The effect of the number of parallel DNA molecules on electric charge transport through 'standing DNA'

We present morphological and electrical characterization of double-stranded DNA (dsDNA) molecules covalently bound to two metal electrodes: an underlying gold surface and a gold nanoparticle (GNP). Conductive atomic force microscope (cAFM) with a metallized tip is used to perform current-voltage (I-V) measurements through dsDNA molecules, connected to GNPs of different diameters 5, 10 and 20?nm. The number of DNA molecules coating the GNP is expected to vary with the surface area of the GNP. This number and the portion of the GNP surface area enabling hybridization of the DNA determine the number of DNA molecules connecting the GNP to the gold surface. The larger the diameter of the GNP the higher the expected number of dsDNA molecules connecting it to the gold surface and thus the expected current. Our results show similar currents for all three GNP sizes, indicating that current flows through the same number of molecules regardless of the diameter of the measured GNP. The measured currents, 220 nA at 2?V, are in accordance with our previous reports (Cohen et al 2005 Proc. Natl Acad. Sci. USA 102 11589-93; Cohen et al 2006 Faraday Discuss. 131 367-76) in which we demonstrated the validity of the experimental system. In particular, for the 5?nm GNP, we conclude that the current possibly flows through two to three molecules, likely only one, and that a single short dsDNA molecule can support at least ～70?nA, and probably 220?nA.     

Chitosan-mediated synthesis of gold nanoparticles by UV photoactivation and their characterization

Recent researches have largely been focused on chitosan, which is deacetylated chitin, the most abundant natural polysaccharide after cellulose. In this paper, we report the fabrication of gold nanoparticles (GNPs) by UV photoactivation in the presence of biopolymeric chitosan and the tracing of the gold salt solution aging. Detailed UV-visible spectroscopy study witnessed the evolution of the surface plasmon resonance (SPR) adsorption during the GNP growth. The effect of chitosan in aqueous solution for the GNP preparation was investigated in detail. The results indicated the size and distribution of GNPs could be controlled over by altering the concentration of chitosan, and the GNP growth during aging was a chitosan-mediated autocatalytic process. Fourier transform infrared spectroscopy (FTIR) showed the hydroxyl in molecular chitosan was oxidized to carbonyl groups in the fabrication of GNPs after aging and nitrogen atoms are the main sites for the complexation of chitosan with Au atoms. Our synthesis method in the present way can be used to form self-assemble monolayers of GNPs and fabricate biosensors based on surface plasmon resonance effect.     

Fluorophore-gold nanoparticle complex for sensitive optical biosensing and imaging

Fluorophores have been extensively used as the signal mediator in biosensing and bioimaging for a long time. Enhancement of fluorescence can amplify the signal, thus improving the sensitivity, enabling earlier and accurate disease detection and diagnosis. Some metal nanoparticles, such as gold and silver, can generate a strong electromagnetic field on their surface (surface plasmon field) upon receiving photonic energy. When a fluorophore is placed in the field, the field can affect the fluorophore electrons participating in fluorescence emission and change the fluorescence output. The change can be from complete quenching to significant enhancement, depending on the metal type, particle size and shape, excitation/emission wavelengths and quantum yield of the fluorophore, and the distance between the fluorophore and the particle surface. In this study, the effects of these parameters on the fluorescence enhancement of commonly used fluorophores by gold nanoparticles (GNPs) are theoretically analyzed. Experimentally, an NIR contrast agent with enhanced fluorescence was developed by carefully tailoring the distance between Cypate (ICG based fluorophore) and a GNP, via biocompatible spacer constructs. The effect of the GNP size (3.7-16.4 nm) and spacer length (3.2-4.6 nm) on fluorescence enhancement was studied, and the spacer length that provided the significant enhancement was determined. The spacer of 3.9 nm with 16.4 nm GNP provided the fluorescence of 360% of the control. The experimental data qualitatively agreed with the theoretical results and, thus, the theoretical analysis can be used as a guide for significantly improving the sensitivity of existing fluorescent contrast agents by properly utilizing GNPs and spacers.     

Assembly of hybrid oligonucleotide modified gold (Au) and alloy nanoparticles building blocks

The alloy-based hybrid materials with macroscopic network arrays were developed by AuAg/Au and AuAgPd/Au nanoparticle composites through oligonucleotides hybridization. AuAg/Au and AuAgPd/Au exhibited distinct organization. The morphology of AuAg/Au conjugation assembled mainly as compact aggregates while AuAgPd/Au hybrid conjugated into the loosen network assemblies. The dehybridization temperatures were studied as a function of molar ratio of alloy/Au. It was found that higher alloy/gold molar ratio led to stronger hybridization for alloy/gold composite, accompanied with increased melting temperature. These results could be interpreted in terms of more alloy nanoparticles bound to a Au particle when the molar ratio of alloy/gold increased. The thermal analysis also showed that AuAg/Au exhibited higher dehybridization temperature. A modified model describing the dehybridization probability of an intact Au/alloy aggregate was performed to support the dehybridization temperature increased with increasing alloy/Au molar ratio. As to more oligonucleotides carried by AuAg (4.9 +/- 1.9 nm) than by AuAgPd (4.4 +/- 1.5 nm) due to larger size in AuAg, the efficient hybridization could result in higher dehybridization temperature in AuAg/Au.     

Controlled synthesis and optical properties of Au and Au@PS nanoparticles

In this study, uniform gold (Au) nanoparticles (NPs) were prepared using seed-mediated growth method. The particle size was controlled by tuning the dosage of seed solution. Au@PS core–shell NPs were then synthesized by introducing a polystyrene (PS) shell (2–3 nm thick) around the core of Au NPs (115 nm). Evaluation of the surface plasmon (SP) optical properties indicated that wavelength of SP resonance of Au NPs increased gradually with increase in the particle size. This red shift was about 0.92 nm per 1 nm increase in particle size. The results also indicated that the zeta potential and optical properties of Au NPs could be adjusted by coating PS on the outside. Therefore, surface modifications and surface coating were effective ways to control the optical properties of Au NPs.     

Electron and phonon transport in Au nanoparticle decorated graphene nanoplatelet nanostructured paper

Monodispersed Au nanoparticles are synthesized on the surface of exfoliated graphene nanoplatelets (GNP) in the presence of polyethyleneimine (PEI) with microwave assisted heating. A highly structured layered Au/GNP "paper" with good flexibility and mechanical robustness is prepared by vacuum assisted self-assembly. The thermal and electrical conductivity of the hybrid paper with and without the Au nanoparticles are investigated after different experimental processing conditions including thermal annealing and cold compaction. Annealing effectively decomposes and removes the adsorbed PEI molecules and improves thermal contact between Au/GNP particles, whereas cold compaction reduces porosity and induces stronger alignment of the Au/GNP within the hybrid paper. Both approaches lead to improvement in electrical and thermal conductivity. It is also found that adjacent GNP particles are electrically connected by the Au nanoparticles but thermally disconnected. It is believed that phonons are scattered at the Au/GNP interfaces, whereas electrons can tunnel across this interface, resulting in a separation of electron and phonon transport within this hybrid paper.     

Deposition of gold nanoparticles on electrospun MgTiO3 ceramic nanofibers

A simple method to deposit spherical gold nanoparticles on the surface of MgTiO3 ceramic nanofibers is presented. Electrospun MgTiO3/poly(vinyl acetate) (PVAc) hybrid nanofibers were calcined at 650 degrees C to obtain phase pure ceramic MgTiO3 nanofibers with 100-150 nm diameters. These ceramic nanofibers were immersed in an aqueous solution of HAuCl4 containing poly(vinyl alcohol) (PVA) as capping agent followed by photoreduction at 365 nm to get a novel Au-MgTiO3 nanocomposite. The formation of gold nanoparticles upon irradiation was confirmed by the appearance of a surface plasmon band (SPB) at 590 nm in the UV-visible absorption spectra. The surface morphology and elemental compositions were analyzed by the scanning electron microscope (SEM) equipped with energy dispersive X-ray (EDX), and transmission electron microscope (TEM). X-ray diffraction (XRD) and selected area diffraction (SAED) pattern in TEM revealed the crystallization of gold by exhibiting strong diffractions correspond to Au(111) and Au(200) crystalline planes in addition to the MgTiO3 diffraction.     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Synthesis of protein–gold nanoparticle hybrid and gold nanoplates in protein aggregates

A straightforward and economically viable approach was developed to biomimetic synthesis of gold nanocrystals by using casein micelles (CMs) without additional reductant. The UV–vis, TEM, SAED, FTIR, DLS and XRD techniques were employed to systematically characterize Au nanocrystals synthesized. Isotropic gold nanoparticle (GNP) and gold nanoplates in good yields (up to 90%) with different sizes can be obtained easily by adjusting the experimental condition. Spherical nanoparticles were obtained with tunable mean sizes at higher pH and casein concentrations. The high colloidal stability of the spherical GNP is attributed to the formation of CM/GNP hybrid under some experimental condition. At lower pH, reaction temperature and casein concentrations, single-crystalline gold nanoplates in good yields (up to 90%) are obtained. The growth of these nanostructures is attributed to an interplay between the faceting tendency of the protein molecules/micelles and the growth kinetics. More importantly, the morphological evolution of large gold nanoplates at different reaction times has been followed, and compared with some earlier protein systems, different formation mechanisms in casein micelles are obtained. The results demonstrate that both the property of individual protein molecules and protein aggregates play important roles in controlling the formation of gold nanocrystals by using amphiphilic protein.     

Microcantilever-based sensors: effect of morphology, adhesion, and cleanliness of the sensing surface on surface stress

The surface stress response of micromechanical cantilever-based sensors was studied as a function of the morphology, adhesion, and cleanliness of the gold sensing surface. Two model systems were investigated: the adsorption of alkanethiol self-assembled monolayers at the gas-solid interface and the potential-controlled adsorption of anions at the liquid-solid interface. The potential-induced surface stress, on a smooth and continuous polycrystalline Au(111)-textured microcantilever in 0.1 M HClO4, is in excellent agreement with macroscopic Au(111) single-crystal electrode results. It is shown that ambient contaminants on the sensing surface dramatically alter the surface stress-potential response. This observation can be misinterpreted as evidence that for polycrystalline Au(111) microcantilever electrodes, surface stress is dominated by surface energy change. Results for anions adsorption on gold are in contrast to the gas-phase model system. We demonstrate that the average grain size of the gold sensing surface strongly influences the magnitude of the surface stress change induced by the adsorption of octanethiol. A 25-fold amplification of the change in surface stress is observed on increasing the average gold grain size of the sensing surface from 90 to 500 nm.     

Nanophotonic switch: gold-in-Ga2O3 peapod nanowires

A novel metal-insulator heterostructure made of twinned Ga2O3 nanowires embedding discrete gold particles along the twin boundary was formed through a reaction between gold, gallium, and silica at 800 degrees C during simple thermal annealing. The Au-in-Ga2O3 peapods spontaneously crystallized under phase separation induced by the formation of twin boundaries. The nanostructures were analyzed by field emission scanning (FESEM) and transmission electron microscopes (FETEM), and their photoresponse was investigated using a double-frequency Nd:YAG laser with a wavelength of 532 nm on a designed single-nanowire device. The surface plasmon resonance (SPR) effects of embedded Au nanoparticles are proposed to be responsible for the remarkable photoresponse of these novel structures.     

Fabrication and optical characteristics of a novel optical fiber doped with the Au nanoparticles

Optical fibers containing gold metal nanoparticles were developed by modified chemical vapor deposition, in which Au(OH)3 and tetraethyl-orthosilicate (TEOS) was used via sol-gel process to incorporate gold metals by providing the reduction atmosphere. The absorption peak appeared near 490 nm was found to be due to the surface plasmon resonance of the gold nanoparticles incorporated in the fiber core.     

On the role of low-energy electrons in the radiosensitization of DNA by gold nanoparticles

Four different gold nanoparticle (GNP) preparations, including naked GNPs and GNPs coated either with thiolated undecane (S-C(11)H(23)), or with dithiolated diethylenetriaminepentaacetic (DTDTPA) or gadolinium (Gd) DTDTPA chelating agents, were synthesized. The average diameters, for each type of nanoparticle, are 5 nm, 10 and 13 nm, respectively. Dry films of plasmid DNA pGEM-3Zf(-), DNA with bound GNPs and DNA with coated GNPs were bombarded with 60 keV electrons. The yields of single and double strand breaks were measured as a function of exposure by electrophoresis. The binding of just one GNP without coating to DNA containing 3197 base pairs increases single and double strand breaks by a factor of 2.3 while for GNPs coated with S-C(11)H(23) this factor is reduced to 1.6. The GNPs coated with DTDTPA and DTDTPA:Gd in the same ratio with the DNA, produce essentially no increment in damage. These results could be explained by the attenuation by the coatings of the intensity of the low-energy photoelectrons emitted from the GNPs. Thus, coatings of GNPs may considerably attenuate the short-range low-energy electrons emitted from gold, leading to a considerable decrease of radiosensitization. According to our results, the highest radiosensitization should be obtained with GNPs having the shortest possible ligand, directed to the DNA of cancer cells.     

Preparation of gold nanoparticles (GNP) aqueous suspensions by a new method involving Tiron

A new method is proposed to produce gold nanoparticles (GNP) by in situ reduction of a gold salt dissolved in water. The reducing agent used is Tiron instead of the citrate anion most often mentioned in literature. The influence of various parameters has been investigated, such as the content of Tiron with respect to that of the precursor of gold HAuCl₄, or the initial pH of the solution after mixing of reactants. It is shown that Tiron also exerts a positive influence as a dispersant, which impedes agglomeration of gold nanoparticles. The typical average size of GNP synthesized in the present work is close to 7 nm.     

Near Infrared Light‐Triggered Drug Generation and Release from Gold Nanoparticle Carriers for Photodynamic Therapy

A photoprecursor Pc 227 is covalently bound onto gold nanoparticles (Au NPs) to produce the known photodynamic therapy (PDT) drug Pc 4 upon 660 nm photoirradiation. The photochemical formation of the photoproduct Pc 4 is identified by spectroscopy, chromatography, and mass spectrometry and its PDT efficacy is equal to Pc 4 when administered non‐covalently by Au NPs, with the added benefit of improved covalent delivery and targeted NIR‐triggered release from the covalent Pc 227‐Au NP conjugate, while during transport the attached Pc 227 is quenched by the Au NP and PDT inactivated.     

Synthesis and characterization of nano-gold composite using Cylindrocladium floridanum and its heterogeneous catalysis in the degradation of 4-nitrophenol

Greener synthesis of nanogold-biocomposite by fungus, Cylindrocladium floridanum was reported in this study. Results revealed that when cultured in static condition for a period of 7d, the fungus accumulated gold nanoparticles on the surface of the mycelia. Bionanocomposites with Au nanocrystals were characterized by UV-Vis spectroscopy, XRD, SEM, EDX and high-resolution TEM. The SPR band of UV-Vis spectrum at 540 nm confirmed the presence of gold nanoparticles on the surface of the fungal mycelia. The fcc (111)-oriented crystalline nature of particles was identified by XRD pattern. The synthesized particles are spherical in shape as evidenced by TEM image. The biocomposites with Au nanoparticles function as an efficient heterogeneous catalyst in the degradation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), in the presence of reducing agent, sodium borohydride which was reflected by UV-Vis spectra of the catalytic reaction kinetics. The reduction of 4-nitrophenol follows pseudo-first-order kinetic model with the reaction rate constant of 2.67 × 10(-2)min(-1) with 5.07 × 10(-6)mol/dm(3) of gold at ca. 25 nm. The rate of the reaction was increased by increasing the concentration of gold nanoparticles from 2.54 × 10(-6) to 12.67 × 10(-6)mol/dm(3) (～ 25 nm) and with reduced size from 53.2 to 18.9 nm respectively. This is the first report on fungal-matrixed gold(0) nanocomposites heterogeneously catalyzing the reduction of the toxic organic pollutant, 4-nitrophenol that enable the recovery and recycling of AuNPs catalysts.     

Zinc porphyrin-driven assembly of gold nanofingers

Nanofingers of gold covered by porphyrins are prepared by a combination of atomic manipulation and surface self-organization. A submonolayer of zinc(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (ZnTBPP) axially ligated to a self-assembled monolayer of 4-aminothiophenol (4-ATP) on Au(111) is prepared and studied using a combination of ultrahigh vacuum techniques. Under the electric field produced by the STM tip, the relatively weakly bound Au surface atoms along the discommensuration lines become mobile due to the strong bond to 4-ATP, while the tendency of the porphyrins towards self-assembly result in a collective motion of gold clusters. The clusters diffuse onto the surface following well-defined pathways along the [112] direction and then reach the step edges where they assembled, thus forming nanofingers. First-principles density functional theory calculations demonstrate the reduction of the binding energies between the surface gold clusters and the substrate induced by adsorption of thiols. Scanning tunneling microscopy images show assemblies across three adjacent discommensuration lines of the Au(111)-(22 x square root 3) reconstruction, which collectively diffuse along these lines to form islands nucleated at step edges.     

Ni针尖/Au基体纳米压痕的分子动力学模拟

采用原子镶嵌势函数（EAM）模拟Ni针尖（约1．5mm）／Au基体纳米压痕过程．研究结果表明,当Ni针尖与Au基体间距离达到一定值时（约0．23 mm）,机械的不稳定性使得针尖与基体间发生跳跃接触,产生纳米压痕和黏附现象（Au原子包裹在Ni针尖周围）．当压头离开基体表面,Ni针尖被拔起,随后在针尖与基体间形成连续的由Au组成的细颈．同时计算得到整个系统在针尖接近基体、跳跃接触、压痕、黏附、形成缩颈和一系列分离过程中的势能变化．     

Synthesis of triangular Au core-Ag shell nanoparticles

In this paper, we demonstrate a simple and reproducible method for the synthesis of triangular Au core-Ag shell nanoparticles. The triangular gold core is obtained by the reduction of gold ions by lemongrass extract. Utilizing the negative charge on the gold nanotriangles, silver ions are bound to their surface and thereafter reduced by ascorbic acid under alkaline conditions. The thickness of the silver shell may be modulated by varying the pH of the reaction medium. The formation of the Au core-Ag shell triangular nanostructures has been followed by UV-vis-NIR Spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM) and atomic force microscopy (AFM) measurements. The sharp vertices of the triangles coupled with the core-shell structure is expected to have potential for application in surface enhanced Raman spectroscopy and in the sensitive detection of biomolecules.     

Structural verification and optical characterization of SiO2–Au–Cu2O nanoparticles

In this paper, SiO₂–Au–Cu₂O core/shell/shell nanoparticles were synthesized by reducing gold chloride on 3-amino-propyl-triethoxysilane molecules attached silica nanoparticle cores for several stages. Cu₂O nanoparticles were synthesized readily with the size of 4–5 nm using a simple route of sol–gel method Then, they were clung to the surface of Au seeds. The morphology of the resultant particles was studied using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Transmission electron microscopy images demonstrate growth of monodispersed gold seeds and Cu₂O nanoparticles in narrow size up to 10 nm and 5 nm, respectively. The presence of gold and Cu₂O coating was confirmed by X-ray diffraction, Fourier transform infrared spectroscopy and UV–Vis spectroscopy. Absorption spectroscopy shows considerably 40 nm blue shift in absorption edge for SiO₂–Au–Cu₂O nanostructure rather than SiO₂–Au core/shell nanoparticles.