Coalescence of oxide nanoparticles: In situ HRTEM observation

The coalescence process of copper oxide particles of 3∼ ∼8 nm was studied by in-situ HRTEM observation with no external heating. We found that merging of two particles is much faster as compared to the reshaping process. The coalescence of pre-aligned nanoparticles leads to the formation of a single nanocrystal. The lattice mismatch between two merged misaligned particles can be released by structural relaxation in small nanoparticles and by interface movement in large nanoparticles. Surface atom migration is the leading mechanism during the whole coalescence process.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.     

Fluorescent silver nanoparticles via exploding wire technique

Aqueous solution containing spherical silver nanoparticles of 20–80 nm size have been generated using a newly developed novel electro-exploding wire (EEW) technique where thin silver wires have been exploded in double distilled water. Structural properties of the resulted nanoparticles have been studied by means of X-ray diffractometer (XRD) and transmission electron microscopy (TEM). The absorption spectrum of the aqueous solution of silver nanoparticles showed the appearance of a broad surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm. The theoretically generated SPR peak seems to be in good agreement with the experimental one. Strong green fluorescence emission was observed from the water-suspended silver nanoparticles excited with light of wavelengths 340, 360 and 390 nm. The fluorescence of silver nanoparticles could be due to the excitation of the surface plasmon coherent electronic motion with the small size effect and the surface effect considerations     

Temperature‐dependent,micro‐Raman spectroscopic study of barium titanate nanoparticles

A comparative, temperature‐dependent (80–500 K at 5 K intervals), micro‐Raman spectroscopic study of 300 and 50 nm diameter ceramic BaTiO₃ nanoparticles was carried out with the purpose of elucidating the nanoparticle size effect on the temperature dependence of the polar and non‐polar phonons. A method for calibrating Raman intensities, along with an iterative spectral fitting algorithm, is proposed for concurrent Raman band position and intensity analysis, increasing the analytical abilities of single temperature point Raman spectroscopy. The 300 nm particles exhibit all three phase transitions, whereas the 50 nm particles do not show evidence of these phase transitions in the same temperature range. The Curie temperature appears to be a phonon converging point, irrespective of the phonon symmetry. An attempt was made to qualitatively relate the temperature‐dependent Raman spectra to complimentary non‐spectroscopic methods, such as heat capacity and X‐ray diffraction studies. The study proves that the temperature‐dependent behavior of the polar phonon, 265 cm⁻¹, can be utilized as a sensitive phase transition probe. Copyright © 2014 John Wiley & Sons, Ltd.     

Photochemical decoration of silver nanoparticles on ZnO nanowires as a three‐dimensional substrate for surface‐enhanced Raman scattering measurement

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurement, a three‐dimensional (3D) SERS substrate was prepared by the decoration of silver nanoparticles (AgNPs) on the side walls of ZnO nanowires. The prepared 3D SERS substrates provide the advantages of highly loaded density of AgNPs, with a large specific surface area to interact with analytes, and the ease for the analytes to access the surfaces of AgNPs. To prepare the substrates, ZnO nanowires were first grown on a glass plate by wet chemical method. By treating SnCl₂ on the surfaces of ZnO nanowires, Ag seeds could be formed on the side wall of the ZnO nanowires, which were further grown to a suitable size for SERS measurements via photochemical reduction. To optimize and understand the influences of the parameters used in preparation of the substrates, the reaction conditions were systematically adjusted and examined. Results indicated that AgNPs could be successfully decorated on the side wall of the ZnO nanowires only by the assistances of SnCl₂. The size and density of AgNPs were affected by both the concentration of silver nitrate and the irradiation time. With optimized condition, the prepared 3D substrates provided an enhancement factor approaching 7 orders of magnitude compared with conventional Raman intensity. Copyright © 2014 John Wiley & Sons, Ltd.     

Insulator-metal transition in a conservative system: An evidence for mobility coalescence in island silver films

Aging, which manifests itself as an irreversible increase in electrical resistance in island metal films is of considerable interest from both academic as well as applications point of view. Aging is attributed to various causes, oxidation of islands and mobility of islands followed by coalescence (mobility coalescence) being the main contenders. The effect of parameters like substrate temperature, substrate cleaning, residual gases in the vacuum chamber, ultrasonic vibration of the substrate, suggest that the mobility coalescence is responsible for the aging in island metal films. Electron microscopy studies show evidence for mobility of islands at high substrate temperatures. The comparison of aging data of island silver films deposited on glass substrates in ultra high vacuum and high vacuum suggests that the oxidation of islands, as being responsible for aging in these films, can be ruled out. Further, under certain conditions of deposition, island silver films exhibit a dramatic and drastic fall in electrical resistance, marking the insulator-metal transition. This interesting transition observed in a conservative system — after the stoppage of deposition of the film — is a clear evidence for mobility coalescence of islands even at room temperature. The sudden fall in resistance is preceded by fluctuations in resistance with time and the fluctuations are attributed to the making and breaking of the percolation path in the film.     

Glass‐embedded silver nanoparticle patterns by masked ion‐exchange process for surface‐enhanced Raman scattering

Glass‐embedded silver nanoparticle patterns were fabricated by masked silver–sodium ion‐exchange process followed by etching to reveal the particles for surface‐enhanced Raman scattering (SERS). The intensity of the enhanced Raman signal is comparable to that of the fluorescence, and the detection limit of 1 nM for Rhodamine 6G has been achieved. Raman images at different etching depths and corresponding morphological images are compared to find optimal SERS signal. Our results demonstrate that silver nanoparticle patterns embedded in glass can be used as SERS‐active substrates. Nanoparticles can be formed in a glass of high optical quality and have potential to be integrated with optical waveguides for a sensor chip. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering assessment of DNA from leaf tissues adsorbed on silver colloidal nanoparticles

In this work, the surface‐enhanced Raman scattering (SERS) spectra of seven genomic DNAs from leaves of chrysanthemum (Dendranthema grandiflora Ramat.), common sundew (Drosera rotundifolia L.), edelweiss (Leontopodium alpinum Cass), Epilobium hirsutum L., Hypericum richeri ssp. transsilvanicum (Čelak) Ciocârlan, rose (Rosa x hybrida L.) and redwood (Sequoia sempervirens D. Don. Endl.), respectively, have been analyzed in the wavenumber range 200–1800 cm⁻¹. The surface‐enhanced Raman vibrational modes for each of these cases, spectroscopic band assignments and structural interpretations of genomic DNAs are reported. A high molecular structural information content can be found in the SERS spectra of these DNAs from leaf tissues. Based on this work, specific plant DNA–ligand interactions or accurate local structure of DNA might be further investigated using surface‐enhanced Raman spectroscopy. Besides, this study will generate information which is valuable in the development of label‐free DNA detection for chemical probing in living cell. Copyright © 2013 John Wiley & Sons, Ltd.     

镧与真空沉积银纳米粒子的金属间化合

根据HumeRothery规则,分析了银与镧两元素之间形成金属间化合物的倾向性,并根据真空蒸发沉积的条件,分析了在真空蒸发沉积情况下镧与银之间形成金属间化合物的可能性.用X射线光电子能谱化学位移方法对真空蒸发沉积的银、镧薄膜进行了分析,结果表明在真空沉积条件下镧与银之间的确形成了金属间化合物. 关键词： 金属间化合物 镧 银 纳米粒子     

Facile synthesis of gelatin‐protected silver nanoparticles for SERS applications

Gelatin‐protected silver nanoparticles have been synthesized by a one‐pot, green method for surface‐enhanced Raman scattering (SERS) applications using gelatin as the reducing and stabilizing agent. The gelatin protection on silver nanoparticle surface helps improve its stability greatly and water dispersibility, while retaining high SERS activity of silver nanoparticles. The gelatin‐protected silver nanoparticles showed SERS signals as low as 100 nM of the typical Raman reporter molecules, RuBPY and R6G and 10 μM of other molecules of interest, melamine and folic acid. Copyright © 2013 John Wiley & Sons, Ltd.     

微乳液法制备纳米银粒子的结构及其荧光现象研究

采用微乳液法合成了不同粒径的纳米银粒子,考察了环己烷和甲苯作为油相对制备纳米银的影响.对纳米银粒子的尺寸与结构进行了表征,观察到近球形多晶粒子,并有孪晶结构存在,对晶体结构的分析表明银粒子存在不同程度的点阵畸变,晶面间距增大.不同粒径的纳米银粒子氯仿体系可呈现荧光光谱,而纳米银甲苯体系则无荧光发射.结合紫外—可见吸收光谱和电子自旋共振谱对该体系的荧光发射机理进行了分析 关键词： 微乳液 纳米银粒子 纳米晶结构 荧光     

Raman scattering of L‐tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination

Vibrational bands of L ‐tryptophan which was adsorbed on Ag nanoparticles (∼10 nm in diameter) have been investigated in the spectral range of 200–1700 cm⁻¹ using surface‐enhanced Raman scattering (SERS) spectroscopy. Compared with the normal Raman scattering (NRS) of L ‐tryptophan in either 0.5 M aqueous solution (NRS‐AS) or solid powder (NRS‐SP), the intensified signals by SERS have made the SERS investigation at a lower molecular concentration (5 × 10⁻⁴ M ) possible. Ab initio calculations at the B3LYP/6‐311G level have been carried out to predict the optimal structure and vibrational wavenumbers for the zwitterionic form of L ‐tryptophan. Facilitated with the theoretical prediction, the observed vibrational modes of L ‐tryptophan in the NRS‐AS, NRS‐SP, and SERS spectra have been analyzed. In the spectroscopic observations, there are no significant changes for the vibrational bands of the indole ring in either NRS‐AS, NRS‐SP, or SERS. In contrast, spectral intensities involving the vibrations of carboxylate and amino groups are weak in NRS‐AS and NRS‐SP, but strong in SERS. The intensity enhancement in the SERS spectrum can reach 10³–10⁴‐fold magnification. On the basis of spectroscopic analysis, the carboxylate and amino groups of L ‐tryptophan are determined to be the preferential terminal groups to attach onto the surfaces of Ag nanoparticles in the SERS measurement. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering of N‐acetylneuraminic acid on silver nanoparticle surface

N‐Acetylneuraminic acid (sialic acid, Neu5Ac) has recently gained interest as a potential marker for a variety of pathophysiological processes, although no Raman study has been reported for this important biomolecule. In this paper, the vibrational properties of Neu5Ac were studied by means of Raman, surface‐enhanced Raman scattering (SERS), and density functional theory calculations. By adsorption of Neu5Ac on silver nanoparticle surface, strongly enhanced Raman intensities are obtained, allowing easy measurement of small amounts of aqueous Neu5Ac (10 µl of a 10⁻⁷ m solution) utilizing low laser power and short exposure time. The mechanism of adsorption of Neu5Ac on the silver surface is discussed on the basis of the experimental and theoretical results. This study demonstrates that SERS can provide an effective tool for development of a label‐free, rapid, and sensitive optical platform for identification of Neu5Ac. Copyright © 2014 John Wiley & Sons, Ltd.     

银纳米颗粒对四苯基卟啉Q带荧光寿命的延长

文章报道了吸附在银纳米颗粒表面的四苯基卟啉(TPP)的Q带荧光寿命的变化.实验发现将银纳米颗粒的表面等离激元共振吸收峰调至与TPP的Q吸收带共振时,会使TPP的Q带荧光寿命得到延长.这是由于银纳米颗粒对表面的光电场有较大的表面等离激元共振增强效应,而处于激发态的TPP分子有较高的极性,这种增强的光电场会对有较高极性的TPP分子有稳定作用,所以延长了其Q带寿命.这对于以卟啉为光敏剂的光动力治疗有重要的意义.     

银纳米颗粒/多孔硅复合材料的制备与气敏性能研究

采用双槽电化学腐蚀法以电阻率为10-15 Ω·cm的p型<100>晶向的单晶硅片制备了孔径约为1.5 μm, 孔深约为15-20 μm的p型多孔硅, 并以此多孔硅作为基底采用无电沉积法通过调控沉积时间在其表面沉积了不同厚度的银纳米颗粒薄膜. 采用扫描电子显微镜和X 射线衍射仪表征了银纳米颗粒/多孔硅复合材料的形貌和微观结构, 结果表明银纳米颗粒较均匀的分布于多孔硅的表面上且沉积时间对产物的形貌有重要影响. 采用静态配气法在室温下研究了银纳米颗粒/多孔硅复合材料对NH₃的气敏性能. 气敏测试结果表明沉积时间对产物的气敏性能影响较大. 当沉积时间较短时, 适量银纳米颗粒掺杂的多孔硅复合材料由于其较高的比表面积以及特殊的形貌和结构, 对NH₃气体表现出较高的灵敏度、优良的响应/恢复性能. 室温下, 其对50 ppm 的NH₃气体的气敏灵敏度可以达到5.8左右.     

SERS of the anti‐inflammatory drug piroxicam adsorbed on the surface of silver or gold colloids as nanocarrier model

Piroxicam is a non‐steroidal anti‐inflammatory drug actually used with limitations because of serious side effects. It is poorly soluble in pure water and exhibit a minimum of four conformers according to the pH conditions of the solution, but not all of them are medically active. In this study, we present, firstly, the Raman characterization of piroxicam in different organic solvents (dimethyl sulfoxide, 1,4‐dioxane, ethanol, 1‐propanol). These results have permitted us to analyze surface‐enhance Raman scattering spectra of piroxicam adsorbed on gold or silver nanoparticles surface at several pHs (1, 2, 4, and 7), imitating the environment of the drug in the body, either in the gastrointestinal tract or in healthy and disease tissues. Results indicate that, below pH = 7, piroxicam is mainly in the zwitterionic conformer, and molecules are oriented parallel to the noble metal surface; however at pH ≥ 7, the main specie detected is the anionic one, differently oriented with respect to the nanoparticle surface. The metal‐piroxicam systems here characterized by surface‐enhance Raman scattering spectroscopy could constitute nanocarriers in future projects of transporting and releasing of the drug in the body. Copyright © 2015 John Wiley & Sons, Ltd.     

Ultrathin silver‐coated gold nanoparticles as suitable substrate for surface‐enhanced Raman scattering

Surface‐enhanced Raman scattering (SERS) is an extremely powerful tool for the analysis of the composition of bimetallic nanoparticle (BNP) surfaces because of the different adsorption schemes adopted by several molecules on different metals, such as Au and Ag. The preparation of BNPs normally implies a change in the plasmonic properties of the core metal. However, for technological applications it could be interesting to synthesize core–shell structures preserving these original plasmonic properties. In this work, we present a facile method for coating colloidal gold nanoparticles (NPs) in solution with a very thin shell of silver. The resulting bimetallic Au@Ag system maintains the optical properties of gold but shows the chemical surface affinity of silver. The effectiveness of the coating method, as well as the progressive silver enrichment of the outermost part of the Au NPs, has been monitored through the SERS spectra of several species (chloride, luteolin, thiophenol and lucigenin), which show different behaviors on gold and silver surfaces. A growth mechanism of the Ag shell is proposed on the basis of the spectroscopic and microscopic data consisting in the formation and deposit of Ag clusters on the Au NP surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering of benzenesulfonamide and sulfanilamide adsorbed on silver nanoparticles

The Surface‐enhanced Raman scattering of benzenesulfonamide and sulfanilamide adsorbed on silver sols was studied. On the basis of the noticeable shifts observed for wavenumbers of the ν_s(OSO), ν(CS), and ν(SN) vibrations with respect to the Raman spectra of the solids and the ionic solutions, we conclude that these molecules are adsorbed on silver nanoclusters at pH ≥ 7 with the aminosulfonyl groups partially deprotonated. The benzenesulfonamide links to the metal through the nitrogen atom of the corresponding azanion, while the sulfanilamide interacts in turn through the nitrogen atoms of the –NH₂ and –SO₂NH^– groups in the para‐position. Additionally, it was found that the most enhanced surface‐enhanced Raman scattering bands, especially the 8a;ν_ring mode, are related to the presence of the charge transfer mechanism. Copyright © 2011 John Wiley & Sons, Ltd.     

Enzyme-induced growth of silver nanoparticles studied on single particle level

Based on their interesting properties, metal nanoparticles show the potential as an analytical tool in electronic (Burmeister et al. 2004), optical (Yguerabide and Yguerabide 1998), and catalytic applications (Liu 2006). Their characteristics depend on the composition, shape, and size of the single particles. These various properties are utilized in many different approaches such as optics, magnetics (Lang et al. 2007), and laser technology (Csaki et al. 2007). We investigated an alternative method for the synthesis of nanoparticles. In this case, an enzyme, horseradish peroxidase, induces a silver deposition and replaces a metal nanoparticle as the reaction seed. Depending on the reaction time, we could obtain particles in a range of few nanometers up to more than 250 nm. For a better understanding of the enzymatic silver deposition process, the silver particles produced by this process were analyzed by SEM, TEM, and atomic force microscopy (AFM) on a single particle level after different enhancement times. The AFM images were utilized for the characterization of particle height and volume to study the enzyme kinetics, i.e., the particle growth process. Thereby, two different phases are described: a first growth phase probably induced by the enzyme-related growth, and a second, more unspecific growth based on the metal deposition onto the silver deposits. These findings may help to use the enzyme-induced silver deposition in a quantitative manner for bioanalytical applications.     

Antibacterial activity of silver and zinc oxide nanoparticles produced by spark discharge in deionized water

Inorganic antibacterial agents such as metal nanoparticles (NPs) are very important in biomedical and pharmaceutical areas. There are many methods of synthesizing these NPs, but all of them have their own disadvantages. In this study, ultrasonic‐assisted spark discharge is employed to produce colloidal silver (Ag) and zinc oxide (ZnO) NPs which are stable without using any stabilizers or surfactants. Different tests such as X‐ray diffraction, field emission scanning electron microscopy, and ultraviolet–visible absorption spectroscopy are used for the characterization of the quantity and quality of these NPs, and their antibacterial activity is evaluated by the disk diffusion method and determination of the minimum inhibitory concentrations against Escherichia coli . The results show that the overall antibacterial activity of Ag NPs is higher than that of ZnO NPs.