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1.
Anisotropic metallic nanoparticles (NPs) have unique optical properties, which lend them to applications such as surface‐enhanced Raman scattering (SERS) spectroscopy. Star‐shaped gold (Au) NPs were prepared in aqueous solutions by the seed‐mediated growth method and tested for Raman enhancement using 2‐mercaptopyridine (2‐MPy) and crystal violet (CV) probing molecules. For both molecules, the SERS activity of the nanostars was notably stronger than that of the spherical Au NPs of similar size. The Raman enhancement factors (EFs) for 2‐MPy on Au nanostars and nanorods are comparable and estimated as greater than 5 orders of magnitude. However, the enhancement for CV on nanostars was significantly higher than for nanorods, in particular at CV concentrations of 100 nM or lower. This article is a US Government work and is in the public domain in the USA. Published in 2008 by John Wiley & Sons, Ltd. 相似文献
2.
Renming Liu Shuangmei Zhu Minzhen Si Zhenquan Liu Deqing Zhang 《Journal of Raman spectroscopy : JRS》2012,43(3):370-379
A simple method is demonstrated to detect DNA at low concentrations on the basis of surface‐enhanced Raman scattering (SERS) via polyvinyl alcohol‐protected silver grasslike patterns (PVA‐Ag GPs) grown on the surface of the common Al substrate. By the SERS measurements of sodium citrate and thymine, the PVA‐Ag GPs are shown to be an excellent SERS substrate with good activity, stability and reproducibility. With the use of the tested molecule of thymine, the enhancement factor of the PVA‐Ag GPs is up to ~1.4 × 108. The PVA‐Ag GPs are also shown to be an excellent SERS substrate with good biocompatibility for DNA detection, and the detection limit is down to ~10−5 mg/g. Meanwhile, the assignations of the Raman bands and the adsorption behaviors of the DNA molecules are also analyzed. In this work, the geometry optimization and the wavenumber analysis of adenine–Ag and guanine–Ag complexes for the ground states are performed using density functional theory, B3LYP functional and the LanL2DZ basis set. The transition energies and the oscillator strengths of adenine–Ag and guanine–Ag for the lowest six singlet excited states were calculated by using the time‐dependent density functional theory method with the same functional and basis set. The results show that the charge transfer in the adenine–Ag and guanine–Ag complexes should be the chemical factor for the SERS of the DNA molecules. Lastly, this method may be employed in large‐scale preparation of substrates that have been widely applied in the Raman analysis of DNA because the fabrication process is simple and inexpensive. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
3.
Andrzej Kudelski Marcin Pisarek Agata Roguska Marcin Hodyski Maria Janik‐Czachor 《Journal of Raman spectroscopy : JRS》2012,43(10):1360-1366
Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al2O3 and TiO2) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al2O3 and TiO2 with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO2‐n/Ti and Ag/Al2O3‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al2O3‐n/Al substrate are distinctly different from those measured for an Ag/TiO2‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO2‐n/Ti and Ag/Al2O3‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
4.
Gediminas Gervinskas Gediminas Seniutinas Jennifer S. Hartley Sasikaran Kandasamy Paul R. Stoddart Narges F. Fahim Saulius Juodkazis 《Annalen der Physik》2013,525(12):907-914
Reactive ion etching was used to fabricate black‐Si over the entire surface area of 4‐inch Si wafers. After 20 min of the plasma treatment, surface reflection well below 2% was achieved over the 300–1000 nm spectral range. The spikes of the black‐Si substrates were coated by gold, resulting in an island film for surface‐enhanced Raman scattering (SERS) sensing. A detection limit of 1 × 10?6 M (at count rate > 102 s?1 . mW?1) was achieved for rhodamine 6G in aqueous solution when drop cast onto a ~ 100‐nm‐thick Au coating. The sensitivity increases for thicker coatings. A mixed mobile‐on‐immobile platform for SERS sensing is introduced by using dog‐bone Au nanoparticles on the Au/black‐Si substrate. The SERS intensity shows a non‐linear dependence on the solid angle (numerical aperture of excitation/collection optics) for a thick gold coating that exhibits a 10 times higher enhancement. This shows promise for augmented sensitivity in SERS applications. 相似文献
5.
We report the observation of large surface‐enhanced Raman scattering (SERS) (106) for 4‐tert‐butylpyridine molecules adsorbed on a silver electrode surface in an electrochemical cell with electrode potential set at − 0.5 V. A decrease in electrode potential to − 0.3 V was accompanied by a decrease in relative intensities of the vibrational modes. However, there were no changes in vibrational wavenumbers. Comparison of both normal solution Raman and SERS spectra shows very large enhancement of the intensities of a1, a2, and b2 modes at laser excitation of 488 nm. Enhancement of the non‐totally symmetric modes indicates the presence of charge transfer as a contributor to the enhancement. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
6.
Surface‐enhanced Raman scattering and density functional theory studies of bis(4‐aminophenyl)sulfone
Guillermo Diaz‐Fleming Freddy Clis Carlos Fredes Marcelo Campos‐Vallette Alvaro E. Aliaga Rainer Koch 《Journal of Raman spectroscopy : JRS》2010,41(2):160-166
Raman and surface‐enhanced Raman scattering (SERS) spectra of dapsone by using colloidal silver nanoparticles have been recorded. Density functional theory was used for the optimization of ground state geometries and simulation of the vibrational spectrum of this molecule. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman as well as the SERS normal modes and the corresponding assignments, along with the modeling of the free dapsone and the one in the presence of the colloidal silver nanoparticles, the importance of the sulfone group on the SERS effect in dapsone was inferred. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
7.
Muhammad A. Khan Timothy P. Hogan B. Shanker 《Journal of Raman spectroscopy : JRS》2008,39(7):893-900
We utilized bulk‐synthesized nanowires (NWs) of germanium dioxide as nanoscale structures that can be coated with noble metals to allow the excitation of surface plasmons over a broad frequency range. The NWs were synthesized on substrates of silicon using gold‐catalyst‐assisted vapor–liquid–solid (VLS) growth mechanism in a simple quartz tube furnace setup. The resulting NWs have diameters of ∼100–200 nm, with lengths averaging ∼10–40 µm and randomly distributed on the substrate. The NWs are subsequently coated with thin films of gold, which provide a surface‐plasmon‐active surface. Surface‐enhanced Raman scattering (SERS) studies with near‐infrared (NIR) excitation at 785 nm show significant enhancement (average enhancement > 106) with good uniformity to detect submonolayer concentrations of 4‐methylbenzenethiol (4‐MBT), trans‐1,2‐bis(4‐pyridyl)ethylene (BPE), and 1,2‐benzendithiol (1,2‐BDT) probe molecules. We also observed an intense, broad continuum in the Raman spectrum of NWs after metal coating, which tended to diminish with the analyte monolayer formation. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
8.
Fanxin Liu Xuhong Ye Chaojun Tang Hongtao Ma 《Journal of Raman spectroscopy : JRS》2013,44(3):393-400
We have demonstrated a novel method to generate the nanostructured substrate that shows a large enhancement with a spatially uniform enhancement factor of approximately 106 in surface enhanced Raman scattering (SERS). The substrates are fabricated using plasma selective etching. First, the Al2O3–TiC template which contains mixed Al2O3 and TiC grains with the diameters of ~400 nm is selected as a base plate. The Al2O3 and TiC grains have different physical properties, such as hardness, which corresponds to different etching rate in a plasma gas. Then, the Al2O3–TiC substrate is selectively etched to generate a random macro‐texture (MT) with different depths using the plasma of mixed gas of Ar and C2H4. Third, the MT substrate is deposited with a silver film (Ag). We further demonstrate that by varying the thickness of Ag layer, the EF is different which is confirmed by the plasmonic localized electric fields calculations using finite difference time domain. Finally, we combine this novel Ag MT substrate with ultrathin dielectric film, and the prepared substrates are coated with a 10 Å ta‐C film. The 10 Å ta‐C film can protect the oxygen‐free Ag in air and prevent Ag ionizing in aqueous solutions. More importantly, the ultrathin ta‐C can release the strongest plasmonic electric field to the outside of ta‐C layer and get a higher electric field than the uncoated Ag substrate. We expect that this method has more potential applications in analytic assays using SERS technology. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
9.
Zhixun Luo Wensheng Yang Yi Luo Aidong Peng Ying Ma Hongbing Fu Jiannian Yao Boon H. Loo 《Journal of Raman spectroscopy : JRS》2011,42(5):951-957
The applicability of surface‐enhanced Raman spectroscopy is demonstrated to probe the adsorption behavior of individual molecules on a Ag electrode. High‐quality SERS spectra of (R)‐di‐2‐naphthylprolinol (DNP) were obtained from ultradilute solutions (10−12 M ) on the Ag‐nanoparticle‐modified Ag electrode, which is attributed to the high electromagnetic (EM) effect of the SERS‐active system as well as to the strong adsorption and interaction of DNP molecules with Ag. The stable SERS spectra present remarkable potential dependence, which gives evidence for the behavior of individual DNP molecules on the Ag surface. Based on statistical analysis for the probability of DNP molecules located in ‘hot spots’, we propose an SERS mechanism for individual molecules in the electrode system, in combination with the hot‐spot model and orientation of the probe molecules. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
10.
Xiangxin Xue Weidong Ruan Libin Yang Wei Ji Yunfei Xie Lei Chen Wei Song Bing Zhao John R. Lombardi 《Journal of Raman spectroscopy : JRS》2012,43(1):61-64
Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
11.
Yumeng You N. A. Purnawirman Hailong Hu Johnson Kasim Huanping Yang Chaoling Du Ting Yu Zexiang Shen 《Journal of Raman spectroscopy : JRS》2010,41(10):1156-1162
We report the surface‐enhanced Raman scattering (SERS) effect from the apex of single‐crystalline Ag nanowires (NWs). We also fabricated tip‐enhanced Raman spectroscopy (TERS) tips by attaching individual Ag NWs to W wires by using the alternating current dielectrophoresis (AC‐DEP) method. The single‐crystalline Ag NW tips could overcome many of the shortcomings of conventional TERS tips. Most importantly, the results obtained from TERS using single‐crystalline metal NWs are very reproducible, and the tips are also reusable. This development represents a significant progress in making TERS a reliable optical characterization technique with nanometer spatial resolution. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
12.
Intensity‐Enhanced Apodization Effect on an Axially Illuminated Circular‐Column Particle‐Lens
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Liyang Yue Bing Yan James N. Monks Rakesh Dhama Zengbo Wang Oleg V. Minin Igor V. Minin 《Annalen der Physik》2018,530(2)
A particle can function as a refractive lens to focus a plane wave, generating a narrow, high intensive, weak‐diverging beam within a sub‐wavelength volume, known as the ‘photonic nanojet’. It is known that apodization method, in the form of an amplitude pupil‐mask centrally situated on a particle‐lens, can further reduce the waist of a photonic nanojet, however, it usually lowers the intensity at the focus due to blocking the incident light. In this paper, the anomalously intensity‐enhanced apodization effect was discovered for the first time via numerical simulation of focusing of the axially illuminated circular‐column particle‐lenses, and a greater than 100% peak intensity increase was realised for the produced photonic nanojets. 相似文献
13.
Xiaoqi Fu Fengli Bei Xin Wang Xujie Yang Lude Lu 《Journal of Raman spectroscopy : JRS》2009,40(9):1290-1295
We report surface‐enhanced Raman scattering (SERS) spectra from 4‐mercaptopyridine (4‐Mpy) adsorbed on sub‐monolayers of α‐Fe2O3 nanocrystals (sphere, spindle, cube). The maximum enhancement factor has been estimated to be about 104 compared to that of 4‐Mpy in solution. A possible mechanism has been proposed that the charge transfer between the α‐Fe2O3 nanocrystals and the 4‐Mpy molecules is most likely responsible for the observed enhancement of Raman intensity of adsorbed 4‐Mpy molecules as surface plasmon resonances have not occurred. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
14.
Juqiang Lin Rong Chen Shangyuan Feng Jianji Pan Buhong Li Guannan Chen Shaojun Lin Chao Li Li‐qing Sun Zufang Huang Haishan Zeng 《Journal of Raman spectroscopy : JRS》2012,43(4):497-502
Combining membrane electrophoresis with surface‐enhanced Raman scattering (SERS) spectroscopy, the serum proteins were first purified and then mixed with silver nanoparticles to perform SERS spectral analysis. Therefore, the spectral signatures were enhanced to high‐fidelity SERS signatures because of the purification procedure of the first step. We used the method to analyze blood plasma samples from nasopharyngeal cancer patients (n = 43) and healthy volunteers (n = 33) for cancer detection. Principle component analysis of the SERS spectra revealed that the data points for the cancer group and the normal group form distinct, completely separated clusters with no overlap. Therefore, the nasopharyngeal cancer group can be unambiguously discriminated from the normal group, i.e., with both diagnostic sensitivity and specificity of 100%. These results are very promising for developing a label‐free, noninvasive, and reliable clinical tool for rapid cancer detection and screening. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
15.
Tatyana Teslova Charlie Corredor Richard Livingstone Tudor Spataru Ronald L. Birke John R. Lombardi M. V. Caamares Marco Leona 《Journal of Raman spectroscopy : JRS》2007,38(7):802-818
The Raman and surface‐enhanced Raman spectra (SERS) of flavone and three of its hydroxy derivatives, 3‐hydroxyflavone (3‐HF) and 5‐hydroxyflavone (5‐HF) and quercetin (3,5,7,3′,4′ pentahydroxyflavone) have been obtained. The normal Raman (NR) spectra were taken in the powder form. The SERS spectra were obtained both on Ag colloids and Ag electrode substrates. Assignments of the spectrally observed normal modes were aided by density functional theory (DFT) calculations using the B3LYP functional and the 6‐31 + G* basis, a split valence polarized basis set with diffuse functions. Excellent fits were obtained for the observed spectra with little or no scaling. The most intense lines of the NR spectra are those in the CO stretching region (near 1600 cm−1). These lines are often weakened by proximity to the surface, while other lines at lower wavenumbers, due to in‐plane ring stretches, tend to be strongly enhanced. The SERS spectrum of flavone is weak both on the colloid and on the electrode, indicating weak attachment to the surface. In contrast, the SERS spectra of the hydroxy derivatives of flavone are intense, indicating the assistance of OH groups in attachment to the surface. The spectra of the various species are compared, and a case study of application to detection of a textile dye (Persian berries), which contains quercetin, is presented. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
16.
An analytical approach using enhanced Raman spectroscopy to record molecular vibrations and associated molecular images within nanometric apertures is presented, which can essentially rival or surpass its counterparts, i.e. fluorescence microscopy, by providing unique structure‐specific information forward to chemical identification and structure elucidation. Utilizing a precise nanolithographic technology and the following chemically electroless silver deposition procedure, we deliberately construct the large scale zero‐mode waveguide array in gold film with embossed silver nanostructures on the bottom of nanowells capable of acquiring enhanced Raman spectra with substantial sensitivity and high chemical fidelity. Two chemicals, aminothiophenol (4‐ATP) and Rhodamine 6G, respectively, are employed as molecular indicators to successfully demonstrate the capability of this analytical strategy by exhibiting high‐quality Raman spectra and 2D chemical‐specific images. With a high magnitude objective (60×), we enable to acquire Raman spectra from a single nanometric aperture and quantitatively determine a peak enhancement factor of 3.63 × 105 for ATP, while 1.25 × 106 to Rhodamine 6G, comparable with a regular nanoparticle‐based surface‐enhanced Raman spectroscopy‐active substrate. Overall, the compelling characteristics of this detection scheme highlight its privileges for interrogating the individual molecular behavior in extremely confined geometry and illustrating the chemical insights of trace components without any labeling reagent and extra sample preparation. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
17.
Charge‐transfer contributions in surface‐enhanced Raman scattering from Ag,Ag2S and Ag2Se substrates
Xiaoqi Fu Tingshun Jiang Qian Zhao Hengbo Yin 《Journal of Raman spectroscopy : JRS》2012,43(9):1191-1195
The degree of charge‐transfer in Ag–4‐mercaptopyridine (Mpy) and Ag2S–4‐Mpy systems is investigated by use of surface‐enhanced Raman spectroscopy (SERS). Ag2S and Ag2Se nanoparticles are prepared on the basis of the former formation of Ag nanoparticles to make the SERS analytical objects comparable. We utilize the intensity of the non‐totally symmetric modes (either b1 or b2) as compared with the totally symmetric a1 modes to measure the degree of charge‐transfer. We find ~25% of charge‐transfer contribution for Ag–4‐Mpy, whereas 81 ~ 93% for Ag2S–4‐Mpy. It means that the charge‐transfer resonance contribution dominates the overall enhancement in SERS of Ag2S–4‐Mpy. Energy level diagram is applied to discuss the likely charge‐transfer transition between Ag, Ag2S, Ag2Se and 4‐Mpy. This article may point out the link among the three main resonance sources and could enable some insights into the electronic pathways available to the metal‐molecule and semiconductor‐molecule systems. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
18.
Surface‐enhanced Raman spectroscopy (SERS) coupled with dendritic silver nanosubstrates was used in this study for rapid detection and characterization of restricted antibiotics. Dendritic silver nanosubstrates were prepared through a simple replacement reaction and stored in deionized water for months. SERS methods with near‐IR excitation at 785 nm using silver nanosubstrates were evaluated for detection of three restricted antibiotics (i.e. enrofloxacin, ciprofloxacin, and chloramphenicol) prepared in standard solutions. SERS was capable of identifying and characterizing three antibiotics quickly and accurately. Silver dendrites exhibit satisfactory and consistent performance with an analytical enhancement factor of ∼104. The limit of detection and limit of quantification for antibiotics could reach the level of 20 ppb. Silver dendrites can be kept in deionized water for up to 6 months with no signs of degradation in SERS performance. These results demonstrate a great potential of using SERS coupled with silver dendrites for rapid detection, classification, and quantification of chemical contaminants. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
19.
Luca Guerrini Jos V. Garcia‐Ramos Concepcin Domingo Santiago Sanchez‐Cortes 《Journal of Raman spectroscopy : JRS》2010,41(5):508-515
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. 相似文献
20.
Regular Hexagonal Gold Nanoprisms Fabricated by a Physical Method: Toward Use as Ultrasensitive Surface‐Enhanced Raman Scattering Substrates
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Yiming Bai Lingling Yan Zhigang Yin Jun Wang Nuofu Chen Jikun Chen Zhanao Tan 《Particle & Particle Systems Characterization》2016,33(5):254-260
A simple physical approach to prepare gold (Au) nanoparticles with sharp edges for increasing surface‐enhanced Raman scattering (SERS) response is presented. The shape evolution process of Au nanoparticles under different fabrication conditions is studied, and a thermodynamic model is adopted to explain the shape transition. Single‐crystalline Au nanoprisms with regular hexagonal shape can be formed at a certain annealing temperature. Coating of these Au nanoprisms with graphene causes them to exhibit a SERS enhancement of 60x. This is the first demonstration of a physical approach to fabricate regular hexagonal Au nanoprisms that exhibit an ultrasensitive SERS effect. Furthermore, the local field distribution of a series of Au nanoprisms with different sizes is simulated to better understand their ultrasensitive SERS performance. 相似文献