic techniques, including UV-visible, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show that the capping/linking shell molecules can be effectively removed to produce controllable surface and optical properties. The data further revealed that the thermally induced evolution of the surface plasmon resonance property of gold nanoparticles is dependent on the chemical nature of the linker molecule. The spectral evolution is discussed in terms of changes in particle size, interparticle distance, and dielectric medium properties, which has important implications for controlled preparation and thermal processing of core-shell nanostructured metal catalysts.