Interactions of ibuprofen with hybrid lipid bilayers probed by complementary surface-enhanced vibrational spectroscopies

The incorporation of small molecules into lipid bilayers is a process of biological importance and clinical relevance that can change the material properties of cell membranes and cause deleterious side effects for certain drugs. Here we report the direct observation, using surface-enhanced Raman and IR spectroscopies (SERS, SEIRA), of the insertion of ibuprofen molecules into hybrid lipid bilayers. The alkanethiol-phospholipid hybrid bilayers were formed onto gold nanoshells by self-assembly, where the underlying nanoshell substrates provided the necessary enhancements for SERS and SEIRA. The spectroscopic data reveal specific interactions between ibuprofen and phospholipid moieties and indicate that the overall hydrophobicity of ibuprofen plays an important role in its intercalation in these membrane mimics.     

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: Origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10⁵, and the detection limit of rhodamine 6G at DAR surfaces was 10⁻⁸ M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications.     

Correlation of surface-enhanced Raman spectroscopy and laser desorption-ionization mass spectrometry acquired from silver nanoparticle substrates

Applying complementary experiments, like laser desorption-ionization mass spectrometry (LDI-MS) and confocal surface-enhanced Raman microscopy, to the same physical sample location has the potential to elucidate the behavior of complex chemical and biochemical systems in ways that are not available to either method applied in isolation. In these experiments surface-enhanced Raman scattering (SERS) and LDI-MS are applied to the same sample spot using a common structure, deposited Ag colloids, both as ionization matrix and simultaneously as enhancing media for surface-enhanced Raman scattering of small organic molecules, dyes and lipids, and the behavior is compared. Three compounds-p-aminothiophenol (ATP), rhodamine 6G and cholesterol-which exhibit different strengths of interaction with Ag are examined in detail by correlated SERS and LDI-MS. The related mechanisms of nanoparticle-assisted desorption-ionization and Raman enhancement are explored by correlating mass and Raman spectra. The correlated spectra highlight the manner in which the different test compounds interact with plasmonic metal nanostructures. These coupled studies yield new insight into the transition of analyte from the metal-solution interface to gaseous ions, including, in the case of organothiols, a rich set of mixed clusters that provide chemical insight into the ion formation process.     

二步电沉积法制备Au/氧化石墨烯复合薄膜作为SERS基底

采用二步电沉积方法在Ti片表面制备了Au-氧化石墨烯（Au-GO）复合薄膜,通过XRD、SEM、XPS等对薄膜的组成、结构和形貌进行了表征,并以罗丹明6G（R6G）为探针分子,对Au-GO/Ti基底的SERS活性进行了表征。结果显示,Au纳米颗粒尺寸约为60 nm,均匀、致密分布于GO表面,该基底显示出较高的SERS活性,对R6G分子的检测极限可达~10^-10 mol·L^-1,增强因子高达约10⁶,且基底显示出良好的稳定性,在冰箱中存放90 d后,SERS活性仅降低30%左右。     

二步电沉积法制备Au/氧化石墨烯复合薄膜作为SERS基底

采用二步电沉积方法在Ti片表面制备了Au-氧化石墨烯（Au-GO）复合薄膜,通过XRD、SEM、XPS等对薄膜的组成、结构和形貌进行了表征,并以罗丹明6G（R6G）为探针分子,对Au-GO/Ti基底的SERS活性进行了表征。结果显示,Au纳米颗粒尺寸约为60 nm,均匀、致密分布于GO表面,该基底显示出较高的SERS活性,对R6G分子的检测极限可达~10^-10 mol·L^-1,增强因子高达约10⁶,且基底显示出良好的稳定性,在冰箱中存放90 d后,SERS活性仅降低30%左右。     

Templated assembly of gold nanoparticles into microscale tubules and their application in surface-enhanced Raman scattering

We report a simple procedure to assemble gold nanoparticles into hollow tubular morphology with micrometer scale, wherein the citrate molecule is used not only as a reducing and capping agent, but also as an assembling template. The nanostructure and growth mechanism of microtubes are explored via SEM, TEM, FTIR spectra, and UV-vis spectra studies. The incorporation of larger gold nanoparticles by electroless plating results in an increase in the diameter of microtubes from 900 nm to about 1.2 microm. The application of the microtubes before and after electroless plating in surface-enhanced Raman scattering (SERS) is investigated by using 4-aminothiophenol (4-ATP) as probe molecules. The results indicate that the microtubes both before and after electroless plating can be used as SERS substrates. The microtubes after electroless plating exhibit excellent enhancement ability.     

Fabrication, characterization, and application in surface-enhanced Raman spectrum of assembled type-I collagen-silver nanoparticle multilayered films

In this paper, we report a facile method for the fabrication of type-I collagen-silver nanoparticles (Ag NPs) multilayered films by utilizing type-I collagen as a medium. These samples were characterized by UV-vis spectra photometer, atomic force microscopy, scanning electron microscopy, and Fourier transform IR spectrum. Experimental results show that collagen molecules serve as effective templates to assemble Ag NPs into multilayer films. These samples exhibit high surface-enhanced Raman scattering (SERS) enhancement abilities. For example, EF(nu(cc)) (EF means enhancement factor) at 1592 cm(-1) in the SERS spectrum of 4-aminothiophenol on seven-layered substrates was calculated to be 1.81 x 10(5), which is larger than that reported in several literatures. The EFs increased as the layer number of multilayer films increases.     

Batch fabrication of disposable screen printed SERS arrays

A novel facile method of fabricating disposable and highly reproducible surface-enhanced Raman spectroscopy (SERS) arrays using screen printing was explored. The screen printing ink containing silver nanoparticles was prepared and printed on supporting materials by a screen printing process to fabricate SERS arrays (6 × 10 printed spots) in large batches. The fabrication conditions, SERS performance and application of these arrays were systematically investigated, and a detection limit of 1.6 × 10(-13) M for rhodamine 6G could be achieved. Moreover, the screen printed SERS arrays exhibited high reproducibility and stability, the spot-to-spot SERS signals showed that the intensity variation was less than 10% and SERS performance could be maintained over 12 weeks. Portable high-throughput analysis of biological samples was accomplished using these disposable screen printed SERS arrays.     

Surface-enhanced Raman scattering sensor for theophylline determination by molecular imprinting on silver nanoparticles

A surface-enhanced Raman scattering (SERS)-based sensor for the determination of theophylline (THO) has been developed by imprinting the target molecules on the surface of silver nanoparticles. The desired recognition sites are generated after template removal and homogeneous distribution on the silver nanoparticles that have been incorporated within polymer matrix by the in situ reduction of theophylline-silver complexes, providing molecular recognition ability and SERS active surfaces. The theophylline molecules, complementary to the shape, size, and functionality of the recognition cavities, can selectively bind to the recognition sites at the surface of silver nanoparticles driven by the formation of hydrogen bonding and surface coordination. It has been demonstrated that the SERS signals of the theophylline molecules captured on the surface of the silver nanoparticles have a good reproducibility and a dose-response relationship to the target analytes, showing the potential for reliable identification and quantification of the bioactive compound. The molecular imprinting-based SERS sensor, like antibodies or enzymes, also possesses the ability to distinguish theophylline from the closely related structure caffeine due to the variations of molecular size and shape as well as the different affinity to silver ions.     

Surface-enhanced raman scattering on dendrimer/metallic nanoparticle layer-by-layer film substrates

In this paper, the fabrication, characterization, and application of unique layer-by-layer (LBL) films of dendrimers and metallic nanoparticles is reported. Silver nanoparticles (d = approximately 20 nm) are produced in solution by sodium citrate reduction and incorporated into thin films with generation 1 and 5 DAB-Am dendrimers (polypropylenimine dendrimers with amino surface groups) by the LBL technique. The resulting nanocomposite films are characterized by UV-visible surface plasmon absorption and atomic force microscopy (AFM) measurements, and employed as substrates for surface-enhanced Raman scattering (SERS) of 2-naphthalenethiol. Through variation of the molecular size (dendrimer generation) and concentration of the cross-linker used, as well as the number of layers produced, the optical properties of several different possible architectures are studied. In the films, Ag nanoparticles are shown to be effectively immobilized and stabilized with increased control over their spacing and aggregation. Moreover, the films are shown to be excellent substrates for SERS measurements, demonstrating significant enhancement capability. As expected, large electromagnetic enhancement of Raman scattering signals is found to be strongly dependent on interparticle coupling between neighboring metallic nanoparticles. Finally, the possibility of detecting SERS signals from architectures with intervening layers between the metal nanoparticles and analyte molecules is explored. It is shown that although there are decreases in intensity with increasing number of intervening layers (as is expected from the distance dependence of SERS), electromagnetic enhancement is still able to function at these distances, thus offering the possibility of developing sensors with external layers that are chemically selective for specific analytes.     

Self-assembled metal colloid films: two approaches for preparing new SERS active substrates

In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.     

Cu掺杂TiO_2作为SERS基底的研究

本文采用溶胶-水热法制备了TiO2及Cu掺杂的TiO2纳米粒子作为表面增强拉曼光谱(SERS)活性基底,观察到当4-巯基苯甲酸吸附在3%Cu掺杂的TiO2表面上时,其SERS信号得到了最大程度的增强.Cu离子掺杂进TiO2晶格时会使TiO2表面的缺陷浓度(表面态)得到增加,一定量的缺陷浓度对TiO2-to-Molecule的电荷转移机理起到促进作用,进一步证明了化学增强机理在SERS现象的贡献.     

Surface-enhanced Raman scattering imaging of single living lymphocytes with multivariate evaluation

This paper is aimed to show the possibility to determine individual organic compounds introduced into single living cells with surface-enhanced Raman spectroscopy (SERS). Surface enhancement was achieved with gold colloids that were allowed to diffuse into lymphocytes. An introduced analyte, rhodamine 6G, could be imaged together with for example nucleotides and amino acids of the cell. Multivariate evaluation of surface-enhanced Raman images proved to be a powerful tool for the separation of spectral information of various intracellular components. The principal component analysis (PCA) enabled identification of spectra containing different chemical information and separation of the spectral contribution of rhodamine 6G from the complex cellular matrix.     

SnO2纳米粒子作为SERS基底的研究

采用溶胶-水热法制备了不同尺寸的SnO2纳米粒子, 并将其作为表面增强拉曼散射(Surface-enhanced Raman scattering, SERS)活性基底, 重点探讨了表面缺陷能级与SERS性能的关系. 观察到4-巯基苯甲酸(4-MBA)吸附在150 ℃水热合成的SnO2纳米粒子上的SERS 信号最强, 随着在空气中煅烧温度的升高, SERS信号逐渐减弱. 分别用透射电子显微镜、 紫外-可见光谱、 荧光光谱、 X射线衍射和X射线光电子能谱对SnO2纳米粒子进行了表征. 结果表明, SnO2纳米粒子的表面氧空位和缺陷等表面性质在增强拉曼散射性能中发挥着重要的作用, 表面氧空位和缺陷等含量越高其SERS信号就越强.     

Surface-enhanced Raman scattering from ordered Ag nanocluster arrays

We have examined the effect of ordered silver nanocluster substrates on the surface-enhanced Raman spectrum of rhodamine 6G (R6G). Triangular shaped silver nanocluster arrays with order on the approximately 100 mum range were prepared using nanosphere lithography. Direct comparisons of R6G surface-enhanced Raman spectroscopy (SERS) signals between ordered nanocluster regions and amorphous Ag regions prepared under identical deposition conditions provide strong evidence of an electromagnetic field enhancement attributed to the unique nanocluster morphology. We have obtained order of magnitude enhancement factors for both 200 and 90 nm Ag nanocluster SERS substrates relative to Ag films.     

Competitive surface-enhanced Raman scattering effects in noble metal nanoparticle-decorated graphene sheets

Herein, noble metal nanoparticle (Au or Ag NP) decorated graphene sheets, fabricated according to a facile one-pot environmentally friendly method, are used as good substrates for the investigation of the combined surface-enhanced Raman scattering (SERS) effect, where both the electromagnetic mechanism and the chemical mechanism effects coexist among the Au or Ag NPs, graphene sheets and the absorbed analytes. Our results show that, in aqueous solution, the SERS effect of both the Au and Ag NPs on the absorbed probe molecules and on graphene is competitive, which varies dependent on the species and the concentration of the absorbed probe molecule. By a detailed comparison of three probe molecules (rhodamine 6G, nile blue A, and 4-aminobenzenethiol) with different coupling abilities to the graphene sheets, we finally attribute this phenomenon to the result of the strong suppressing effect of the macrocyclic probe molecules on the SERS of graphene, induced by charge transfer, as the probe molecules are coupled to the graphene sheets. This competitive effect is a non-ignorable phenomenon when graphene/Au or Ag nanocomposites are used as SERS substrates, and our study may deepen our understanding of the SERS mechanism.     

复合SERS基底的构建及性质

通过自组装方法以对巯基苯胺(PATP)为偶联分子, 在石英基片上构筑了多种形貌的银钠米粒子单层结构和三明治结构. 研究了组装膜在不同激发线下表面增强拉曼散射(SERS)的增强差异. 研究结果表明, 单层基底和三明治基底中偶联分子的SERS信号因银纳米粒子间的电磁场耦合而显著增强, 且在三明治结构中增强更加明显. 对复合SERS基底增强因子进行计算可知, 复合SERS基底的表面等离子体共振(SPR)峰与激发线的匹配程度越好, 其增强因子越大. 在三明治结构中更易发生PATP分子转变为对巯基偶氮苯(DMAB)分子的激光诱导催化偶联反应. 另外, 该激光诱导催化偶联反应与激发波长密切相关.     

Surface-enhanced raman spectra of dyes and organic acids in silver solutions: chloride ion effect

We have recorded surface-enhanced Raman (SER) spectra of two different classes of compounds, cationic dyes and organic acids, and studied their chloride ion effects on the surface-enhanced Raman scattering (SERS) activities of the silver solution. For the positive charge dyes, rhodamine 6G (R6G) and 1,1'-dimethyl-2,2'-cyanine iodide (DECI), no SERS could be observed without the addition of chloride ions because of lack of the electrostatic interaction between the dye species and the silver particles in the silver solution. The chloride ions served to enlarge silver particles and to contribute the existence of the surface active sites, making the silver solution SERS active to the dye samples. Surface-enhanced resonance Raman scattering (SERRS) intensity of the dye molecules increased with the chloride ion concentration. After reaching a maximum intensity, a Cl- quenching effect on the intensity took place. For the organic acids, benzoic acid and p-aminobenzoic acid (PABA), SERS could be observed without the coexistence of chloride ions. The intensity of the Raman scattering did not vary significantly in the presence of small amount of chloride ion. At high Cl- concentration, quenching SERS intensity began to take effect.     

Peptide mesocrystals as templates to create an Au surface with stronger surface-enhanced Raman spectroscopic properties

The design and fabrication of various nanostructures with predefined geometry and composition is a big challenge of nanotechnology. Here we demonstrate an Au nanoflake film replicated from a self-assembled, well-ordered, dipeptide flower-like hierarchical architecture. Such morphology can give rise to useful and remarkable surface-enhanced Raman spectroscopy (SERS) properties. We obtained these nanostructures by using a scaffold of flake-built spherical dipeptide aggregations. Gold nanoparticles were sputtered on the surface of as-assembled dipeptide by an etching system. After removing the dipeptide templates by ethanol, a metal crust was left with a morphology similar to that of the dipeptide hierarchical structure. The different steps within the process were monitored by using electron microscopy, energy-dispersive spectrum (EDS) analysis and atomic force microscopy (AFM). Cyclic voltammetry and Raman spectra were employed to prove the SERS effect of the obtained Au substrates. The enhancement factor is estimated to be about 10(4) for 4-mercaptobenzoic acid (4-MBA) molecules on the Au nanoflake surfaces.     

帽状铜纳米粒子的制备及表面增强拉曼散射活性研究

采用真空热蒸发法在SiO₂纳米粒子自组装单层膜上沉积铜薄膜制备了帽状铜纳米粒子。用扫描电镜、原子力显微镜和紫外-可见-近红外分光光度计对帽状复合纳米粒子的表面形貌和光学性质进行了表征。以亚甲基蓝和吡啶-(2-偶氮-4)间苯二酚为探针分子,研究了该复合纳米粒子的表面增强拉曼散射(SERS)活性。通过比较吸附在不同基底上的吡啶-(2-偶氮-4)间苯二酚的谱峰强度,探讨了SERS效应与表面等离子体共振(SPR)的关系。