Probing Enzyme-Surface Interactions via Protein Engineering and Single-Molecule Techniques

Science.gov (United States)

2017-06-26

SECURITY CLASSIFICATION OF: The overall objective of this research was to exploit protein engineering and fluorescence single-molecule methods to...enhance our understanding of the interaction of proteins and surfaces. Given this objective, the specific aims of this research were to: 1) exploit the...incorporation of unnatural amino acids in proteins to introduce single-molecule probes (i.e., fluorophores for fluorescence resonance energy transfer

Applications of the surface enhanced Raman scattering (SERS)

International Nuclear Information System (INIS)

Picquart, M.; Haro P, E.; Bernard, S.

2007-01-01

Full text: Vibration spectroscopy techniques are used for many times to identify substances, determine molecular structure and quantify them, independently of their physical state. Raman spectroscopy as infrared absorption permit to access the vibration energy levels of molecules. In the second case, the permanent dipolar moment is involved while in the first one it is the polarizability (and the induced dipolar moment). Unfortunately, the classical Raman spectroscopy is low sensitive in particular in the case of biological molecules. On the opposite, the surface enhanced Raman spectroscopy (SERS) offers great potentialities. In this case, the molecules are adsorbed on a rough surface or on nanoparticles of gold or silver and the: signal can be increased by a factor of 10 7 to 10 8 . Moreover, the spectral enhancement is greater for the vibrations of the functional group of the molecule adsorbed on the substrate. In this work, we present the main theoretical bases of SERS, and some results obtain on different systems. (Author)

Surface enhanced Raman spectroscopy on a flat graphene surface

Science.gov (United States)

Xu, Weigao; Ling, Xi; Xiao, Jiaqi; Dresselhaus, Mildred S.; Kong, Jing; Xu, Hongxing; Liu, Zhongfan; Zhang, Jin

2012-01-01

Surface enhanced Raman spectroscopy (SERS) is an attractive analytical technique, which enables single-molecule sensitive detection and provides its special chemical fingerprints. During the past decades, researchers have made great efforts towards an ideal SERS substrate, mainly including pioneering works on the preparation of uniform metal nanostructure arrays by various nanoassembly and nanotailoring methods, which give better uniformity and reproducibility. Recently, nanoparticles coated with an inert shell were used to make the enhanced Raman signals cleaner. By depositing SERS-active metal nanoislands on an atomically flat graphene layer, here we designed a new kind of SERS substrate referred to as a graphene-mediated SERS (G-SERS) substrate. In the graphene/metal combined structure, the electromagnetic “hot” spots (which is the origin of a huge SERS enhancement) created by the gapped metal nanoislands through the localized surface plasmon resonance effect are supposed to pass through the monolayer graphene, resulting in an atomically flat hot surface for Raman enhancement. Signals from a G-SERS substrate were also demonstrated to have interesting advantages over normal SERS, in terms of cleaner vibrational information free from various metal-molecule interactions and being more stable against photo-induced damage, but with a comparable enhancement factor. Furthermore, we demonstrate the use of a freestanding, transparent and flexible “G-SERS tape” (consisting of a polymer-layer-supported monolayer graphene with sandwiched metal nanoislands) to enable direct, real time and reliable detection of trace amounts of analytes in various systems, which imparts high efficiency and universality of analyses with G-SERS substrates. PMID:22623525

Simulating Surface-Enhanced Hyper-Raman Scattering Using Atomistic Electrodynamics-Quantum Mechanical Models.

Science.gov (United States)

Hu, Zhongwei; Chulhai, Dhabih V; Jensen, Lasse

2016-12-13

Surface-enhanced hyper-Raman scattering (SEHRS) is the two-photon analogue of surface-enhanced Raman scattering (SERS), which has proven to be a powerful tool to study molecular structures and surface enhancements. However, few theoretical approaches to SEHRS exist and most neglect the atomistic descriptions of the metal surface and molecular resonance effects. In this work, we present two atomistic electrodynamics-quantum mechanical models to simulate SEHRS. The first is the discrete interaction model/quantum mechanical (DIM/QM) model, which combines an atomistic electrodynamics model of the nanoparticle with a time-dependent density functional theory description of the molecule. The second model is a dressed-tensors method that describes the molecule as a point-dipole and point-quadrupole object interacting with the enhanced local field and field-gradients (FG) from the nanoparticle. In both of these models, the resonance effects are treated efficiently by means of damped quadratic response theory. Using these methods, we simulate SEHRS spectra for benzene and pyridine. Our results show that the FG effects in SEHRS play an important role in determining both the surface selection rules and the enhancements. We find that FG effects are more important in SEHRS than in SERS. We also show that the spectral features of small molecules can be accurately described by accounting for the interactions between the molecule and the local field and FG of the nanoparticle. However, at short distances between the metal and molecule, we find significant differences in the SEHRS enhancements predicted using the DIM/QM and the dressed-tensors methods.

Surface plasmon-enhanced molecular fluorescence induced by gold nanostructures

International Nuclear Information System (INIS)

Teng, Y.; Ueno, K.; Shi, X.; Aoyo, D.; Misawa, H.; Qiu, J.

2012-01-01

The authors report on surface plasmon-enhanced fluorescence of Eosin Y molecules induced by gold nanostructures. Al 2 O 3 films deposited by atomic layer deposition with sub-nanometer resolution were used as the spacer layer to control the distance between molecules and the gold surface. As the thickness of the Al 2 O 3 film increased, the fluorescence intensity first increased and then decreased. The highest enhancement factor is achieved with a 1 nm Al 2 O 3 film. However, the trend for the fluorescence lifetime is the opposite. It first decreased and then increased. The changes in the fluorescence quantum yield were also calculated. The yield shows a similar trend to the fluorescence intensity. The competition between the surface plasmon-induced increase in the radiative decay rate and the gold-induced fluorescence quenching is responsible for the observed phenomenon. In addition, this competition strongly depends on the thickness of the spacer layer between Eosin Y molecules and the gold surface. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Enhanced photochemistry on metal surfaces

International Nuclear Information System (INIS)

Goncher, G.M.; Parsons, C.A.; Harris, C.B.

1984-01-01

Due to the fast relaxation of molecular excited states in the vicinity of a metal or semiconductor surface, few observations of surface photochemistry have been reported. The following work concerns the surface-enhanced photo-reactions of a variety of physisorbed molecules on roughened Ag surfaces. In summary, photodecomposition leads to a graphitic surface carbon product which is monitored via surface-enhanced Raman scattering. In most cases an initial two-photon molecular absorption step followed by further absorption and fragmentation is thought to occur. Enhancement of the incident fields occurs through roughness-mediated surface plasmon resonances. This mechanism provides the amplified electromagnetic surface fields responsible for the observed photodecomposition. The photodecomposition experiments are performed under ultra-high vacuum. Surface characterization of the roughened surfaces was done by Scanning Electron Microscopy (SEM), and electron-stimulated emission. The SEM revealed morphology on the order of 300-400 A. This size of roughness feature, when modelled as isolated spheres should exhibit the well-known Mie resonances for light of the correct wavelengths. For protrusions existing on a surface these Mie resonances can be thought of as a coupling of the light with the surface plasmon. Experimental verification of these resonances was provided by the electron-stimulated light emission results. These showed that a polished Ag surface emitted only the expected transition radiation at the frequency of the Ag bulk plasmon. Upon roughening, however, a broad range of lower frequencies extending well into the visible are seen from electron irradiation of the surface. Large enhancements are expected for those frequencies which are able to couple into the surface modes

Surface-Enhanced Raman Scattering Physics and Applications

CERN Document Server

Kneipp, Katrin; Kneipp, Harald

2006-01-01

Almost 30 years after the first reports on surface-enhanced Raman signals, the phenomenon of surface-enhanced Raman scattering (SERS) is now well established. Yet, explaining the enhancement of a spectroscopic signal by fouteen orders of magnitude continues to attract the attention of physicists and chemists alike. And, at the same time and rapidly growing, SERS is becoming a very useful spectroscopic tool with exciting applications in many fields. SERS gained particular interest after single-molecule Raman spectroscopy had been demonstrated. This bookl summarizes and discusses present theoretical approaches that explain the phenomenon of SERS and reports on new and exciting experiments and applications of the fascinating spectroscopic effect.

Surface-Enhanced Raman Spectroscopy of Dye and Thiol Molecules Adsorbed on Triangular Silver Nanostructures: A Study of Near-Field Enhancement, Localization of Hot-Spots, and Passivation of Adsorbed Carbonaceous Species

Directory of Open Access Journals (Sweden)

Manuel R. Gonçalves

2012-01-01

Full Text Available Surface-enhanced Raman spectroscopy (SERS of thiols and dye molecules adsorbed on triangular silver nanostructures was investigated. The SERS hot-spots are localized at the edges and corners of the silver triangular particles. AFM and SEM measurements permit to observe many small clusters formed at the edges of triangular particles fabricated by nanosphere lithography. Finite-element calculations show that near-field enhancements can reach values of more than 200 at visible wavelengths, in the gaps between small spherical particles and large triangular particles, although for the later no plasmon resonance was found at the wavelengths investigated. The regions near the particles showing strong near-field enhancement are well correlated with spatial localization of SERS hot-spots done by confocal microscopy. Silver nanostructures fabricated by thermal evaporation present strong and fast fluctuating SERS activity, due to amorphous carbon contamination. Thiols and dye molecules seem to be able to passivate the undesired SERS activity on fresh evaporated silver.

Enhanced post wash retention of combed DNA molecules by varying multiple combing parameters.

Science.gov (United States)

Yadav, Hemendra; Sharma, Pulkit

2017-11-01

Recent advances in genomics have created a need for efficient techniques for deciphering information hidden in various genomes. Single molecule analysis is one such technique to understand molecular processes at single molecule level. Fiber- FISH performed with the help of DNA combing can help us in understanding genetic rearrangements and changes in genome at single DNA molecule level. For performing Fiber-FISH we need high retention of combed DNA molecules post wash as Fiber-FISH requires profuse washing. We optimized combing process involving combing solution, method of DNA mounting on glass slides and coating of glass slides to enhance post-wash retention of DNA molecules. It was found that average number of DNA molecules observed post-wash per field of view was maximum with our optimized combing solution. APTES coated glass slides showed lesser retention than PEI surface but fluorescent intensity was higher in case of APTES coated surface. Capillary method used to mount DNA on glass slides also showed lesser retention but straight DNA molecules were observed as compared to force flow method. Copyright © 2017 Elsevier Inc. All rights reserved.

Small Molecules that Enhance the Catalytic Efficiency of HLA-DM

International Nuclear Information System (INIS)

Nicholson, M.; Moradi, B.; Seth, N.; Xing, X.; Cuny, G.; Stein, R.; Wucherpfenning, K.

2006-01-01

HLA-DM (DM) plays a critical role in Ag presentation to CD4 T cells by catalyzing the exchange of peptides bound to MHC class II molecules. Large lateral surfaces involved in the DM:HLA-DR (DR) interaction have been defined, but the mechanism of catalysis is not understood. In this study, we describe four small molecules that accelerate DM-catalyzed peptide exchange. Mechanistic studies demonstrate that these small molecules substantially enhance the catalytic efficiency of DM, indicating that they make the transition state of the DM:DR/peptide complex energetically more favorable. These compounds fall into two functional classes: two compounds are active only in the presence of DM, and binding data for one show a direct interaction with DM. The remaining two compounds have partial activity in the absence of DM, suggesting that they may act at the interface between DM and DR/peptide. A hydrophobic ridge in the DMβ1 domain was implicated in the catalysis of peptide exchange because the activity of three of these enhancers was substantially reduced by point mutations in this area

Ultrafast surface-enhanced Raman spectroscopy.

Science.gov (United States)

Keller, Emily L; Brandt, Nathaniel C; Cassabaum, Alyssa A; Frontiera, Renee R

2015-08-07

Ultrafast surface-enhanced Raman spectroscopy (SERS) with pico- and femtosecond time resolution has the ability to elucidate the mechanisms by which plasmons mediate chemical reactions. Here we review three important technological advances in these new methodologies, and discuss their prospects for applications in areas including plasmon-induced chemistry and sensing at very low limits of detection. Surface enhancement, arising from plasmonic materials, has been successfully incorporated with stimulated Raman techniques such as femtosecond stimulated Raman spectroscopy (FSRS) and coherent anti-Stokes Raman spectroscopy (CARS). These techniques are capable of time-resolved measurement on the femtosecond and picosecond time scale and can be used to follow the dynamics of molecules reacting near plasmonic surfaces. We discuss the potential application of ultrafast SERS techniques to probe plasmon-mediated processes, such as H2 dissociation and solar steam production. Additionally, we discuss the possibilities for high sensitivity SERS sensing using these stimulated Raman spectroscopies.

Laterally enhanced growth of electrodeposited Au to form ultrathin films on nonconductive surfaces

International Nuclear Information System (INIS)

Kobayashi, Chiaki; Saito, Mikiko; Homma, Takayuki

2012-01-01

We investigated the laterally enhanced growth of electrodeposited Au for fabricating nanogap electrodes. To enhance the lateral growth, we carried out electrodeposition over patterned electrodes onto a SiO 2 surface modified with self-assembled monolayers (SAMs) or dendrimers with amine groups. The morphology and thickness of the Au films were controlled by adjusting deposition conditions such as duration, applied potential, and Au ion concentration in the bath. To investigate the mechanism of the laterally enhanced growth, the surface states of SAM- or dendrimer-modified SiO 2 were analyzed by X-ray photoelectron spectroscopy (XPS). The XPS results indicate the existence of organic molecules and Au ions on the SiO 2 surface, which suggests that laterally enhanced growth is induced by the Au ions coordinated on the amine groups of the organic molecules. To further analyze the mechanism of the laterally enhanced growth, we investigated the relationship between the morphology of the laterally enhanced growth of Au and the amount of Au ions on organic molecules. The laterally enhanced growth of Au is expected to be useful for fabricating thin film nanogap electrodes.

Surface-enhanced Raman scattering on gold nanotrenches and nanoholes

KAUST Repository

Yue, Weisheng

2012-04-01

Dependent effects on edge-to-edge distance and incidence polarization in surface-enhanced Raman Scattering (SERS) were studied in detection of 4-mercaptopyridine (4-MPy) molecules absorbed on gold nanotrenches and nanoholes. The gold nanostructures with controllable size and period were fabricated using electron-beam lithography. Large SERS enhancement in detection of 4-MPy molecules on both nanostructred substrates was observed. The SERS enhancement increased exponentially with decrease of edge to-edge distance for both the nanotrenches and nanoholes while keeping the sizes of the nanotrenches and nanoholes unchanged. Investigation of polarization dependence showed that the SERS enhancement of nanotrenches was much more sensitive to the incidence polarizations than that of nanoholes. © 2012 American Scientific Publishers.

Surface Passivation for Single-molecule Protein Studies

Science.gov (United States)

Chandradoss, Stanley D.; Haagsma, Anna C.; Lee, Young Kwang; Hwang, Jae-Ho; Nam, Jwa-Min; Joo, Chirlmin

2014-01-01

Single-molecule fluorescence spectroscopy has proven to be instrumental in understanding a wide range of biological phenomena at the nanoscale. Important examples of what this technique can yield to biological sciences are the mechanistic insights on protein-protein and protein-nucleic acid interactions. When interactions of proteins are probed at the single-molecule level, the proteins or their substrates are often immobilized on a glass surface, which allows for a long-term observation. This immobilization scheme may introduce unwanted surface artifacts. Therefore, it is essential to passivate the glass surface to make it inert. Surface coating using polyethylene glycol (PEG) stands out for its high performance in preventing proteins from non-specifically interacting with a glass surface. However, the polymer coating procedure is difficult, due to the complication arising from a series of surface treatments and the stringent requirement that a surface needs to be free of any fluorescent molecules at the end of the procedure. Here, we provide a robust protocol with step-by-step instructions. It covers surface cleaning including piranha etching, surface functionalization with amine groups, and finally PEG coating. To obtain a high density of a PEG layer, we introduce a new strategy of treating the surface with PEG molecules over two rounds, which remarkably improves the quality of passivation. We provide representative results as well as practical advice for each critical step so that anyone can achieve the high quality surface passivation. PMID:24797261

Surface enhanced Raman scattering

CERN Document Server

Furtak, Thomas

1982-01-01

In the course of the development of surface science, advances have been identified with the introduction of new diagnostic probes for analytical characterization of the adsorbates and microscopic structure of surfaces and interfaces. Among the most recently de­ veloped techniques, and one around which a storm of controversy has developed, is what has now been earmarked as surface enhanced Raman scattering (SERS). Within this phenomenon, molecules adsorbed onto metal surfaces under certain conditions exhibit an anomalously large interaction cross section for the Raman effect. This makes it possible to observe the detailed vibrational signature of the adsorbate in the ambient phase with an energy resolution much higher than that which is presently available in electron energy loss spectroscopy and when the surface is in contact with a much larger amount of material than that which can be tolerated in infrared absorption experiments. The ability to perform vibrational spectroscopy under these conditions would l...

The synthesis of four-layer gold-silver-polymer-silver core-shell nanomushroom with inbuilt Raman molecule for surface-enhanced Raman scattering

Science.gov (United States)

Jiang, Tao; Wang, Xiaolong; Zhou, Jun

2017-12-01

A facial two-step reduction method was proposed to synthesize four-layer gold-silver-polymer-silver (Au@Ag@PSPAA@Ag) core-shell nanomushrooms (NMs) with inbuilt Raman molecule. The surface-enhanced Raman scattering (SERS) intensity of 4MBA adhered on the surface of Au core gradually increased with the modification of middle Ag shell and then Ag mushroom cap due to the formation of two kinds of ultra-small interior nanogap. Compared with the initial Au nanoparticles, the SERS enhancement ratio of the Au@Ag@PSPAA@Ag NMs approached to nearly 40. The novel core-shell NMs also exhibited homogeneous SERS signals for only one sample and reproducible signals for 10 different samples, certified by the low relative standard deviation values of less than 10% and 15% for the character peaks of 4-mercaptobenzoic acid, respectively. Such a novel four-layer core-shell nanostructure with reliable SERS performance has great potential application in quantitative SERS-based immunoassay.

Photochemical dynamics of surface oriented molecules

International Nuclear Information System (INIS)

Ho, W.

1992-01-01

The period 8/01/91-7/31/92 is the first year of a new project titled ''Photochemical Dynamics of Surface Oriented Molecules'', initiated with DOE Support. The main objective of this project is to understand the dynamics of elementary chemical reactions by studying photochemical dynamics of surface-oriented molecules. In addition, the mechanisms of photon-surface interactions need to be elucidated. The strategy is to carry out experiments to measure the translational energy distribution, as a function of the angle from the surface normal, of the photoproducts by time-of-flight (TOF) technique by varying the photon wavelength, intensity, polarization, and pulse duration. By choosing adsorbates with different bonding configuration, the effects of adsorbate orientation on surface photochemical dynamics can be studied

Surface-enhanced Raman scattering on gold nanotrenches and nanoholes

KAUST Repository

Yue, Weisheng; Yang, Yang; Wang, Zhihong; Chen, Longqing; Wong, Ka Chun; Syed, Ahad A.; Chen, Zong; Wang, Xianbin

2012-01-01

Dependent effects on edge-to-edge distance and incidence polarization in surface-enhanced Raman Scattering (SERS) were studied in detection of 4-mercaptopyridine (4-MPy) molecules absorbed on gold nanotrenches and nanoholes. The gold nanostructures

Facile synthesis of terminal-alkyne bioorthogonal molecules for live -cell surface-enhanced Raman scattering imaging through Au-core and silver/dopamine-shell nanotags.

Science.gov (United States)

Chen, Meng; Zhang, Ling; Yang, Bo; Gao, Mingxia; Zhang, Xiangmin

2018-03-01

Alkyne is unique, specific and biocompatible in the Raman-silent region of the cell, but there still remains a challenge to achieve ultrasensitive detection in living systems due to its weak Raman scattering. Herein, a terminal alkyne ((E)-2-[4-(ethynylbenzylidene)amino]ethane-1-thiol (EBAE)) with surface-enhanced Raman scattering is synthesized. The EBAE molecule possesses S- and C-termini, which can be directly bonded to gold nanoparticles and dopamine/silver by forming the Au-S chemical bond and the carbon-metal bond, respectively. The distance between Raman reporter and AuNPs/AgNPs can be reduced, contributing to forming hot-spot-based SERS substrate. The alkyne functionalized nanoparticles are based on Au core and encapsulating polydopamine shell, defined as Au-core and dopamine/Ag-shell (ACDS). The bimetallic ACDS induce strong SERS signals for molecular imaging that arise from the strong electromagnetic field. Furthermore, the EBAE provides a distinct peak in the cellular Raman-silent region with nearly zero background interference. The EBAE Raman signals could be tremendously enhanced when the Raman reporter is located at the middle of the Au-core and dopamine/Ag-shell. Therefore, this work could have huge potential benefits for the highly sensitive detection of intercellular information delivery by connecting the recognition molecules in biomedical diagnostics. Graphical abstract Terminal-alkyne-functionalized Au-core and silver/dopamine-shell nanotags for live-cell surface-enhanced Raman scattering imaging.

Surface-Enhanced Raman Spectroscopy of Dye and Thiol Molecules Adsorbed on Triangular Silver Nano structures: A Study of Near-Field Enhancement, Localization of Hot-Spots, and Passivation of Adsorbed Carbonaceous Species

International Nuclear Information System (INIS)

Goncalves, M.R.; Marti, O.; Fabian Enderle, F.

2012-01-01

Surface-enhanced Raman spectroscopy (SERS) of thiols and dye molecules adsorbed on triangular silver nanostructures was investigated. The SERS hot-spots are localized at the edges and corners of the silver triangular particles. AFM and SEM measurements permit to observe many small clusters formed at the edges of triangular particles fabricated by nanosphere lithography. Finite-element calculations show that near-field enhancements can reach values of more than 200 at visible wavelengths, in the gaps between small spherical particles and large triangular particles, although for the later no plasmon resonance was found at the wavelengths investigated. The regions near the particles showing strong near-field enhancement are well correlated with spatial localization of SERS hot-spots done by confocal microscopy. Silver nanostructures fabricated by thermal evaporation present strong and fast fluctuating SERS activity, due to amorphous carbon contamination. Thiols and dye molecules seem to be able to passivate the undesired SERS activity on fresh evaporated silver. excitation: by far-field illumination of metal nanostructures or rough metal Raman scattering cross-section of gold-palladium target Temporal Fluctuation in SERS Temporal and spectral fluctuations.

Indium nanoparticles for ultraviolet surface-enhanced Raman spectroscopy

Science.gov (United States)

Das, Rupali; Soni, R. K.

2018-05-01

Ultraviolet Surface-enhanced Raman spectroscopy (UVSERS) has emerged as an efficient molecular spectroscopy technique for ultra-sensitive and ultra-low detection of analyte concentration. The generic SERS substrates based on gold and silver nanostructures have been extensively explored for high local electric field enhancement only in visible-NIR region of the electromagnetic spectrum. The template synthesis of controlled nanoscale size metallic nanostructures supporting localized surface plasmon resonance (LSPR) in the UV region have been recently explored due to their ease of synthesis and potential applications in optoelectronic, catalysis and magnetism. Indium (In0) nanoparticles exhibit active surface plasmon resonance (SPR) in ultraviolet (UV) and deep-ultaviolet (DUV) region with optimal absorption losses. This extended accessibility makes indium a promising material for UV plasmonic, chemical sensing and more recently in UV-SERS. In this work, spherical indium nanoparticles (In NPs) were synthesized by modified polyol reduction method using NaBH4 having local surface plasmon resonance near 280 nm. The as-synthesized spherical In0 nanoparticles were then coated with thin silica shells of thickness ˜ 5nm by a modified Stober method protecting the nanoparticles from agglomeration, direct contact with the probed molecules as well as prevent oxidation of the nanoparticles. Morphological evolution of In0 nanoparticles and SiO2 coating were characterized by transmission electron microscope (TEM). An enhanced near resonant shell-isolated SERS activity from thin film of tryptophan (Tryp) molecules deposited on indium coated substrates under 325nm UV excitation was observed. Finite difference time domain (FDTD) method is employed to comprehend the experimental results and simulate the electric field contours which showed amplified electromagnetic field localized around the nanostructures. The comprehensive analysis indicates that indium is a promising alternate

Chloride ion-dependent surface-enhanced Raman scattering study of biotin on the silver surface

International Nuclear Information System (INIS)

Liu Fangfang; Gu Huaimin; Yuan Xiaojuan; Dong Xiao; Lin Yue

2011-01-01

In the present paper, the surface enhanced Raman scattering (SERS) technique was employed to study the SERS spectra of biotin molecules formed on the silver surface. The adsorption geometries of biotin molecules on the silver surface were analyzed based on the SERS data. It can be found that most vibration modes show a Raman shift in silver sol after the addition of sodium chloride solution. In addition, The Raman signals of biotin become weaker and weaker with the increase of the concentration of sodium chloride. This may be due to that the interaction between chloride ions and silver particles is stronger than the interaction between biotin molecules and silver particles. When the concentration of sodium chloride in silver colloid is higher than 0.05mol/L, superfluous chloride ions may form an absorption layer so that biotin can not be adsorbed on silver surface directly. The changes in intensity and profile shape in the SERS spectra suggest different adsorption behavior and surface-coverage of biotin on silver surface. The SERS spectra of biotin suggest that the contribution of the charge transfer mechanism to SERS may be dominant.

Theory of hyperbolic stratified nanostructures for surface-enhanced Raman scattering

Science.gov (United States)

Wong, Herman M. K.; Dezfouli, Mohsen Kamandar; Axelrod, Simon; Hughes, Stephen; Helmy, Amr S.

2017-11-01

We theoretically investigate the enhancement of surface enhanced Raman spectroscopy (SERS) using hyperbolic stratified nanostructures and compare to metal nanoresonators. The photon Green function of each nanostructure within its environment is first obtained from a semianalytical modal theory, which is used in a quantum optics formalism of the molecule-nanostructure interaction to model the SERS spectrum. An intuitive methodology is presented for calculating the single-molecule enhancement factor (SMEF), which is also able to predict known experimental SERS enhancement factors of a gold nanodimer. We elucidate the important figures-of-merit of the enhancement and explore these for different designs. We find that the use of hyperbolic stratified materials can enhance the photonic local density of states (LDOS) by close to two times in comparison to pure metal nanostructures, when both designed to work at the same operating wavelengths. However, the increased LDOS is accompanied by higher electric field concentration within the lossy hyperbolic material, which leads to increased quenching that serves to reduce the overall detected SERS enhancement in the far field. For nanoresonators with resonant localized surface plasmon wavelengths in the near-infrared, the SMEF for the hyperbolic stratified nanostructure is approximately one order of magnitude lower than the pure metal counterpart. Conversely, we show that by detecting the Raman signal using a near-field probe, hyperbolic materials can provide an improvement in SERS enhancement compared to using pure metal nanostructures when the probe is sufficiently close (<50 nm ) to the Raman active molecule at the plasmonic hotspot.

Molecule scattering from insulator and metal surfaces

International Nuclear Information System (INIS)

Moroz, Iryna; Ambaye, Hailemariam; Manson, J R

2004-01-01

Calculations are carried out and compared with data for the scattering of CH 4 molecules from a LiF(001) surface and for O 2 scattering from Al(111). The theory is a mixed classical-quantum formalism that includes energy and momentum transfers between the surface and projectile for translational and rotational motions as well as internal mode excitation of the projectile molecule. The translational and rotational degrees of freedom couple most strongly to multiphonon excitations of the surface and are treated with classical dynamics. Internal vibrational excitations of the molecules are treated with a semiclassical formalism with extension to arbitrary numbers of modes and arbitrary quantum numbers. Calculations show good agreement for the dependence on incident translational energy, incident beam angle and surface temperature when compared with data for energy-resolved intensity spectra and angular distributions

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Science.gov (United States)

Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

2010-08-01

Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Nanogap embedded silver gratings for surface plasmon enhanced fluorescence

Science.gov (United States)

Bhatnagar, Kunal

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal and dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures have shown to provide very efficient and extreme light concentration at the nano-scale in recent years. The enhanced electric field produced within a few hundred nanometers of these surfaces can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences and improving the qualities and capabilities of fluorescence based detectors and imaging equipment remains a big challenge for industry manufacturers. We report a novel fabrication technique for producing nano-gap embedded periodic grating substrates on the nanoscale using a store bought HD-DVD and conventional soft lithography procedures. Polymethylsilsesquioxane (PMSSQ) polymer is used as the ink for the micro-contact printing process with PDMS stamps obtained from the inexpensive HD-DVDs as master molds. Fluorescence enhancement factors of up to 118 times were observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for a robust and inexpensive optical system with applications such as low-level fluorescence based analyte detection, single molecule imaging, and surface enhanced Raman studies. Preliminary results in single molecule experiments have also been obtained by imaging individual 3 nm and 20 nm dye-doped nanoparticles attached to the silver plasmonic gratings using epi-fluorescence microscopy.

Surface-enhanced raman optical data storage system

Science.gov (United States)

Vo-Dinh, Tuan

1994-01-01

An improved Surface-Enhanced Raman Optical Data Storage System (SERODS) is disclosed. In the improved system, entities capable of existing in multiple reversible states are present on the storage device. Such entities result in changed Surface-Enhanced Raman Scattering (SERS) when localized state changes are effected in less than all of the entities. Therefore, by changing the state of entities in localized regions of a storage device, the SERS emissions in such regions will be changed. When a write-on device is controlled by a data signal, such a localized regions of changed SERS emissions will correspond to the data written on the device. The data may be read by illuminating the surface of the storage device with electromagnetic radiation of an appropriate frequency and detecting the corresponding SERS emissions. Data may be deleted by reversing the state changes of entities in regions where the data was initially written. In application, entities may be individual molecules which allows for the writing of data at the molecular level. A read/write/delete head utilizing near-field quantum techniques can provide for a write/read/delete device capable of effecting state changes in individual molecules, thus providing for the effective storage of data at the molecular level.

Aligned gold nanoneedle arrays for surface-enhanced Raman scattering

International Nuclear Information System (INIS)

Yang Yong; Huang Zhengren; Jiang Dongliang; Tanemura, Masaki; Yamaguchi, Kohei; Li Zhiyuan; Huang Yingping; Kawamura, Go; Nogami, Masayuki

2010-01-01

A simple Ar + -ion irradiation route has been developed to prepare gold nanoneedle arrays on glass substrates for surface-enhanced Raman scattering (SERS)-active substrates. The nanoneedles exhibited very sharp tips with an apex diameter of 20 nm. These arrays were evaluated as potential SERS substrates using malachite green molecules and exhibited a SERS enhancement factor of greater than 10 8 , which is attributed to the localized electron field enhancement around the apex of the needle and the surface plasmon coupling originating from the periodic structure. This work demonstrates a new technique for producing controllable and reproducible SERS substrates potentially applicable for chemical and biological assays.

Surface functionalization of aluminosilicate nanotubes with organic molecules

Directory of Open Access Journals (Sweden)

Wei Ma

2012-02-01

Full Text Available The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid (HT3P and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid 1,1-dioxide (HT3OP, on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene (P3HT chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid.

Surface enhanced Raman scattering spectroscopic waveguide

Science.gov (United States)

Lascola, Robert J; McWhorter, Christopher S; Murph, Simona H

2015-04-14

A waveguide for use with surface-enhanced Raman spectroscopy is provided that includes a base structure with an inner surface that defines a cavity and that has an axis. Multiple molecules of an analyte are capable of being located within the cavity at the same time. A base layer is located on the inner surface of the base structure. The base layer extends in an axial direction along an axial length of an excitation section. Nanoparticles are carried by the base layer and may be uniformly distributed along the entire axial length of the excitation section. A flow cell for introducing analyte and excitation light into the waveguide and a method of applying nanoparticles may also be provided.

Surface-enhanced Raman spectroscopy bioanalytical, biomolecular and medical applications

CERN Document Server

Procházka, Marek

2016-01-01

This book gives an overview of recent developments in RS and SERS for sensing and biosensing considering also limitations, possibilities and prospects of this technique. Raman scattering (RS) is a widely used vibrational technique providing highly specific molecular spectral patterns. A severe limitation for the application of this spectroscopic technique lies in the low cross section of RS. Surface-enhanced Raman scattering (SERS) spectroscopy overcomes this problem by 6-11 orders of magnitude enhancement compared with the standard RS for molecules in the close vicinity of certain rough metal surfaces. Thus, SERS combines molecular fingerprint specificity with potential single-molecule sensitivity. Due to the recent development of new SERS-active substrates, labeling and derivatization chemistry as well as new instrumentations, SERS became a very promising tool for many varied applications, including bioanalytical studies and sensing. Both intrinsic and extrinsic SERS biosensing schemes have been employed to...

Focused ion beam-fabricated Au micro/nanostructures used as a surface enhanced Raman scattering-active substrate for trace detection of molecules and influenza virus

Energy Technology Data Exchange (ETDEWEB)

Lin, Ying-Yi; Liao, Jiunn-Der; Ju, Yu-Hung; Chang, Chia-Wei [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Shiau, Ai-Li, E-mail: jdliao@mail.ncku.edu.tw [Department of Microbiology and Immunology, National Cheng Kung University, No 1, University Road, Tainan 70101, Taiwan (China)

2011-05-06

The focused ion beam (FIB) technique was used to precisely fabricate patterned Au micro/nanostructures (fibAu). The effects of surface enhanced Raman scattering (SERS) on the fibAu samples were investigated by adjusting the geometrical, dimensional, and spacing factors. The SERS mechanism was evaluated using low-concentration rhodamine 6G (R6G) molecules, physically adsorbed or suspended on/within the micro/nanostructures. The results indicated that for detecting R6G molecules, hexagon-like micro/nanostructures induced a higher electromagnetic mechanism (EM) due to the availability of multiple edges and small curvature. By decreasing the dimensions from 300 to 150 nm, the laser-focused area contained an increasing number of micro/nanostructures and therefore intensified the excitation of SERS signals. Moreover, with an optimized geometry and dimensions of the micro/nanostructures, the relative intensity/surface area value reached a maximum as the spacing was 22 nm. An exponential decrease was found as the spacing was increased, which most probably resulted from the loss of EM. The spacing between the micro/nanostructures upon the fibAu was consequently regarded as the dominant factor for the detection of R6G molecules. By taking an optimized fibAu to detect low-concentration influenza virus, the amino acids from the outermost surface of the virus can be well distinguished through the SERS mechanism.

Ag coated microneedle based surface enhanced Raman scattering probe for intradermal measurements

Science.gov (United States)

Yuen, Clement; Liu, Quan

2013-06-01

We propose a silver coated microneedle to detect test molecules, including R6G and glucose, positioned at a depth of more than 700 μm below a skin phantom surface for mimicking intradermal surface-enhanced Raman scattering measurements.

Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

International Nuclear Information System (INIS)

Berlanga, Isadora; Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo; Gómez, Victoria Alejandra; Aliaga-Alcalde, Núria; Fuenzalida, Victor; Flores, Marcos

2017-01-01

Highlights: • Thiophene curcuminoid molecules deposited on a gold surface by immersion. • Molecular dynamic studies of the molecular arrangement approaching the surface. • XPS and STM studies showing different arrangement of the molecules on the surface. • Molecular Interaction with surface depends on the sulfur position in thiophene rings. • Temporal evolution of the molecular arrangement on the surface. - Abstract: We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Berlanga, Isadora [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo [Departamento de Ciencia de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Beaucheff 851, Santiago (Chile); Gómez, Victoria Alejandra [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Aliaga-Alcalde, Núria [ICREA (Institució Catalana de Recerca i Estudis Avançats), Passeig Lluís Companys, 23, 08018, Barcelona (Spain); CSIC-ICMAB (Institut de Ciència dels Materials de Barcelona), Campus de la Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain); Fuenzalida, Victor [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Flores, Marcos, E-mail: mflorescarra@ing.uchile.cl [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); and others

2017-01-15

Highlights: • Thiophene curcuminoid molecules deposited on a gold surface by immersion. • Molecular dynamic studies of the molecular arrangement approaching the surface. • XPS and STM studies showing different arrangement of the molecules on the surface. • Molecular Interaction with surface depends on the sulfur position in thiophene rings. • Temporal evolution of the molecular arrangement on the surface. - Abstract: We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

Surface-enhanced Raman scattering from silver electrodes

International Nuclear Information System (INIS)

Trott, G.R.

1982-01-01

The chemical and physical origins of the anomalously large enhancement of the Raman scattering cross section for molecules adsorbed on silver electrodes in an electrochemical cell were investigated. The effect of the chemical reactions which occur during the anodization/activation procedure were studied using the Ag-CN system. It was shown that the function of the anodization process is to roughen the electrode surface and create an activated site for bonding to the cyanide. A new nonelectrochemical technique for activating the silver surface, along with a study of the enhanced cyanide Raman scattering in different background electrolytes, showed that the Raman active entity on the surface must be a silver-cyanide complex. In order to study the physical mechanism of the enhancement, the angular dependence of the scattered radiation was measured from pyridine adsorbed on an evaporated silver electrode. Both polycrystalline and single crystalline silver films were used. The angular dependence of the scattered radiation from these films showed that the metal surface was controlling the directional properties of the scattered radiation, and not the polarizability tensor of the adsorbate. Based on these experimental results, it was concluded that for weakly roughened silver electrodes the source of the anomalous enhancement is due to a resonant Raman scattering process

Plasmonic nanostructures for surface-enhanced Raman spectroscopy

Science.gov (United States)

Jiang, Ruiqian

In the last three decades, a large number of different plasmonic nanostructures have attracted much attention due to their unique optical properties. Those plasmonic nanostructures include nanoparticles, nanoholes and metal nanovoids. They have been widely utilized in optical devices and sensors. When the plasmonic nanostructures interact with the electromagnetic wave and their surface plasmon frequency match with the light frequency, the electrons in plasmonic nanostructures will resonate with the same oscillation as incident light. In this case, the plasmonic nanostructures can absorb light and enhance the light scattering. Therefore, the plasmonic nanostructures can be used as substrate for surface-enhanced Raman spectroscopy to enhance the Raman signal. Using plasmonic nanostructures can significantly enhance Raman scattering of molecules with very low concentrations. In this thesis, two different plasmonic nanostructures Ag dendrites and Au/Ag core-shell nanoparticles are investigated. Simple methods were used to produce these two plasmonic nanostructures. Then, their applications in surface enhanced Raman scattering have been explored. Ag dendrites were produced by galvanic replacement reaction, which was conducted using Ag nitrate aqueous solution and copper metal. Metal copper layer was deposited at the bottom side of anodic aluminum oxide (AAO) membrane. Silver wires formed inside AAO channels connected Ag nitrate on the top of AAO membrane and copper layer at the bottom side of AAO. Silver dendrites were formed on the top side of AAO. The second plasmonic nanostructure is Au/Ag core-shell nanoparticles. They were fabricated by electroless plating (galvanic replacement) reaction in a silver plating solution. First, electrochemically evolved hydrogen bubbles were used as template through electroless deposition to produce hollow Au nanoparticles. Then, the Au nanoparticles were coated with Cu shells in a Cu plating solution. In the following step, a Ag

Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

Science.gov (United States)

Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

2018-03-01

The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

Confined Catalysis in the g-C3N4/Pt(111) Interface: Feasible Molecule Intercalation, Tunable Molecule-Metal Interaction, and Enhanced Reaction Activity of CO Oxidation.

Science.gov (United States)

Wang, Shujiao; Feng, Yingxin; Yu, Ming'an; Wan, Qiang; Lin, Sen

2017-09-27

The deposition of a two-dimensional (2D) atomic nanosheet on a metal surface has been considered as a new route for tuning the molecule-metal interaction and surface reactivity in terms of the confinement effect. In this work, we use first-principles calculations to systematically explore a novel nanospace constructed by placing a 2D graphitic carbon nitride (g-C 3 N 4 ) nanosheet over a Pt(111) surface. The confined catalytic activity in this nanospace is investigated using CO oxidation as a model reaction. With the inherent triangular pores in the g-C 3 N 4 overlayer being taken advantage of, molecules such as CO and O 2 can diffuse to adsorb on the Pt(111) surface underneath the g-C 3 N 4 overlayer. Moreover, the mechanism of intercalation is also elucidated, and the results reveal that the energy barrier depends mainly on the properties of the molecule and the channel. Importantly, the molecule-catalyst interaction can be tuned by the g-C 3 N 4 overlayer, considerably reducing the adsorption energy of CO on Pt(111) and leading to enhanced reactivity in CO oxidation. This work will provide important insight for constructing a promising nanoreactor in which the following is observed: The molecule intercalation is facile; the molecule-metal interaction is efficiently tuned; the metal-catalyzed reaction is promoted.

Bare and protected sputtered-noble-metal films for surface-enhanced Raman spectroscopy

Science.gov (United States)

Talaga, David; Bonhommeau, Sébastien

2014-11-01

Sputtered silver and gold films with different surface morphologies have been prepared and coated with a benzenethiol self-assembled monolayer. Rough noble metal films showed strong Raman features assigned to adsorbed benzenethiol molecules upon irradiation over a wide energy range in the visible spectrum, which disclosed the occurrence of a significant surface-enhanced Raman scattering with maximal enhancement factors as high as 6 × 106. In addition, the adsorption of ethanethiol onto silver surfaces hinders their corrosion over days while preserving mostly intact enhancement properties of naked silver. This study may be applied to develop stable and efficient metalized probes for tip-enhanced Raman spectroscopy.

Enhanced photothermal lens using a photonic crystal surface

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yunfei; Liu, Longju [Department of Electrical and Computer Engineering, 2128 Coover Hall, Iowa State University, Ames,Iowa 50011 (United States); Zhao, Xiangwei [State Key Laboratory of Bioelectronics, School of Biological Science and Medical Engineering,Southeast University, Nanjing, Jiangsu 211189 (China); Lu, Meng, E-mail: menglu@iastate.edu [Department of Electrical and Computer Engineering, 2128 Coover Hall, Iowa State University, Ames,Iowa 50011 (United States); Department of Mechanical Engineering, Iowa State University, Ames, Iowa 50011 (United States)

2016-08-15

A photonic crystal (PC)-enhanced photothermal lens (PTL) is demonstrated for the detection of optically thin light absorption materials. The PC-enhanced PTL system is based on a pump-probe scheme consisting of a PC surface, pump laser beam, and probe laser beam. Heated by the pump beam, light absorption materials on the PC surface generate the PTL and cause a substantial change to the guided-mode resonance supported by the PC structure. The change of the PC resonance is detected using the probe laser beam by measuring its reflectivity from the PC surface. When applied to analyze dye molecules deposited on the PC substrate, the developed system is capable of enhancing the PTL signal by 10-fold and reducing the lowest distinguishable concentration by 8-fold, in comparison to measuring without utilizing the PC resonance. The PC-enhanced PTL was also used to detect gold nanoparticles on the PC surface and exhibited a 20-fold improvement of the lowest distinguishable concentration. The PC-enhanced PTL technology offers a potential tool to obtain the absorption signatures of thin films in a broad spectral range with high sensitivity and inexpensive instrumentation. As a result, this technology will enable a broad range of applications of photothermal spectroscopy in chemical analysis and biomolecule sensing.

Adsorption of ethyl xanthate on ZnS(110) surface in the presence of water molecules: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Long, Xianhao [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Chen, Jianhua, E-mail: jhchen@gxu.edu.cn [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Guangxi Colleges and University Key Laboratory of Minerals Engineering, 530004 (China); Chen, Ye, E-mail: fby18@126.com [College of Resources and Metallurgy, Guangxi University, Nanning 530004 (China)

2016-05-01

Graphical abstract: - Highlights: • Adsorption of water molecules decreases the reactivity of surface Zn atom. • Copper impurities decrease the band gap of ZnS surface. • Copper impurities enhance the adsorption of xanthate on the ZnS surface. • Water molecules have little influence on the properties of Cu-substituted ZnS surface. • The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface. - Abstracts: The interaction of collector with the mineral surface plays a very important role in the froth flotation of sphalerite. The adsorptions occurred at the interface between the mineral surface and waters; however most of DFT simulations are performed in vacuum, without consideration of water effect. Semiconductor surface has an obvious proximity effect, which will greatly influence the surface reactivity. To understand the mechanism of xanthate interacting with sphalerite surface in the presence of water molecules, the ethyl xanthate molecule adsorption on un-activated and Cu-activated ZnS(110) surface in the absence and presence of water molecules were performed using the density functional theory (DFT) method. The calculated results show that the adsorption of water molecules dramatically changes the properties of ZnS surface, resulting in decreasing the reactivity of surface Zn atoms with xanthate. Copper activation of ZnS surface changes the surface properties, leading to the totally different adsorption behaviors of xanthate. The presence of waters has little influence on the properties of Cu-activated ZnS surface. The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface, which would result in the formation of dixanthogen.

Enhanced compatibility of chemically modified titanium surface with periodontal ligament cells

International Nuclear Information System (INIS)

Kado, T.; Hidaka, T.; Aita, H.; Endo, K.; Furuichi, Y.

2012-01-01

Highlights: ► Cell-adhesive molecules were covalently immobilized on a Ti surface. ► Immobilized cell-adhesive molecules maintained native function on the Ti surface. ► Immobilized collagen enhanced adhesion of periodontal ligament cells to the Ti. - Abstract: A simple chemical modification method was developed to immobilize cell-adhesive molecules on a titanium surface to improve its compatibility with human periodontal ligament cells (HPDLCs).The polished titanium disk was immersed in 1% (v/v) p-vinylbenzoic acid solution for 2 h to introduce carboxyl groups onto the surface. After rinsing with distilled deionized water, the titanium disk was dipped into 1.47% 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide solution containing 0.1 mg/ml Gly-Arg-Gly-Asp-Ser (GRGDS), human plasma fibronectin (pFN), or type I collagen from calf skin (Col) to covalently immobilize the cell-adhesive molecules on the titanium surface via formation of peptide bonds. X-ray photoelectron spectroscopy analyses revealed that cell-adhesive molecules were successfully immobilized on the titanium surfaces. The Col-immobilized titanium surface revealed higher values regarding nano rough characteristics than the as-polished titanium surface under scanning probe microscopy. The number of HPDLCs attached to both the pFN- and Col-immobilized titanium surfaces was twice that attached to the as-polished titanium surfaces. The cells were larger with the cellular processes that stretched to a greater extent on the pFN- and Col-immobilized titanium surfaces than on the as-polished titanium surface (p < 0.05). HPDLCs on the Col-immobilized titanium surfaces showed more extensive expression of vinculin at the tips of cell projections and more contiguously along the cell outline than on the as-polished, GRGDS-immobilized and pFN-immobilized titanium surfaces. It was concluded that cell-adhesive molecules successfully immobilized on the titanium surface and improved the compatibility of the surface

Chiral Molecule-Enhanced Extinction Ratios of Quantum Dots Coupled to Random Plasmonic Structures.

Science.gov (United States)

Bezen, Lior; Yochelis, Shira; Jayarathna, Dilhara; Bhunia, Dinesh; Achim, Catalina; Paltiel, Yossi

2018-03-06

Devices based on self-assembled hybrid colloidal quantum dots (CQDs) coupled with specific organic linker molecules are a promising way to simply realize room-temperature, spectrally tunable light detectors. Nevertheless, this type of devices usually has low quantum efficiency. Plasmonics has been shown as an efficient tool in guiding and confining light at nanoscale dimensions. As plasmonic modes exhibit highly confined fields, they locally increase light-matter interactions and consequently enhance the performance of CQD-based photodetectors. Recent publications presented experimental results of large extinction enhancement from a monolayer of CQDs coupled to random gold nanoislands using a monolayer of organic alkyl linkers. We report here that a twofold larger extinction enhancement in the visible spectrum is observed when a monolayer of helical chiral molecules connects the CQDs to the gold structure instead of a monolayer of achiral linkers. We also show that this effect provides insight into the chirality of the molecules within the monolayer. In future work, we plan to evaluate the potential of these results to be used in the construction of a more efficient and sensitive photon detector based on surface QDs, as well as to supply a simple way to map the chirality of a single chiral monolayer.

Nanometer-scale discernment of field emission from tungsten surface with single carbon monoxide molecule

Science.gov (United States)

Matsunaga, Soichiro; Suwa, Yuji; Katagiri, Souichi

2017-12-01

Unusual quantized beam fluctuations were found in the emission current from a cold-field emitter (CFE) operating in an extremely high vacuum of 10-10 Pa. To clarify the microscopic mechanism behind these fluctuations, we developed a new calculation method to evaluate the field emission from a heterogeneous surface under a strong electric field of 4 × 109 V/m by using the local potential distribution obtained by a first-principles calculation, instead of by using the work function. As a result of the first-principles calculations of a single molecule adsorbed on a tungsten surface, we found that dissociative adsorption of a carbon monoxide (CO) molecule enhances the emission current by changing the potential barrier in the area surrounding the C and O adatoms when these two atoms are placed at their most stable positions. It is also found that the migration of the O atom from the most stable position reduces the emission current. These types of enhancement and reduction of the emission current quantitatively explain the observed quantized fluctuations of the CFE emission current.

Dielectric platforms for surface-enhanced spectroscopies (Conference Presentation)

Science.gov (United States)

Maier, Stefan A.

2016-03-01

Plasmonic nanostructures serve as the main backbone of surface enhanced sensing methodologies, yet the associated optical losses lead to localized heating as well as quenching of molecules, complicating their use for enhancement of fluorescent emission. Additionally, conventional plasmonic materials are limited to operation in the visible part of the spectrum. We will elucidate how nanostructures consisting of conventional and polar dielectrics can be employed as a highly promising alternative platform. Dielectric nanostructures can sustain scattering resonances due to both electric and magnetic Mie modes. We have recently predicted high enhanced local electromagnetic field hot spots in dielectric nanoantenna dimers, with the hallmark of spot sizes comparable to those achievable with plasmonic antennas, but with lower optical losses. Here, we will present first experimental evidence for both fluorescence and Raman enhancement in dielectric nanoantennas, including a direct determination of localized heating, and compare to conventional Au dimer antennas. The second part of the talk will focus on the mid-infrared regime of the electromagnetic spectrum, outlining possibilities for surface enhanced infrared absorption spectroscopy based on polar and hyperbolic dielectrics.

Controlling surface adsorption to enhance the selectivity of porphyrin based gas sensors

Energy Technology Data Exchange (ETDEWEB)

Evyapan, M., E-mail: mevyapan@gmail.com [Department of Physics, University of Balikesir, Balikesir, 10145 (Turkey); Chemical and Biological Engineering, University of Sheffield, Mappin Building, S1 3JD (United Kingdom); Dunbar, A.D.F. [Chemical and Biological Engineering, University of Sheffield, Mappin Building, S1 3JD (United Kingdom)

2016-01-30

Graphical abstract: The enhancement in the selectivity of the vapor sensing properties of free base porphyrin by controlling the size of the pores in the surface structure was carried out. It can be used as a size selective surface layer which limits the diffusion of analyte molecules into the sensor and in extreme cases stopping the diffusion completely. - Highlights: • Surface of a thin film takes and important part for its sensing characteristics. • A systematic surface modification was carried out in order to control the vapor accessibility. • Size dependant surfaces were fabricated. • Vapor diffusion through into thin film was controlled by modifying the surface structure. • Remarkable quantitative results showed the control on selectivity of the sensor by controlling the surface. - Abstract: This study reports an enhancement in the selectivity of the vapor sensing properties of free base porphyrin 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO) Langmuir–Schaefer (LS) films. These sensors respond by changing color upon adsorption of the analyte gas to the sensor surface. The enhanced selectivity is achieved by adding selective barrier layers of 4-tert-Butylcalix[4]arene, 4-tert-Butylcalix[6]arene and 4-tert-Butylcalix[8]arene embedded in PMMA (Poly(methyl methacrylate)) on top of the porphyrin sensor films to control the gaseous adsorption onto the sensor surface. The Langmuir properties of EHO, PMMA and calix[n]arene monolayers were investigated by surface pressure–area (Π–A) isotherms in order to determine the most efficient transfer pressure. Six layer EHO films were transferred onto glass and silicon substrates to investigate their optical and structural characteristics. The three different calix[n]arenes were embedded within PMMA layers to act as the selective barrier layers which were deposited on top of the six layer EHO films. The different calix[n]arene molecules vary in size and each was mixed with PMMA in

Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

Science.gov (United States)

Law, Cheryl Suwen; Sylvia, Georgina M; Nemati, Madieh; Yu, Jingxian; Losic, Dusan; Abell, Andrew D; Santos, Abel

2017-03-15

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au 3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.

Amphiphilic Bio-molecules/ZnO Interface: Enhancement of Bio-affinity and Dispersibility

International Nuclear Information System (INIS)

Meng Xiu-Qing; Fang Yun-Zhang; Wu Feng-Min

2012-01-01

The dispersibility of bio-molecules such as lecithins on the surface of ZnO nanowires are investigated for biosensor applications. Lecithins can be absorbed on an as-synthesized ZnO nanowire surface in the form of sub-micro sized clusters, while scattering well on those annealed under oxygen atmosphere. Wettability analysis reveals that the as-synthesized ZnO nanowires bear a super-hydrophobic surface, which convents to superhydrophilic after oxygen annealing. First-principles calculations indicate that the adsorption energy of ZnO with water is about 0.2 eV at a distance of 2 Å when it is superhydrophilic, suggesting that lecithin can be absorbed on the hydrophilic surface stably at this distance and the bio-affinity can be enhanced under this condition. (condensed matter: structure, mechanical and thermal properties)

Wavelength modulated surface enhanced (resonance) Raman scattering for background-free detection.

Science.gov (United States)

Praveen, Bavishna B; Steuwe, Christian; Mazilu, Michael; Dholakia, Kishan; Mahajan, Sumeet

2013-05-21

Spectra in surface-enhanced Raman scattering (SERS) are always accompanied by a continuum emission called the 'background' which complicates analysis and is especially problematic for quantification and automation. Here, we implement a wavelength modulation technique to eliminate the background in SERS and its resonant version, surface-enhanced resonance Raman scattering (SERRS). This is demonstrated on various nanostructured substrates used for SER(R)S. An enhancement in the signal to noise ratio for the Raman bands of the probe molecules is also observed. This technique helps to improve the analytical ability of SERS by alleviating the problem due to the accompanying background and thus making observations substrate independent.

Self-assembled monolayer of designed and synthesized triazinedithiolsilane molecule as interfacial adhesion enhancer for integrated circuit

Directory of Open Access Journals (Sweden)

Wang Fang

2011-01-01

Full Text Available Abstract Self-assembled monolayer (SAM with tunable surface chemistry and smooth surface provides an approach to adhesion improvement and suppressing deleterious chemical interactions. Here, we demonstrate the SAM comprising of designed and synthesized 6-(3-triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol molecule, which can enhance interfacial adhesion to inhibit copper diffusion used in device metallization. The formation of the triazinedithiolsilane SAM is confirmed by X-ray photoelectron spectroscopy. The adhesion strength between SAM-coated substrate and electroless deposition copper film was up to 13.8 MPa. The design strategy of triazinedithiolsilane molecule is expected to open up the possibilities for replacing traditional organosilane to be applied in microelectronic industry.

Surface enhanced infrared spectroscopy using interacting gold nanowires

Energy Technology Data Exchange (ETDEWEB)

Neubrech, Frank; Weber, Daniel; Pucci, Annemarie [Kirchhoff-Institut fuer Physik, Heidelberg (Germany); Shen, Hong [Universite Troyes, Troyes (France); Lamy de la Chapelle, Marc [Universite Paris 13, Bobigny (France)

2009-07-01

We performed surface enhanced infrared spectroscopy (SEIRS) of molecules adsorbed on gold nanowires using synchrotron light of the ANKA IR-beamline at the Forschungszentrum Karlsruhe (Germany). Arrays of gold nanowires with interparticle spacings down to 30nm were prepared by electron beam lithography. The interparticle distance was reduced further by wet-chemically increasing the size of the gold nanowires. The growth of the wires was proofed using IR spectroscopy as well as scanning electron microscopy. After this preparation step, appropriate arrays of nanowires with an interparticle distance down to a few nanometers were selected to demonstrate the surface enhanced infrared spectroscopy of one monolayer octadecanthiol (ODT). As know from SEIRS studies using single gold nanowires, the spectral position of the antenna-like resonance in relation to the absorption bands of ODT (2850cm-1 and 2919cm-1) is crucial for both, the lineshape of the molecular vibration and the signal enhancement. In contrast to single nanowires studies, a further increase of the enhanced signals is expected due to the interaction of the electromagnetic fields of the close-by nanowires.

Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces.

Science.gov (United States)

Dunwell, M; Wang, Junhua; Yan, Y; Xu, B

2017-01-04

The adsorption of alkali and tetraalkylammonium cations on Pt is investigated using surface enhanced infrared absorption spectroscopy and carbon monoxide as a probe molecule. Alkali cations exhibit a stronger adsorption than organic cations, with potassium showing the strongest effect, followed by sodium and lithium.

Small molecules enhance CRISPR genome editing in pluripotent stem cells.

Science.gov (United States)

Yu, Chen; Liu, Yanxia; Ma, Tianhua; Liu, Kai; Xu, Shaohua; Zhang, Yu; Liu, Honglei; La Russa, Marie; Xie, Min; Ding, Sheng; Qi, Lei S

2015-02-05

The bacterial CRISPR-Cas9 system has emerged as an effective tool for sequence-specific gene knockout through non-homologous end joining (NHEJ), but it remains inefficient for precise editing of genome sequences. Here we develop a reporter-based screening approach for high-throughput identification of chemical compounds that can modulate precise genome editing through homology-directed repair (HDR). Using our screening method, we have identified small molecules that can enhance CRISPR-mediated HDR efficiency, 3-fold for large fragment insertions and 9-fold for point mutations. Interestingly, we have also observed that a small molecule that inhibits HDR can enhance frame shift insertion and deletion (indel) mutations mediated by NHEJ. The identified small molecules function robustly in diverse cell types with minimal toxicity. The use of small molecules provides a simple and effective strategy to enhance precise genome engineering applications and facilitates the study of DNA repair mechanisms in mammalian cells. Copyright © 2015 Elsevier Inc. All rights reserved.

Molecular recognition of chromophore molecules to amine terminated surfaces

International Nuclear Information System (INIS)

Flores-Perez, Rosangelly; Ivanisevic, Albena

2007-01-01

We report the design and characterization of quartz surfaces that can bind to three retinal based chromophores. The amine terminated surfaces were engineered in order to mimic the environment of the opsin protein that accommodates binding of chromophore molecules in the human eye. Each surface coupling step was characterized by water contact angle measurements, ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and transmission infrared spectroscopy. The spectroscopic techniques confirmed that the three chromophore molecules can bind to the surface using a Schiff base mode. Our data suggests that the availability of the amine groups on the surface is critical in the accommodation of the binding of different chromophores

Generation of nanospikes via laser ablation of metals in liquid environment and their activity in surface-enhanced Raman scattering of organic molecules

Energy Technology Data Exchange (ETDEWEB)

Truong, S. Lau; Levi, G.; Bozon-Verduraz, F. [ITODYS, UMR-CNRS 7086, Universite Paris 7-Denis Diderot, 2, place Jussieu, 75251 Paris cedex 05 (France); Petrovskaya, A.V.; Simakin, A.V. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38 Vavilov street, 119991 Moscow (Russian Federation); Shafeev, G.A. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, 38 Vavilov street, 119991 Moscow (Russian Federation)], E-mail: shafeev@kapella.gpi.ru

2007-12-15

The formation of dense arrays of nanospikes occurs under laser ablation of bulk targets (Ag, Au, Ta, Ti) immersed in liquids such as water or ethanol. The average height of spikes is 50 nm and their density on the target amounts to 10{sup 10} cm{sup -2}. The effect is observed with sufficiently short laser pulses. In particular, either a 350 ps or a 90 ps Nd:YAG lasers are used in their fundamental harmonics. The nanospikes are characterized by UV-Visible reflection spectrometry and atomic force microscopy. The oscillations of electrons within nanospikes result in a permanent coloration of the surface and a modification of the optical reflection spectra of the metal. Scanning the laser beam along the metal surface allows its nanostructuring over extended areas ({approx}1 cm{sup 2}). The nanostructured Ag surface shows enhanced Raman scattering of acridine molecules at a concentration of 10{sup -5} M/l, whereas the initial Ag targets do not show any signal within the accuracy of measurements.

Click chemistry based biomolecular conjugation monitoring using surface-enhanced Raman spectroscopy mapping

DEFF Research Database (Denmark)

Palla, Mirko; Kumar, Shiv; Li, Zengmin

2016-01-01

We describe here a novel surface-enhanced Raman spectroscopy (SERS) based technique for monitoring the conjugation of small molecules by the well-known click reaction between an alkyne and azido moiety on the partner molecules. The monitoring principle is based on the loss of the characteristic...... alkyne/azide Raman signal with triazole formation in the reaction as a function of time. Since these universal Raman reporter groups are specific for click reactions, this method may facilitate a broad range of applications for monitoring the conjugation efficiency of molecules in diverse areas...

Current-induced switching of magnetic molecules on topological insulator surfaces

Science.gov (United States)

Locane, Elina; Brouwer, Piet W.

2017-03-01

Electrical currents at the surface or edge of a topological insulator are intrinsically spin polarized. We show that such surface or edge currents can be used to switch the orientation of a molecular magnet weakly coupled to the surface or edge of a topological insulator. For the edge of a two-dimensional topological insulator as well as for the surface of a three-dimensional topological insulator the application of a well-chosen surface or edge current can lead to a complete polarization of the molecule if the molecule's magnetic anisotropy axis is appropriately aligned with the current direction. For a generic orientation of the molecule a nonzero but incomplete polarization is obtained. We calculate the probability distribution of the magnetic states and the switching rates as a function of the applied current.

Stochastic models for surface diffusion of molecules

Energy Technology Data Exchange (ETDEWEB)

Shea, Patrick, E-mail: patrick.shea@dal.ca; Kreuzer, Hans Jürgen [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 3J5 (Canada)

2014-07-28

We derive a stochastic model for the surface diffusion of molecules, starting from the classical equations of motion for an N-atom molecule on a surface. The equation of motion becomes a generalized Langevin equation for the center of mass of the molecule, with a non-Markovian friction kernel. In the Markov approximation, a standard Langevin equation is recovered, and the effect of the molecular vibrations on the diffusion is seen to lead to an increase in the friction for center of mass motion. This effective friction has a simple form that depends on the curvature of the lowest energy diffusion path in the 3N-dimensional coordinate space. We also find that so long as the intramolecular forces are sufficiently strong, memory effects are usually not significant and the Markov approximation can be employed, resulting in a simple one-dimensional model that can account for the effect of the dynamics of the molecular vibrations on the diffusive motion.

Fano-induced spontaneous emission enhancement of molecule placed in a cluster of asymmetrically-arranged metallic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Le, Khai Q., E-mail: khai.lequang@hoasen.edu.vn [Faculty of Science and Technology, Hoa Sen University, Ho Chi Minh (Viet Nam); Department of Electrical Engineering, University of Minnesota, Duluth, MN 55812 (United States); Bai, Jing [Department of Electrical Engineering, University of Minnesota, Duluth, MN 55812 (United States); Nguyen, H.P.T. [Department of Electrical and Computer Engineering, New Jersey Institute of Technology, NJ 07102 (United States)

2016-05-15

We demonstrate that plasmonic Fano resonance significantly boosts spontaneous emission rate of a single emitter, e.g. atom, molecule and quantum dot, over a moderately broad emission spectrum. An emission enhancement of up to 140 times compared to the system with no external inclusion at tunable frequencies is achieved, providing a new complementary enhancement mechanism. Fano resonance is induced in clusters of four asymmetric-arranged nanoparticles with ultra-small inter-particle gaps. It is shown to play a dominant role in light-emitting enhancement, mediated by combined localized surface plasmon resonances.

Near-Field Enhanced Photochemistry of Single Molecules in a Scanning Tunneling Microscope Junction.

Science.gov (United States)

Böckmann, Hannes; Gawinkowski, Sylwester; Waluk, Jacek; Raschke, Markus B; Wolf, Martin; Kumagai, Takashi

2018-01-10

Optical near-field excitation of metallic nanostructures can be used to enhance photochemical reactions. The enhancement under visible light illumination is of particular interest because it can facilitate the use of sunlight to promote photocatalytic chemical and energy conversion. However, few studies have yet addressed optical near-field induced chemistry, in particular at the single-molecule level. In this Letter, we report the near-field enhanced tautomerization of porphycene on a Cu(111) surface in a scanning tunneling microscope (STM) junction. The light-induced tautomerization is mediated by photogenerated carriers in the Cu substrate. It is revealed that the reaction cross section is significantly enhanced in the presence of a Au tip compared to the far-field induced process. The strong enhancement occurs in the red and near-infrared spectral range for Au tips, whereas a W tip shows a much weaker enhancement, suggesting that excitation of the localized plasmon resonance contributes to the process. Additionally, using the precise tip-surface distance control of the STM, the near-field enhanced tautomerization is examined in and out of the tunneling regime. Our results suggest that the enhancement is attributed to the increased carrier generation rate via decay of the excited near-field in the STM junction. Additionally, optically excited tunneling electrons also contribute to the process in the tunneling regime.

Surface Enhanced Raman Scattering Substrates Made by Oblique Angle Deposition: Methods and Applications

Directory of Open Access Journals (Sweden)

Hin On Chu

2017-02-01

Full Text Available Surface Enhanced Raman Spectroscopy presents a rapid, non-destructive method to identify chemical and biological samples with up to single molecule sensitivity. Since its discovery in 1974, the technique has become an intense field of interdisciplinary research, typically generating >2000 publications per year since 2011. The technique relies on the localised surface plasmon resonance phenomenon, where incident light can couple with plasmons at the interface that result in the generation of an intense electric field. This field can propagate from the surface from the metal-dielectric interface, so molecules within proximity will experience more intense Raman scattering. Localised surface plasmon resonance wavelength is determined by a number of factors, such as size, geometry and material. Due to the requirements of the surface optical response, Ag and Au are typical metals used for surface enhanced Raman applications. These metals then need to have nano features that improve the localised surface plasmon resonance, several variants of these substrates exist; surfaces can range from nanoparticles in a suspension, electrochemically roughened electrodes to metal nanostructures on a substrate. The latter will be the focus of this review, particularly reviewing substrates made by oblique angle deposition. Oblique angle deposition is the technique of growing thin films so that the material flux is not normal to the surface. Films grown in this fashion will possess nanostructures, due to the atomic self-shadowing effect, that are dependent mainly on the deposition angle. Recent developments, applications and highlights of surface enhanced Raman scattering substrates made by oblique angle deposition will be reviewed.

Electromagnetic theories of surface-enhanced Raman spectroscopy.

Science.gov (United States)

Ding, Song-Yuan; You, En-Ming; Tian, Zhong-Qun; Moskovits, Martin

2017-07-07

Surface-enhanced Raman spectroscopy (SERS) and related spectroscopies are powered primarily by the concentration of the electromagnetic (EM) fields associated with light in or near appropriately nanostructured electrically-conducting materials, most prominently, but not exclusively high-conductivity metals such as silver and gold. This field concentration takes place on account of the excitation of surface-plasmon (SP) resonances in the nanostructured conductor. Optimizing nanostructures for SERS, therefore, implies optimizing the ability of plasmonic nanostructures to concentrate EM optical fields at locations where molecules of interest reside, and to enhance the radiation efficiency of the oscillating dipoles associated with these molecules and nanostructures. This review summarizes the development of theories over the past four decades pertinent to SERS, especially those contributing to our current understanding of SP-related SERS. Special emphasis is given to the salient strategies and theoretical approaches for optimizing nanostructures with hotspots as efficient EM near-field concentrating and far-field radiating substrates for SERS. A simple model is described in terms of which the upper limit of the SERS enhancement can be estimated. Several experimental strategies that may allow one to approach, or possibly exceed this limit, such as cascading the enhancement of the local and radiated EM field by the multiscale EM coupling of hierarchical structures, and generating hotspots by hybridizing an antenna mode with a plasmonic waveguide cavity mode, which would result in an increased local field enhancement, are discussed. Aiming to significantly broaden the application of SERS to other fields, and especially to material science, we consider hybrid structures of plasmonic nanostructures and other material phases and strategies for producing strong local EM fields at desired locations in such hybrid structures. In this vein, we consider some of the numerical

Single-molecule conductivity of non-redox and redox molecules at pure and gold-mined Au(111)-electrode surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Chi, Qijin; Ulstrup, Jens

The structure, two-dimensional organization, and function of molecules immobilized on solid surfaces can be addressed in a degree of detail that has reached the level of the single-molecule. In this context redox molecules are “smart” molecules adding sophisticated electronic function. Redox meta...

Surface-enhanced Raman scattering on molecular self-assembly in nanoparticle-hydrogel composite.

Science.gov (United States)

Miljanić, Snezana; Frkanec, Leo; Biljan, Tomislav; Meić, Zlatko; Zinić, Mladen

2006-10-24

Surface-enhanced Raman scattering has been applied to study weak intermolecular interactions between small organic gelling molecules involved in the silver nanoparticle-hydrogel composite formation. Assembly and disassembly of the gelator molecules in close vicinity to embedded silver nanoparticles were followed by changes in Raman intensity of the amide II and carboxyl vibrational bands, whereas the strength of the bands related to benzene modes remained constant. This implied that the gelator molecules were strongly attached to the silver particles through the benzene units, while participating in gel structure organization by intermolecular hydrogen bonding between oxalyl amide and carboxyl groups.

Surface-enhanced FAST CARS: en route to quantum nano-biophotonics

Science.gov (United States)

Voronine, Dmitri V.; Zhang, Zhenrong; Sokolov, Alexei V.; Scully, Marlan O.

2018-02-01

Quantum nano-biophotonics as the science of nanoscale light-matter interactions in biological systems requires developing new spectroscopic tools for addressing the challenges of detecting and disentangling weak congested optical signals. Nanoscale bio-imaging addresses the challenge of the detection of weak resonant signals from a few target biomolecules in the presence of the nonresonant background from many undesired molecules. In addition, the imaging must be performed rapidly to capture the dynamics of biological processes in living cells and tissues. Label-free non-invasive spectroscopic techniques are required to minimize the external perturbation effects on biological systems. Various approaches were developed to satisfy these requirements by increasing the selectivity and sensitivity of biomolecular detection. Coherent anti-Stokes Raman scattering (CARS) and surface-enhanced Raman scattering (SERS) spectroscopies provide many orders of magnitude enhancement of chemically specific Raman signals. Femtosecond adaptive spectroscopic techniques for CARS (FAST CARS) were developed to suppress the nonresonant background and optimize the efficiency of the coherent optical signals. This perspective focuses on the application of these techniques to nanoscale bio-imaging, discussing their advantages and limitations as well as the promising opportunities and challenges of the combined coherence and surface enhancements in surface-enhanced coherent anti-Stokes Raman scattering (SECARS) and tip-enhanced coherent anti-Stokes Raman scattering (TECARS) and the corresponding surface-enhanced FAST CARS techniques. Laser pulse shaping of near-field excitations plays an important role in achieving these goals and increasing the signal enhancement.

Surface-enhanced FAST CARS: en route to quantum nano-biophotonics

Directory of Open Access Journals (Sweden)

Voronine Dmitri V.

2018-02-01

Full Text Available Quantum nano-biophotonics as the science of nanoscale light-matter interactions in biological systems requires developing new spectroscopic tools for addressing the challenges of detecting and disentangling weak congested optical signals. Nanoscale bio-imaging addresses the challenge of the detection of weak resonant signals from a few target biomolecules in the presence of the nonresonant background from many undesired molecules. In addition, the imaging must be performed rapidly to capture the dynamics of biological processes in living cells and tissues. Label-free non-invasive spectroscopic techniques are required to minimize the external perturbation effects on biological systems. Various approaches were developed to satisfy these requirements by increasing the selectivity and sensitivity of biomolecular detection. Coherent anti-Stokes Raman scattering (CARS and surface-enhanced Raman scattering (SERS spectroscopies provide many orders of magnitude enhancement of chemically specific Raman signals. Femtosecond adaptive spectroscopic techniques for CARS (FAST CARS were developed to suppress the nonresonant background and optimize the efficiency of the coherent optical signals. This perspective focuses on the application of these techniques to nanoscale bio-imaging, discussing their advantages and limitations as well as the promising opportunities and challenges of the combined coherence and surface enhancements in surface-enhanced coherent anti-Stokes Raman scattering (SECARS and tip-enhanced coherent anti-Stokes Raman scattering (TECARS and the corresponding surface-enhanced FAST CARS techniques. Laser pulse shaping of near-field excitations plays an important role in achieving these goals and increasing the signal enhancement.

Scattering of atoms by molecules adsorbed at solid surfaces

International Nuclear Information System (INIS)

Parra, Zaida.

1988-01-01

The formalism of collisional time-correlation functions, appropriate for scattering by many-body targets, is implemented to study energy transfer in the scattering of atoms and ions from molecules adsorbed on metal surfaces. Double differential cross-sections for the energy and angular distributions of atoms and ions scattered by a molecule adsorbed on a metal surface are derived in the limit of impulsive collisions and within a statistical model that accounts for single and double collisions. They are found to be given by the product of an effective cross-section that accounts for the probability of deflection into a solid angle times a probability per unit energy transfer. A cluster model is introduced for the vibrations of an adsorbed molecule which includes the molecular atoms, the surface atoms binding the molecule, and their nearest neighbors. The vibrational modes of CO adsorbed on a Ni(001) metal surface are obtained using two different cluster models to represent the on-top and bridge-bonding situations. A He/OC-Ni(001) potential is constructed from a strongly repulsive potential of He interacting with the oxygen atom in the CO molecule and a van der Waals attraction accounting for the He interaction with the free Ni(001) surface. A potential is presented for the Li + /OC-Ni(001) where a coulombic term is introduced to account for the image force. Trajectory studies are performed and analyzed in three dimensions to obtain effective classical cross-sections for the He/OC-Ni(001) and Li + /OC-Ni(001) systems. Results for the double differential cross-sections are presented as functions of scattering angles, energy transfer and collisional energy. Temperature dependence results are also analyzed. Extensions of the approach and inclusion of effects such as anharmonicity, collisions at lower energies, and applications of the approach to higher coverages are discussed

Effect of concentration and pH on the surface-enhanced Raman scattering of captopril on nano-colloidal silver surface

Science.gov (United States)

Gao, Junxiang; Gu, Huaimin; Liu, Fangfang; Dong, Xiao; Xie, Min; Hu, Yongjun

2011-07-01

In this report, Raman and surface-enhanced Raman scattering (SERS) spectra of captopril are studied in detail. Herein, the Raman bands are assigned by the density functional theory (DFT) calculations and potential energy distributions (PED) based on internal coordinates of the molecule, which are found to be in good agree with the experimental values. Furthermore, the concentration and pH dependence of the SERS intensity of the molecule is discussed. By analyzing the intensities variation of SERS bands of the different concentrations of captopril solution, it can be concluded that the molecules orientation adsorbed on the silver nanoparticles surface change with the change of the concentrations. The variation of SERS spectra of captopril with the change of pH suggests that the interaction among the adsorbates with Ag cluster depend on the protonated state of the adsorbate and the aggregation of silver nanoparticles.

Detection of Surface-Linked Polychlorinated Biphenyls using Surface-Enhanced Raman Scattering Spectroscopy

DEFF Research Database (Denmark)

Rindzevicius, Tomas; Barten, Jan; Vorobiev, Mikhail

2017-01-01

We present an improved procedure for analytical detection of toxic polychlorinated biphenyls (PCB) using surface-enhanced Raman scattering (SERS) spectroscopy. A gold-capped silicon nanopillar substrate was utilized to concentrate PCB molecules within an area of high electromagnetic fields through...... formation of microsized nanopillar clusters, and consequently, so-called “hot spots” can be formed. In order to improve PCB detection limit, 3,3',4,4'-tetrachlorobiphenyl (PCB77) compounds were chemically modified with a – SCH3 (PCB77-SCH3) group. Experimental and numerical analysis of vibrational modes...

Surface-enhanced localized surface plasmon resonance biosensing of avian influenza DNA hybridization using subwavelength metallic nanoarrays

Energy Technology Data Exchange (ETDEWEB)

Kim, Shin Ae; Jang, Sung Min; Kim, Sung June [School of Electrical Engineering and Computer Science, Seoul National University, Seoul 151-742 (Korea, Republic of); Byun, Kyung Min [Department of Biomedical Engineering, Kyung Hee University, Yongin 446-701 (Korea, Republic of); Kim, Kyujung; Kim, Donghyun [Program of Nanomedical Science and Technology, Yonsei University, Seoul 120-749 (Korea, Republic of); Ma, Kyungjae; Oh, Youngjin [School of Electrical and Electronic Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of); Kim, Sung Guk [College of Veterinary Medicine, Cornell University, Ithaca, New York 14853 (United States); Shuler, Michael L, E-mail: kmbyun@khu.ac.kr [Department of Biomedical Engineering, Cornell University, Ithaca, New York 14853 (United States)

2010-09-03

We demonstrated enhanced localized surface plasmon resonance (SPR) biosensing based on subwavelength gold nanoarrays built on a thin gold film. Arrays of nanogratings (1D) and nanoholes (2D) with a period of 200 nm were fabricated by electron-beam lithography and used for the detection of avian influenza DNA hybridization. Experimental results showed that both nanoarrays provided significant sensitivity improvement and, especially, 1D nanogratings exhibited higher SPR signal amplification compared with 2D nanohole arrays. The sensitivity enhancement is associated with changes in surface-limited reaction area and strong interactions between bound molecules and localized plasmon fields. Our approach is expected to improve both the sensitivity and sensing resolution and can be applicable to label-free detection of DNA without amplification by polymerase chain reaction.

Tetrahedral cluster and pseudo molecule: New approaches to Calculate Absolute Surface Energy of Zinc Blende (111)/(-1-1-1) Surface

Science.gov (United States)

Zhang, Yiou; Zhang, Jingzhao; Tse, Kinfai; Wong, Lun; Chan, Chunkai; Deng, Bei; Zhu, Junyi

Determining accurate absolute surface energies for polar surfaces of semiconductors has been a great challenge in decades. Here, we propose pseudo-hydrogen passivation to calculate them, using density functional theory approaches. By calculating the energy contribution from pseudo-hydrogen using either a pseudo molecule method or a tetrahedral cluster method, we obtained (111)/(-1-1-1) surfaces energies of Si, GaP, GaAs, and ZnS with high self-consistency. Our findings may greatly enhance the basic understandings of different surfaces and lead to novel strategies in the crystal growth. We would like to thank Su-huai Wei for helpful discussions. Computing resources were provided by the High Performance Cluster Computing Centre, Hong Kong Baptist University. This work was supported by the start-up funding and direct Grant with the Project.

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

Science.gov (United States)

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Formation of gold nanorods and gold nanorod films for surface-enhanced Raman scattering spectroscopy

International Nuclear Information System (INIS)

Trotsyuk, L.L.; Kulakovich, O.S.; Shabunya-Klyachkovskaya, E.V.; Gaponenko, S.V.; Vashchenko, S.V.

2016-01-01

The formation of gold nanorods as well as thin films prepared via electrostatic deposition of gold nanorods has been investigated. The obtained gold nanorods films have been used as substrates for the surface-enhanced Raman scattering analysis of sulfur-free organic molecules mitoxantrone and malachite green as well as inorganic malachite microcrystals for the first time. The additional modification of films with L-cysteine allows one to significantly extend the use of gold nanorods for the surface-enhanced Raman scattering analysis. (authors)

Switching behavior of double-decker single molecule magnets on a metal surface

Energy Technology Data Exchange (ETDEWEB)

Fu, Yingshuang; Schwoebel, Joerg; Hoffmann, Germar; Brede, Jens; Wiesendanger, Roland [University of Hamburg, Hamburg (Germany); Dillulo, Andrew [Ohio University, Athens (United States); Klyatskaya, Svetlana [Karlsruhe Institute of Technology, Karlsruhe (Germany); Ruben, Mario [Karlsruhe Institute of Technology, Karlsruhe (Germany); Universite de Strasbourg, Strasbourg (France)

2011-07-01

Single molecule magnets (SMM) are most promising materials for spin based molecular electronics. Due to their large magnetic anisotropy stabilized by inside chemical bonds, SMM can potentially be used for information storage at the single molecule level. For applications, it is of importance to adsorb the SMM onto surfaces and to study their subsequent conformational, electronic and magnetic properties. We have investigated the adsorption behavior of Tb and Dy based double-decker SMM on an Ir(111) surface with low temperature scanning tunneling microscopy and spectroscopy. It is found that Tb double-decker molecules bind tightly to the Ir(111) surface. By resonantly injecting tunneling electrons into its LUMO or HOMO state, the Tb double-decker molecule can be switched from a four-lobed structure to an eight-lobed structure. After switching, energy positions of the HOMO and LUMO states both shift closer to the Fermi level. Dy double-decker molecules also exhibit the same switching properties on the Ir(111) surface. The switching behavior of the molecules is tentatively attributed to a conformational change of the double-decker molecular frame.

Label-Enhanced Surface Plasmon Resonance: A New Concept for Improved Performance in Optical Biosensor Analysis

Directory of Open Access Journals (Sweden)

Niko Granqvist

2013-11-01

Full Text Available Surface plasmon resonance (SPR is a well-established optical biosensor technology with many proven applications in the study of molecular interactions as well as in surface and material science. SPR is usually applied in the label-free mode which may be advantageous in cases where the presence of a label may potentially interfere with the studied interactions per se. However, the fundamental challenges of label-free SPR in terms of limited sensitivity and specificity are well known. Here we present a new concept called label-enhanced SPR, which is based on utilizing strongly absorbing dye molecules in combination with the evaluation of the full shape of the SPR curve, whereby the sensitivity as well as the specificity of SPR is significantly improved. The performance of the new label-enhanced SPR method was demonstrated by two simple model assays: a small molecule assay and a DNA hybridization assay. The small molecule assay was used to demonstrate the sensitivity enhancement of the method, and how competitive assays can be used for relative affinity determination. The DNA assay was used to demonstrate the selectivity of the assay, and the capabilities in eliminating noise from bulk liquid composition variations.

Label-Enhanced Surface Plasmon Resonance: A New Concept for Improved Performance in Optical Biosensor Analysis

Science.gov (United States)

Granqvist, Niko; Hanning, Anders; Eng, Lars; Tuppurainen, Jussi; Viitala, Tapani

2013-01-01

Surface plasmon resonance (SPR) is a well-established optical biosensor technology with many proven applications in the study of molecular interactions as well as in surface and material science. SPR is usually applied in the label-free mode which may be advantageous in cases where the presence of a label may potentially interfere with the studied interactions per se. However, the fundamental challenges of label-free SPR in terms of limited sensitivity and specificity are well known. Here we present a new concept called label-enhanced SPR, which is based on utilizing strongly absorbing dye molecules in combination with the evaluation of the full shape of the SPR curve, whereby the sensitivity as well as the specificity of SPR is significantly improved. The performance of the new label-enhanced SPR method was demonstrated by two simple model assays: a small molecule assay and a DNA hybridization assay. The small molecule assay was used to demonstrate the sensitivity enhancement of the method, and how competitive assays can be used for relative affinity determination. The DNA assay was used to demonstrate the selectivity of the assay, and the capabilities in eliminating noise from bulk liquid composition variations. PMID:24217357

Influencing the bonding and assembly of a multiterminal molecule on a metal surface

Energy Technology Data Exchange (ETDEWEB)

Lukas, Maya; Doessel, Kerrin; Fink, Karin; Fuhr, Olaf [Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, D-76021 Karlsruhe (Germany); DFG Center of Functional Nanostructures (CFN), D-76049 Karlsruhe (Germany); Schramm, Alexandrina; Stroh, Christophe [Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, D-76021 Karlsruhe (Germany); Mayor, Marcel [Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, D-76021 Karlsruhe (Germany); DFG Center of Functional Nanostructures (CFN), D-76049 Karlsruhe (Germany); University of Basel, Department of Chemistry, CH-4056 Basel (Switzerland); Loehneysen, Hilbert von [Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, D-76021 Karlsruhe (Germany); DFG Center of Functional Nanostructures (CFN), D-76049 Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Physics Institute and Institute for Solid State Physics, D-76049 Karlsruhe (Germany)

2011-07-01

The bond of a molecule to a metallic electrode is known to have a crucial influence on the molecular conductance. As electronic functionalities are integrated into molecules or several subunits are connected to a three-dimensional multiterminal molecule, it is not obvious that a ''well-known'' chemical linker group will lead to the bonding configuration known from simpler molecules. We investigated a series of tripodal molecules on metal surfaces by STM. The chemical linker groups and the complex connecting the three wire-units are varied. We find that the position of molecules on the surface is governed by a subtle balance of intermolecular and molecule-surface interactions, partly in strong contrast to expectations. This emphasizes the need to characterize the nature of molecule-electrode contacts along with the investigation of the electronic conductance.

Energy redistribution in diatomic molecules on surfaces

International Nuclear Information System (INIS)

Asscher, M.; Somorjai, G.A.

1984-04-01

Translational and internal degrees of freedom of a scattered beam of NO molecules from a Pt(111) single crystal surface were measured as a function of scattering angle and crystal temperature in the range 450 to 1250K. None of the three degrees of freedom were found to fully accommodate to the crystal temperature, the translational degree being the most accommodated and the rotational degree of freedom the least. A precursor state model is suggested to account for the incomplete accommodation of translational and vibrational degrees of freedom as a function of crystal temperature and incident beam energy. The vibrational accommodation is further discussed in terms of a competition between desorption and vibrational excitation processes, thus providing valuable information on the interaction between vibrationally excited molecules and surfaces. Energy transfer into rotational degrees of freedom is qualitatively discussed

Selection of conformational states in surface self-assembly for a molecule with eight possible pairs of surface enantiomers

DEFF Research Database (Denmark)

Nuermaimaiti, Ajiguli; Schultz-Falk, Vickie; Lind Cramer, Jacob

2016-01-01

Self-assembly of a molecule with many distinct conformational states, resulting in eight possible pairs of surface enantiomers, is investigated on a Au(111) surface under UHV conditions. The complex molecule is equipped with alkyl and carboxyl moieties to promote controlled self-assembly of lamel......Self-assembly of a molecule with many distinct conformational states, resulting in eight possible pairs of surface enantiomers, is investigated on a Au(111) surface under UHV conditions. The complex molecule is equipped with alkyl and carboxyl moieties to promote controlled self......-assembly of lamellae structures. From statistical analysis of Scanning Tunnelling Microscopy (STM) data we observe a clear selection of specific conformational states after self-assembly. Using Density Functional Theory (DFT) calculations we rationalise how this selection is correlated to the orientation of the alkyl...

Mathematical model for biomolecular quantification using surface-enhanced Raman spectroscopy based signal intensity distributions

DEFF Research Database (Denmark)

Palla, Mirko; Bosco, Filippo Giacomo; Yang, Jaeyoung

2015-01-01

This paper presents the development of a novel statistical method for quantifying trace amounts of biomolecules by surface-enhanced Raman spectroscopy (SERS) using a rigorous, single molecule (SM) theory based mathematical derivation. Our quantification framework could be generalized for planar...

Review of Recent Progress of Plasmonic Materials and Nano-Structures for Surface-Enhanced Raman Scattering

Directory of Open Access Journals (Sweden)

Alan X. Wang

2015-05-01

Full Text Available Surface-enhanced Raman scattering (SERS has demonstrated single-molecule sensitivity and is becoming intensively investigated due to its significant potential in chemical and biomedical applications. SERS sensing is highly dependent on the substrate, where excitation of the localized surface plasmons (LSPs enhances the Raman scattering signals of proximate analyte molecules. This paper reviews research progress of SERS substrates based on both plasmonic materials and nano-photonic structures. We first discuss basic plasmonic materials, such as metallic nanoparticles and nano-rods prepared by conventional bottom-up chemical synthesis processes. Then, we review rationally-designed plasmonic nano-structures created by top-down approaches or fine-controlled synthesis with high-density hot-spots to provide large SERS enhancement factors (EFs. Finally, we discuss the research progress of hybrid SERS substrates through the integration of plasmonic nano-structures with other nano-photonic devices, such as photonic crystals, bio-enabled nanomaterials, guided-wave systems, micro-fluidics and graphene.

Surface-Enhanced Raman Spectroscopy

Indian Academy of Sciences (India)

IAS Admin

weak Raman signal, which facilitates identification in chemi- cal and biological systems. Recently, single-molecule Raman scattering has enhanced the detection sensitivity limit of ... was working on the molecular diffraction of light, which ulti-.

Efficient surface enhanced Raman scattering on confeito-like gold nanoparticle-adsorbed self-assembled monolayers.

Science.gov (United States)

Chang, Chia-Chi; Imae, Toyoko; Chen, Liang-Yih; Ujihara, Masaki

2015-12-28

Confeito-like gold nanoparticles (AuNPs; average diameter = 80 nm) exhibiting a plasmon absorption band at 590 nm were adsorbed through immersion-adsorption on two self-assembled monolayers (SAMs) of 3-aminopropyltriethoxysilane (APTES-SAM) and polystyrene spheres coated with amine-terminated poly(amido amine) dendrimers (DEN/PS-SAM). The surface enhanced Raman scattering (SERS) effect on the SAM substrates was examined using the molecules of a probe dye, rhodamine 6G (R6G). The Raman scattering was strongly intensified on both substrates, but the enhancement factor (>10,000) of the AuNP/DEN/PS-SAM hierarchy substrate was 5-10 times higher than that of the AuNP/APTES-SAM substrate. This strong enhancement is attributed to the large surface area of the substrate and the presence of hot spots. Furthermore, analyzing the R6G concentration dependence of SERS suggested that the enhancement mechanism effectively excited the R6G molecules in the first layer on the hot spots and invoked the strong SERS effect. These results indicate that the SERS activity of confeito-like AuNPs on SAM substrates has high potential in molecular electronic devices and ultrasensitive analyses.

A monolayer of hierarchical silver hemi-mesoparticles with tunable surface topographies for highly sensitive surface-enhanced Raman spectroscopy

Science.gov (United States)

Zhu, Shuangmei; Fan, Chunzhen; Mao, Yanchao; Wang, Junqiao; He, Jinna; Liang, Erjun; Chao, Mingju

2016-02-01

We proposed a facile green synthesis system to synthesize large-scale Ag hemi-mesoparticles monolayer on Cu foil. Ag hemi-mesoparticles have different surface morphologies on their surfaces, including ridge-like, meatball-like, and fluffy-like shapes. In the reaction, silver nitrate was reduced by copper at room temperature in dimethyl sulfoxide via the galvanic displacement reaction. The different surface morphologies of the Ag hemi-mesoparticles were adjusted by changing the reaction time, and the hemi-mesoparticle surface formed fluffy-spherical nanoprotrusions at longer reaction time. At the same time, we explored the growth mechanism of silver hemi-mesoparticles with different surface morphologies. With 4-mercaptobenzoic acid as Raman probe molecules, the fluffy-like silver hemi-mesoparticles monolayer with the best activity of surface enhanced Raman scattering (SERS), the enhancement factor is up to 7.33 × 107 and the detection limit can reach 10-10M. SERS measurements demonstrate that these Ag hemi-mesoparticles can serve as sensitive SERS substrates. At the same time, using finite element method, the distribution of the localized electromagnetic field near the particle surface was simulated to verify the enhanced mechanism. This study helps us to understand the relationship between morphology Ag hemi-mesoparicles and the properties of SERS.

Ion-enhanced gas-surface chemistry: The influence of the mass of the incident ion

International Nuclear Information System (INIS)

Gerlach-Meyer, U.; Coburn, J.W.; Kay, E.

1981-01-01

There are many examples of situations in which a gas-surface reaction rate is increased when the surface is simultaneously subjected to energetic particle bombardment. There are several possible mechanisms which could be involved in this radiation-enhanced gas-surface chemistry. In this study, the reaction rate of silicon, as determined from the etch yield, is measured during irradiation of the Si surface with 1 keV He + , Ne + , and Ar + ions while the surface is simultaneously subjected to fluxes of XeF 2 or Cl 2 molecules. Etch yields as high as 25 Si atoms/ion are observed for XeF 2 and Ar + on Si. A discussion is presented of the extent to which the results clarify the mechanisms responsible for ion-enhanced gas-surface chemistry. (orig.)

Magnetic memory of a single-molecule quantum magnet wired to a gold surface.

Science.gov (United States)

Mannini, Matteo; Pineider, Francesco; Sainctavit, Philippe; Danieli, Chiara; Otero, Edwige; Sciancalepore, Corrado; Talarico, Anna Maria; Arrio, Marie-Anne; Cornia, Andrea; Gatteschi, Dante; Sessoli, Roberta

2009-03-01

In the field of molecular spintronics, the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. Although simple paramagnetic molecules can show surface-induced magnetic ordering and hysteresis when deposited on ferromagnetic surfaces, information storage at the molecular level requires molecules exhibiting an intrinsic remnant magnetization, like the so-called single-molecule magnets (SMMs). These have been intensively investigated for their rich quantum behaviour but no magnetic hysteresis has been so far reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, we have now found that robust, tailor-made Fe(4) complexes retain magnetic hysteresis at gold surfaces. Our results demonstrate that isolated SMMs can be used for storing information. The road is now open to address individual molecules wired to a conducting surface in their blocked magnetization state, thereby enabling investigation of the elementary interactions between electron transport and magnetism degrees of freedom at the molecular scale.

Silver-coated Si nanograss as highly sensitive surface-enhanced Raman spectroscopy substrates

Energy Technology Data Exchange (ETDEWEB)

Tang, Jing; Kuo, Huei Pei; Hu, Min; Li, Zhiyong; Williams, R.S. [Hewlett-Packard Laboratories, Information and Quantum Systems Laboratory, Palo Alto, CA (United States); Ou, Fung Suong [Hewlett-Packard Laboratories, Information and Quantum Systems Laboratory, Palo Alto, CA (United States); Rice University, Department of Applied Physics, Houston, TX (United States); Stickle, William F. [Hewlett-Packard Company, Advanced Diagnostic Lab, Corvallis, OR (United States)

2009-09-15

We created novel surface-enhanced Raman spectroscopy (SERS) substrates by metalization (Ag) of Si nanograss prepared by a Bosch process which involves deep reactive ion etching of single crystalline silicon. No template or lithography was needed for making the Si nanograss, thus providing a simple and inexpensive method to achieve highly sensitive large-area SERS substrates. The dependence of the SERS effect on the thickness of the metal deposition and on the surface morphology and topology of the substrate prior to metal deposition was studied in order to optimize the SERS signals. We observed that the Ag-coated Si nanograss can achieve uniform SERS enhancement over large area ({proportional_to}1 cm x 1 cm) with an average EF (enhancement factor) of 4.2 x 10{sup 8} for 4-mercaptophenol probe molecules. (orig.)

[Study on the surface-enhanced Raman spectrum of trimethoprim].

Science.gov (United States)

Zhang, Jin-zhi; Wang, Yuan

2003-02-01

A new method is given in this paper to study the spectra of trimethoprim by using the surface-enhanced Raman spectrum (SERS) technology and the highly efficient thin layer chromatography (TLC) dissociation technology. The results of SERS indicate that the main vibrant spectral band can be obtained by TLC in the samples of about 6 micrograms. The expansion and contraction of pyrimidine ring can be obviously increased and the molecule information can be exactly presented under the action of silver particles.

Enhanced resolution imaging of ultrathin ZnO layers on Ag(111) by multiple hydrogen molecules in a scanning tunneling microscope junction

Science.gov (United States)

Liu, Shuyi; Shiotari, Akitoshi; Baugh, Delroy; Wolf, Martin; Kumagai, Takashi

2018-05-01

Molecular hydrogen in a scanning tunneling microscope (STM) junction has been found to enhance the lateral spatial resolution of the STM imaging, referred to as scanning tunneling hydrogen microscopy (STHM). Here we report atomic resolution imaging of 2- and 3-monolayer (ML) thick ZnO layers epitaxially grown on Ag(111) using STHM. The enhanced resolution can be obtained at a relatively large tip to surface distance and resolves a more defective structure exhibiting dislocation defects for 3-ML-thick ZnO than for 2 ML. In order to elucidate the enhanced imaging mechanism, the electric and mechanical properties of the hydrogen molecular junction (HMJ) are investigated by a combination of STM and atomic force microscopy. It is found that the HMJ shows multiple kinklike features in the tip to surface distance dependence of the conductance and frequency shift curves, which are absent in a hydrogen-free junction. Based on a simple modeling, we propose that the junction contains several hydrogen molecules and sequential squeezing of the molecules out of the junction results in the kinklike features in the conductance and frequency shift curves. The model also qualitatively reproduces the enhanced resolution image of the ZnO films.

Surface-confined electroactive molecules for multistate charge storage information.

Science.gov (United States)

Mas-Torrent, M; Rovira, C; Veciana, J

2013-01-18

Bi-stable molecular systems with potential for applications in binary memory devices are raising great interest for device miniaturization. Particular appealing are those systems that operate with electrical inputs since they are compatible with existing electronic technologies. The processing of higher memory densities in these devices could be accomplished by increasing the number of memory states in each cell, although this strategy has not been much explored yet. Here we highlight the recent advances devoted to the fabrication of charge-storage molecular surface-confined devices exhibiting multiple states. Mainly, this goal has been realized immobilizing a variety (or a combination) of electroactive molecules on a surface, although alternative approaches employing non-electroactive systems have also been described. Undoubtedly, the use of molecules with chemically tunable properties and nanoscale dimensions are raising great hopes for the devices of the future in which molecules can bring new perspectives such as multistability.

Spinterface between tris(8-hydroxyquinoline)metal(III) molecules and magnetic surfaces: a first-principles study

Science.gov (United States)

Jiang, W.; Wang, Jingying; Dougherty, Daniel; Liu, Feng; Feng Liu Team; Daniel Dougherty Team

Using first-principles calculations, we have systematically investigated the hybridization between tris(8-hydroxyquinoline)metal(III) (Mq3, M = Fe, Cr, Al) molecules and magnetic substrates (Co and Cr). Mq3 with different central metal elements but the same organic framework has dramatically different interaction with different magnetic substrates, which affect the interface state significantly. AFM coupling was observed between magnetic Mq3 molecules and ferromagnetic (Co) as well as antiferromagnetic (Cr) substrate, manifested with a superexchange and direct exchange interaction, respectively. Such strong magnetic interfacial coupling may open a gap around the Fermi level and significantly change interface transport properties. Nonmagnetic Alq3 molecule was found to enhance the interface spin polarization due to hybridization between the lowest unoccupied molecular orbitals (LUMO) of Alq3 and metallic surface state. These findings will help better understand spinterface and shed new light on future application of Mq3 molecules in spintronics devices. This work was support by NSF-MRSEC (DMR-1121252) and DOE-BES (DE-FG02-04ER46148).

Single atom and-molecules chemisorption on solid surfaces

International Nuclear Information System (INIS)

Anda, E.V.; Ure, J.E.; Majlis, N.

1981-01-01

A simplified model for the microscopic interpretation of single atom and- molecules chemisorption on metallic surfaces is presented. An appropriated hamiltonian for this problem is resolved, through the Green's function formalism. (L.C.) [pt

Plasmonic tunnel junctions for single-molecule redox chemistry.

Science.gov (United States)

de Nijs, Bart; Benz, Felix; Barrow, Steven J; Sigle, Daniel O; Chikkaraddy, Rohit; Palma, Aniello; Carnegie, Cloudy; Kamp, Marlous; Sundararaman, Ravishankar; Narang, Prineha; Scherman, Oren A; Baumberg, Jeremy J

2017-10-20

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots. Here, surface-enhanced Raman spectroscopy allows us to track these hot-electron-induced chemical reduction processes in a series of different aromatic molecules. We demonstrate that by increasing the tunnelling barrier height and the dephasing strength, a transition from coherent to hopping electron transport occurs, enabling observation of redox processes in real time at the single-molecule level.

Intense Visible Luminescence in CdSe Quantum Dots by Efficiency Surface Passivation with H2O Molecules

Directory of Open Access Journals (Sweden)

Hyeoung Woo Park

2012-01-01

Full Text Available We have investigated the effect of water (H2O cooling and heat treatment on the luminescence efficiency of core CdSe quantum dots (QDs. The photoluminescence (PL quantum yield of the CdSe QDs was enhanced up to ~85%, and some periodic bright points were observed in wide color ranges during the heat treatment of QDs mixed with H2O. The PL enhancement of QDs could be attributed to the recovery of QDs surface traps by unreacted ligands confined within the hydrophilic H2O molecule containers.

Single DNA molecules as probes for interrogating silica surfaces after various chemical treatments

International Nuclear Information System (INIS)

Liu Xia; Wu Zhan; Nie Huagui; Liu Ziling; He Yan; Yeung, E.S.

2007-01-01

We examined the adsorption of single YOYO-1-labeled λ-DNA molecules at glass surfaces after treatment with various chemical cleaning methods by using total internal reflection fluorescence microscopy (TIRFM). The characteristics of these surfaces were further assessed using contact angle (CA) measurements and atomic force microscopy (AFM). By recording the real-time dynamic motion of DNA molecules at the liquid/solid interface, subtle differences in adsorption affinities were revealed. The results indicate that the driving force for adsorption of DNA molecules on glass surfaces is mainly hydrophobic interaction. We also found that surface topography plays a role in the adsorption dynamics

Surface-enhanced Raman scattering (SERS) of riboflavin on nanostructured Ag surfaces: The role of excitation wavelength, plasmon resonance and molecular resonance

Science.gov (United States)

Šubr, Martin; Kuzminova, Anna; Kylián, Ondřej; Procházka, Marek

2018-05-01

Optimization of surface-enhanced Raman scattering (SERS)-based sensors for (bio)analytical applications has received much attention in recent years. For optimum sensitivity, both the nanostructure fabrication process and the choice of the excitation wavelength used with respect to the specific analyte studied are of crucial importance. In this contribution, detailed SERS intensity profiles were measured using gradient nanostructures with the localized surface-plasmon resonance (LSPR) condition varying across the sample length and using riboflavin as the model biomolecule. Three different excitation wavelengths (633 nm, 515 nm and 488 nm) corresponding to non-resonance, pre-resonance and resonance excitation with respect to the studied molecule, respectively, were tested. Results were interpreted in terms of a superposition of the enhancement provided by the electromagnetic mechanism and intrinsic properties of the SERS probe molecule. The first effect was dictated mainly by the degree of spectral overlap between the LSPR band, the excitation wavelength along with the scattering cross-section of the nanostructures, while the latter was influenced by the position of the molecular resonance with respect to the excitation wavelength. Our experimental findings contribute to a better understanding of the SERS enhancement mechanism.

Nanocoating of titanium implant surfaces with organic molecules. Polysaccharides including glycosaminoglycans

DEFF Research Database (Denmark)

Gurzawska, Katarzyna Aleksandra; Svava, Rikke; Jørgensen, Niklas Rye

2012-01-01

Long-term stability of titanium implants are dependent on a variety of factors. Nanocoating with organic molecules is one of the method used to improve osseointegration. Nanoscale modification of titanium implants affects surface properties, such as hydrophilicity, biochemical bonding capacity...... and roughness. This influences cell behaviour on the surface such as adhesion, proliferation and differentiation of cells as well as the mineralization of the extracellular matrix at the implant surfaces. The aim of the present systematic review was to describe organic molecules used for surface nanocoating...... nanocoatings. The included in vivo studies, showed improvement of bone interface reactions measured as increased Bone-to-Implant Contact length and Bone Mineral Density adjacent to the polysaccharide coated surfaces. Based on existing literature, surface modification with polysaccharide and glycosaminoglycans...

DNA origami as biocompatible surface to match single-molecule and ensemble experiments

Science.gov (United States)

Gietl, Andreas; Holzmeister, Phil; Grohmann, Dina; Tinnefeld, Philip

2012-01-01

Single-molecule experiments on immobilized molecules allow unique insights into the dynamics of molecular machines and enzymes as well as their interactions. The immobilization, however, can invoke perturbation to the activity of biomolecules causing incongruities between single molecule and ensemble measurements. Here we introduce the recently developed DNA origami as a platform to transfer ensemble assays to the immobilized single molecule level without changing the nano-environment of the biomolecules. The idea is a stepwise transfer of common functional assays first to the surface of a DNA origami, which can be checked at the ensemble level, and then to the microscope glass slide for single-molecule inquiry using the DNA origami as a transfer platform. We studied the structural flexibility of a DNA Holliday junction and the TATA-binding protein (TBP)-induced bending of DNA both on freely diffusing molecules and attached to the origami structure by fluorescence resonance energy transfer. This resulted in highly congruent data sets demonstrating that the DNA origami does not influence the functionality of the biomolecule. Single-molecule data collected from surface-immobilized biomolecule-loaded DNA origami are in very good agreement with data from solution measurements supporting the fact that the DNA origami can be used as biocompatible surface in many fluorescence-based measurements. PMID:22523083

Anchoring of alkyl chain molecules on oxide surface using silicon alkoxide

Energy Technology Data Exchange (ETDEWEB)

Narita, Ayumi, E-mail: narita.ayumi@jaea.go.jp [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Graduate School of Science and Engineering, Ibaraki University, Bunnkyo, Mito-shi, Ibaraki-ken 310-8512 (Japan); Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Yaita, Tsuyoshi [Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 (Japan); Graduate School of Science and Engineering, Ibaraki University, Bunnkyo, Mito-shi, Ibaraki-ken 310-8512 (Japan)

2012-01-01

Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides.

Advances on the nanostructuration of magnetic molecules on surfaces: the case of single-molecule magnets (SMM).

Science.gov (United States)

Gómez-Segura, Jordi; Veciana, Jaume; Ruiz-Molina, Daniel

2007-09-28

SMMs exhibit slow magnetization relaxation rates characteristic of nanodomain particles whose origin is however on individual molecules. For this reason, they have attracted much interest due to their potential applications in high-density information storage devices and quantum computing applications, where for instance, each molecule can be used as a magnetic bit of information. However, for this to become a reality, several basic studies such as their deposition on surfaces are still highly required. Here we will revise all the experimental approximations that have been so far reported for their addressing, nanostructuration and study on surfaces, from the use of stamps as templates to their anchorage to gold surface through the use of thiol-based ligands. It is also important to emphasize that the results and methodologies described along this review are applicable not only to SMMs but to any molecular material.

Nano-Gap Embedded Plasmonic Gratings for Surface Plasmon Enhanced Fluorescence

Science.gov (United States)

Bhatnagar, Kunal; Bok, Sangho; Korampally, Venumadhav; Gangopadhyay, Shubhra

2012-02-01

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal/dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures on the sub wavelength scale have been shown to provide very efficient and extreme light concentration at the nano-scale. The enhanced electric field produced within a few hundred nanometers of these structures can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences. Improving the qualities and capabilities of fluorescence based detectors and imaging equipment has been a big challenge to the industry manufacturers. We report the novel fabrication of nano-gap embedded periodic grating substrates on the nanoscale using micro-contact printing and polymethylsilsesquioxane (PMSSQ) polymer. Fluorescence enhancement of up to 118 times was observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for low-level fluorescence detection and single molecule imaging.

Investigating Nanoscale Electrochemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

Science.gov (United States)

Zaleski, Stephanie; Wilson, Andrew J; Mattei, Michael; Chen, Xu; Goubert, Guillaume; Cardinal, M Fernanda; Willets, Katherine A; Van Duyne, Richard P

2016-09-20

The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation of heterogeneous chemical reactions with high sensitivity. Specifically, SERS methodologies are well-suited to study electron transfer (ET) reactions, which lie at the heart of numerous fundamental processes: electrocatalysis, solar energy conversion, energy storage in batteries, and biological events such as photosynthesis. Heterogeneous ET reactions are commonly monitored by electrochemical methods such as cyclic voltammetry, observing billions of electrochemical events per second. Since the first proof of detecting single molecules by redox cycling, there has been growing interest in examining electrochemistry at the nanoscale and single-molecule levels. Doing so unravels details that would otherwise be obscured by an ensemble experiment. The use of optical spectroscopies, such as SERS, to elucidate nanoscale electrochemical behavior is an attractive alternative to traditional approaches such as scanning electrochemical microscopy (SECM). While techniques such as single-molecule fluorescence or electrogenerated chemiluminescence have been used to optically monitor electrochemical events, SERS methodologies, in particular, have shown great promise for exploring electrochemistry at the nanoscale. SERS is ideally suited to study nanoscale electrochemistry because the Raman-enhancing metallic, nanoscale substrate duly serves as the working electrode material. Moreover, SERS has the ability to directly probe single molecules without redox cycling and can achieve nanoscale spatial resolution in combination with super-resolution or scanning probe microscopies. This Account summarizes the latest progress from the Van Duyne and Willets groups toward understanding nanoelectrochemistry using Raman spectroscopic methodologies. The first half of this Account highlights three techniques that have been recently used to probe few- or single-molecule electrochemical

Hyperthermal surface ionization mass spectrometry of organic molecules: monoterpenes

International Nuclear Information System (INIS)

Kishi, Hiroshi; Fujii, Toshihiro.

1997-01-01

This paper describes an experimental study on the influence of kinetic energy of fast monoterpene molecules on the surface ionization efficiency and on the mass spectral patterns, using rhenium oxide (ReO 2 ) surface. Molecular kinetic energy, given to the molecules through the acceleration in the seeded supersonic molecular beam, ranged from 1 to 10 eV. Hyperthermal surface ionization mass spectra (HSIMS) were taken for various incident kinetic energies and surface temperatures. The observed mass spectra were interpreted in a purely empirical way, by means of evidence from the previous investigations, and they were compared with conventional EI techniques and with the thermal energy surface ionization technique (SIOMS; Surface Ionization Organic Mass Spectrometry). Ionization efficiency (β) was also studied. Under hyperthermal surface ionization (HSI) conditions, many kinds of fragment ions, including quite abundant odd electron ions (OE +· ) are observed. HSIMS patterns of monoterpenes are different among 6-isomers, contrary to those of SIOMS and EIMS, where very similar patterns for isomers are observed. HSIMS patterns are strongly dependent on the molecular kinetic energies. The surface temperature does not affect much the spectral patterns, but it controls the total amount of ion formation. We conclude from these mass spectral findings, HSI-mechanism contains an impulsive process of ion formation, followed by the fragmentation process as a results of the internal energies acquired through the collision processes. (author)

On the chemical enhancement in SERS

Science.gov (United States)

Jensen, Lasse

2012-12-01

In Surface-enhanced Raman scattering (SERS), the Raman signal of a molecule adsorbed on a metal surface is enhanced by many orders of magnitude. This provides a "finger-print" of molecules which can be used in ultrasensitive sensing devises. Here we present a time-dependent density functional theory (TDDFT) study of the molecule-surface chemical coupling in SERS. A systematic study of the chemical enhancement (CHEM) of meta-and para-substituted pyridines interacting with a small silver cluster (Ag20) is presented. We find that the magnitude of chemical enhancement is governed to a large extent by the energy difference between the highest occupied energy level (HOMO) of the metal and the lowest unoccupied energy level (LUMO) of the molecule. A two-state approximation shows that the enhancement scales roughly as (ωX/ω¯e)4, where accent="true">ω¯e is an average excitation energy between the HOMO of the metal and the LUMO of the molecule and wX the HOMO-LUMO gap of the free molecule. Furthermore, we demonstrate that it is possible to control the CHEM enhancement by switching a dithienylethene photoswitch from its closed form to its open form. The open form of the photoswitch is found to be the strongest Raman scatterer when adsorbed on the surface whereas the opposite is found for the free molecule. This trend is explained using the simple two-state approximation.

Isotope separation using vibrationally excited molecules

International Nuclear Information System (INIS)

Woodroffe, J.A.; Keck, J.C.

1977-01-01

A system for isotope separation or enrichment wherein molecules of a selected isotope type in a flow of molecules of plural isotope types are vibrationally excited and collided with a background gas to provide enhanced diffusivity for the molecules of the selected isotope type permitting their separate collection. The system typically is for the enrichment of uranium using a uranium hexafluoride gas in combination with a noble gas such as argon. The uranium hexafluoride molecules having a specific isotope of uranium are vibrationally excited by laser radiation. The vibrational energy is converted to a translation energy upon collision with a particle of the background gas and the added translation energy enhances the diffusivity of the selected hexafluoride molecules facilitating its condensation on collection surfaces provided for that purpose. This process is periodically interrupted and the cryogenic flow halted to permit evaporation of the collected molecules to provide a distinct, enriched flow

Controlled enzymatic cutting of DNA molecules adsorbed on surfaces using soft lithography

Science.gov (United States)

Auerbach, Alyssa; Budassi, Julia; Shea, Emily; Zhu, Ke; Sokolov, Jonathan

2013-03-01

The enzyme DNase I was applied to adsorbed and aligned DNA molecules (Lamda, 48.5 kilobase pairs (kbp), and T4, 165.6 kbp), stretched linearly on a surface, by stamping with a polydimethylsiloxane (PDMS) grating. The DNAs were cut by the enzyme into separated, micron-sized segments along the length of the molecules at positions determined by the grating dimensions (3-20 microns). Ozone-treated PDMS stamps were coated with DNase I solutions and placed in contact with surface-adsorbed DNA molecules deposited on a 750 polymethylmethacrylate (PMMA) film spun-cast onto a silicon substrate. The stamps were applied under pressure for times up to 15 minutes at 37 C. The cutting was observed by fluorescence microscopy imaging of DNA labeled with YOYO dye. Cutting was found to be efficient despite the steric hindrance due to surface attachment of the molecules. Methods for detaching and separating the cut segments for sequencing applications will be discussed. Supported by NSF-DMR program.

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

Science.gov (United States)

Varadhan, Purushothaman; Fu, Hui-Chun; Priante, Davide; Retamal, Jose Ramon Duran; Zhao, Chao; Ebaid, Mohamed; Ng, Tien Khee; Ajia, Idirs; Mitra, Somak; Roqan, Iman S; Ooi, Boon S; He, Jr-Hau

2017-03-08

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm 2 at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Water molecule-enhanced CO2 insertion in lanthanide coordination polymers

International Nuclear Information System (INIS)

Luo Liushan; Huang Xiaoyuan; Wang Ning; Wu Hongyan; Chen Wenbin; Feng Zihao; Zhu Huiping; Peng Xiaoling; Li Yongxian; Huang Ling; Yue Shantang; Liu Yingliang

2009-01-01

Two new lanthanide coordination polymers H 2 N(CH 3 ) 2 .[Eu III 2 (L 1 ) 3 (L 2 )] (1, L 1 =isophthalic acid dianion, L 2 =formic acid anion) and [La III (2,5-PDC)(L 2 )](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L 2 ) is not contained in the stating materials, but arises from the water molecule-enhanced CO 2 insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks. - Graphical abstract: Two new lanthanide coordination polymers involving water molecule-enhanced CO 2 insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

International Nuclear Information System (INIS)

Chang, Hyejin; Chae, Jinjoo; Jeong, Hong; Kang, Homan; Lee, Yoonsik

2014-01-01

We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature

Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

Energy Technology Data Exchange (ETDEWEB)

Chang, Hyejin; Chae, Jinjoo; Jeong, Hong [Department of Chemistry Education, Seoul (Korea, Republic of); Kang, Homan; Lee, Yoonsik [Interdisciplinary Program in Nano-Science and Technology, Pohang (Korea, Republic of)

2014-03-15

We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature.

Theory of the reaction dynamics of small molecules on metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

2016-09-09

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H₂, H₂O and CH₄ on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

Electromagnetic study of surface enhanced Raman scattering of plasmonic-biomolecule: An interaction between nanodimer and single biomolecule

Science.gov (United States)

Pandey, Gyanendra Krishna; Pathak, Nilesh Kumar; Uma, R.; Sharma, R. P.

2017-04-01

In this article we have investigated the electromagnetic surface enhanced Raman scattering (SERS) of single biomolecule adsorbed at the surface of spherical nanodimer. The SERS mechanism has been studied using first principle approach for spherical nanodimer geometry. The coupling of plasmonic concept to biomolecule results the broadband tunable enhancement in Raman gain factor. In this observation the enhancement factor was observed around ≈ 1015. The plasmonic properties of metal nanodimer are analysed in terms of surface plasmon resonances, extinction efficiency and polarisability that have been derived under quasistatic approximation. In this paper, various facets like interdipole separation, molecule distance and size of the plasmonic nanogeometry are taken into account to analyse the Raman gain factor. We also observe that the frequency range expands sufficiently which increases the broad detectability range of the molecule which generates signal even in the outside of Raman range i.e. in between IR to UV region. Lastly, the extinction spectra and electric field profile have been evaluated at resonance wavelength 364 nm. The comparison between electrostatic approach and numerical approach (using DDA) has also been done in terms of extinction spectra.

Single molecule SERS: Perspectives of analytical applications

Czech Academy of Sciences Publication Activity Database

Vlčková, B.; Pavel, I.; Sládková, M.; Šišková, K.; Šlouf, Miroslav

834-836, - (2007), s. 42-47 ISSN 0022-2860. [European Congress on Molecular Spectroscopy /28./. Istanbul, 03.09.2006-08.09.2006] R&D Projects: GA ČR GA203/04/0688 Institutional research plan: CEZ:AV0Z40500505 Keywords : surface-enhanced Raman scattering (SERS) * surface-enhanced resonance Raman (SERRS) * single molecule SERS Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.486, year: 2007

Gold split-ring resonators (SRRs) as substrates for surface-enhanced raman scattering

KAUST Repository

Yue, Weisheng

2013-10-24

We used gold split ring resonators (SRRs) as substrates for surface-enhanced Raman scattering (SERS). The arrays of SRRs were fabricated by electron-beam lithography in combination with plasma etching. In the detection of rhodamine 6G (R6G) molecules, SERS enhancement factors of the order of 105 was achieved. This SERS enhancement increased as the size of the split gap decrease as a consequence of the matching between the resonance wavelength of the SRRs and the excitation wavelength of SERS. As the size of the split gap decreased, the localized surface plasmon resonance shifted to near the excitation wavelength and, thus, resulted in the increase in the electric field on the nanostructures. We used finite integration method (FIT) to simulate numerically the electromagnetic properties of the SRRs. The results of the simulation agreed well with our experimental observations. We anticipate this work will provide an approach to manipulate the SERS enhancement by modulating the size of split gap with SRRs without affecting the area and structural arrangement. © 2013 American Chemical Society.

Gold split-ring resonators (SRRs) as substrates for surface-enhanced raman scattering

KAUST Repository

Yue, Weisheng; Yang, Yang; Wang, Zhihong; Chen, Longqing; Wang, Xianbin

2013-01-01

We used gold split ring resonators (SRRs) as substrates for surface-enhanced Raman scattering (SERS). The arrays of SRRs were fabricated by electron-beam lithography in combination with plasma etching. In the detection of rhodamine 6G (R6G) molecules, SERS enhancement factors of the order of 105 was achieved. This SERS enhancement increased as the size of the split gap decrease as a consequence of the matching between the resonance wavelength of the SRRs and the excitation wavelength of SERS. As the size of the split gap decreased, the localized surface plasmon resonance shifted to near the excitation wavelength and, thus, resulted in the increase in the electric field on the nanostructures. We used finite integration method (FIT) to simulate numerically the electromagnetic properties of the SRRs. The results of the simulation agreed well with our experimental observations. We anticipate this work will provide an approach to manipulate the SERS enhancement by modulating the size of split gap with SRRs without affecting the area and structural arrangement. © 2013 American Chemical Society.

Fluorescent scattering by molecules embedded in small particles

International Nuclear Information System (INIS)

1982-01-01

Studies are reported in these areas: double resonance in fluorescent and Raman scattering; surface enhanced Raman scattering; fluorescence by molecules embedded in small particles; fluorescence by a liquid droplet; and fluorescence by conical pits in surfaces

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting

KAUST Repository

Varadhan, Purushothaman; Fu, Hui-chun; Priante, Davide; Duran Retamal, Jose Ramon; Zhao, Chao; Ebaid, Mohamed; Ng, Tien Khee; Ajia, Idris A.; Mitra, Somak; Roqan, Iman S.; Ooi, Boon S.; He, Jr-Hau

2017-01-01

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of −31 mA/cm at −0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting

KAUST Repository

Varadhan, Purushothaman

2017-02-08

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of −31 mA/cm at −0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Surface-enhanced Raman scattering from graphene covered gold nanocap arrays

Science.gov (United States)

Long, Kailin; Luo, Xiaoguang; Nan, Haiyan; Du, Deyang; Zhao, Weiwei; Ni, Zhenhua; Qiu, Teng

2013-11-01

This work reports an efficient method to fabricate large-area flexible substrates for surface enhanced Raman scattering (SERS) application. Our technique is based on a single-step direct imprint process via porous anodic alumina stamps. Periodic hexagonal arrangements of porous anodic alumina stamps are transferred to the polyethylene terephthalate substrates by mechanically printing process. Printed nanocaps will turn into "hot spots" for electromagnetic enhancement with a deposited gold film by high vacuum evaporation. The gaps between the nanocaps are controllable with a tight correspondence to the thickness of the deposited gold, which dramatically influence the enhancement factor. After covered with a single-layer graphene sheet, the gold nanocap substrate can be further optimized with an extra enhancement of Raman signals, and it is available for the trace detection of probe molecules. This convenient, simple, and low-cost method of making flexible SERS-active substrates potentially opens a way towards biochemical analysis and disease detection.

High surface enhanced Raman scattering activity of BN nanosheets–Ag nanoparticles hybrids

International Nuclear Information System (INIS)

Yang, Shanshan; Zhang, Zhaochun; Zhao, Jun; Zheng, Houli

2014-01-01

Highlights: • Boron nitride–silver nanohybrid was acquired through a liquid-phase reducing route. • The composite shown a high-quality SERS activity. • 2-Mercaptobenzimidazole was chemisorbed on silver surface in vertical orientation. -- Abstract: A facile liquid-phase reducing route was developed to modify boron nitride (BN) nanosheets with silver nanoparticles (AgNPs) in order to fabricate BN–AgNPs hybrids with high surface enhanced Raman scattering (SERS) activity. The layered structure and morphology of BN–AgNPs nanohybrids were characterized by transmission electron microscopy and atomic force microscopy, meanwhile, Fourier transform infrared spectroscopy and ultraviolet–visible were used for studying optical properties and surface plasmon resonance applied to the optical sensor. The SERS of adsorbed 2-mercaptobenzimidazole (MBI) molecule was investigated which shown that the BN–AgNPs substrate exhibited a very strong SERS activity, offering a great potential application in molecular probe sensor. On the basis of the analysis of SERS and the Raman surface selection rules, we could draw a conclusion that the MBI molecule was adsorbed upright on the AgNPs surface through the sulphur and nitrogen atoms. What is more, the cyclic voltammetry experiment indicated the electrochemically irreversible behavior of BN–AgNPs nanohybrids in KCl solution

Low-energy electron scattering from molecules, biomolecules and surfaces

CERN Document Server

Carsky, Petr

2011-01-01

Since the turn of the 21st century, the field of electron molecule collisions has undergone a renaissance. The importance of such collisions in applications from radiation chemistry to astrochemistry has flowered, and their role in industrial processes such as plasma technology and lighting are vital to the advancement of next generation devices. Furthermore, the development of the scanning tunneling microscope highlights the role of such collisions in the condensed phase, in surface processing, and in the development of nanotechnology.Low-Energy Electron Scattering from Molecules, Biomolecule

Potential energy surface from spectroscopic data in the photodissociation of polyatomic molecules

International Nuclear Information System (INIS)

Kim, Hwa Joong; Kim, Young Sik

2001-01-01

The time-dependent tracking inversion method is studied to extract the potential energy surface of the electronic excited state in the photodissociation of triatomic molecules. Based on the relay of the regularized inversion procedure and time-dependent wave packet propagation, the algorithm extracts the underlying potential energy surface piece by tracking the time-dependent data, which can be synthesized from Raman excitation profiles. We have demonstrated the algorithm to extract the potential energy surface of electronic excited state for NO 2 molecule where the wave packet split on a saddle-shaped surface. Finally, we describe the merits of the time-dependent tracking inversion method compared with the time-dependent inversion method and discussed several extensions of the algorithm

Reaction dynamics of small molecules at metal surfaces

International Nuclear Information System (INIS)

Samson, P.A.

1999-09-01

The dissociation-desorption dynamics of D 2 upon the Sn/Pt(111) surface alloy are dependent on the surface concentration of Sn. The p(2 x 2) Sn/Pt(111) alloy surface (Θ Sn = 0.25 ML), is initially ∼30 times less reactive towards D 2 adsorption than clean Pt(111). On the (√3 x √3) R30 deg Sn/Pt(111) alloy surface (Θ Sn = 0.33 ML), increased inhibition of D 2 adsorption is reported, with S o ∼ 10 -5 at low energy, coinciding with the loss of stable Pt 3 hollow sites and a significant reduction in the D atom binding energy. Sticking on the √3 alloy is activated with an increased energy threshold of ∼280 meV, with no evidence that vibration enhances dissociation. The barrier to dissociation remains in the entrance channel before the D 2 bond begins to stretch. Vibrational excitation is, however, observed in nitrogen desorption from the catalytic reaction of NO + H 2 over Pd(110). For a surface at 600 K, N 2 vibrational state population ratios of P(v=1/v=0) = 0.50 ± 0.05 and P(v=2/v=0) = 0.60 ± 0.20 are reported. Desorption occurs via the N(ad) + N(ad) recombination channel with little energy released into translation and rotation. The translational energy release observed is dependent on the N 2 vibrational state, with translational temperatures of 425 K, 315 K and 180 K reported for the v=0, 1 and 2 states respectively. Sub-thermal energy releases and normally directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d NN responsible for the product vibrational excitation. Although N 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (∼10 -6 to 10 -7 ). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe 4 N. Scanning tunnelling

Two-Dimensional Titanium Carbide (MXene) as Surface-Enhanced Raman Scattering Substrate

Energy Technology Data Exchange (ETDEWEB)

Sarycheva, Asia [Drexel Univ., Philadelphia, PA (United States); Makaryan, Taron [Drexel Univ., Philadelphia, PA (United States); Maleski, Kathleen [Drexel Univ., Philadelphia, PA (United States); Satheeshkumar, Elumalai [National Cheng Kung Univ., Tainan (Taiwan); National Institute of Technology-Trichy, Tamil Nadu (India); Melikyan, Armen [Russian-Armenian (Slavonic) State Univ., Yerevan (Armenia); Minassian, Hayk [A. Alikhanian National Science Lab., Yerevan (Armenia); Yoshimura, Masahiro [National Cheng Kung Univ., Tainan (Taiwan); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

2017-08-22

Here, noble metal (gold or silver) nanoparticles or patterned films are typically used as substrates for surface-enhanced Raman spectroscopy (SERS). Two-dimensional (2D) carbides and nitrides (MXenes) exhibit unique electronic and optical properties, including metallic conductivity and plasmon resonance in the visible or near-infrared range, making them promising candidates for a wide variety of applications. Herein, we show that 2D titanium carbide, Ti₃C₂T_x, enhances Raman signal from organic dyes on a substrate and in solution. As a proof of concept, MXene SERS substrates were manufactured by spray-coating and used to detect several common dyes, with calculated enhancement factors reaching ~10⁶. Titanium carbide MXene demonstrates SERS effect in aqueous colloidal solutions, suggesting the potential for biomedical or environmental applications, where MXene can selectively enhance positively charged molecules.

Structural and electronic properties of single molecules and organic layers on surfaces

NARCIS (Netherlands)

Sotthewes, Kai

2016-01-01

Single molecules and organic layers on well-defined solid surfaces have attracted tremendous attention owing to their interesting physical and chemical properties. The ultimate utility of single molecules or self-assembled monolayers (SAMs) for potential applications is critically dependent on the

Fluorescence enhancement of modified silver nanoparticles.

Science.gov (United States)

Liu, Meicen; Zhang, Zhenglong; Liu, Gaining; Dong, Jun; Sun, Yu; Zheng, Hairong; Li, Guian

2011-11-01

Surface enhanced fluorescence (SEF) effect of acridine orange fluorophore in the proximity of silver nanoparticles (NPs) has been investigated experimentally in the aqueous solution system. It was found that the SEF effect could be influenced by the distribution of the NPs and the separation between the fluorophore molecule and metal surface. The fluorescence enhancement was improved significantly when Ag NPs was capped with 4-Aminothiophenol (PATP) that was acted as an isolating layer between the metal surface and fluorophore molecules. The results suggest that a proper distribution of metallic NPs and proper separation between fluorophore molecule and the particle surface are important for obtaining an optimal SEF effect.

Surface single-molecule dynamics controlled by entropy at low temperatures

Science.gov (United States)

Gehrig, J. C.; Penedo, M.; Parschau, M.; Schwenk, J.; Marioni, M. A.; Hudson, E. W.; Hug, H. J.

2017-02-01

Configuration transitions of individual molecules and atoms on surfaces are traditionally described using an Arrhenius equation with energy barrier and pre-exponential factor (attempt rate) parameters. Characteristic parameters can vary even for identical systems, and pre-exponential factors sometimes differ by orders of magnitude. Using low-temperature scanning tunnelling microscopy (STM) to measure an individual dibutyl sulfide molecule on Au(111), we show that the differences arise when the relative position of tip apex and molecule changes by a fraction of the molecule size. Altering the tip position on that scale modifies the transition's barrier and attempt rate in a highly correlated fashion, which results in a single-molecular enthalpy-entropy compensation. Conversely, appropriately positioning the STM tip allows selecting the operating point on the compensation line and modifying the transition rates. The results highlight the need to consider entropy in transition rates of single molecules, even at low temperatures.

Tip enhancement

CERN Document Server

Kawata, Satoshi

2007-01-01

This book discusses the recent advances in the area of near-field Raman scattering, mainly focusing on tip-enhanced and surface-enhanced Raman scattering. Some of the key features covered here are the optical structuring and manipulations, single molecule sensitivity, analysis of single-walled carbon nanotubes, and analytic applications in chemistry, biology and material sciences. This book also discusses the plasmonic materials for better enhancement, and optical antennas. Further, near-field microscopy based on second harmonic generation is also discussed. Chapters have been written by some of the leading scientists in this field, who present some of their recent work in this field.·Near-field Raman scattering·Tip-enhanced Raman spectroscopy·Surface-enhanced Raman spectroscopy·Nano-photonics·Nanoanalysis of Physical, chemical and biological materials beyond the diffraction limits·Single molecule detection

Quantitative monitoring of two simultaneously binding species using Label-Enhanced surface plasmon resonance.

Science.gov (United States)

Eng, Lars; Garcia, Brandon L; Geisbrecht, Brian V; Hanning, Anders

2018-02-26

Surface plasmon resonance (SPR) is a well-established method for biomolecular interaction studies. SPR monitors the binding of molecules to a solid surface, embodied as refractive index changes close to the surface. One limitation of conventional SPR is the universal nature of the detection that results in an inability to qualitatively discriminate between different binding species. Furthermore, it is impossible to directly discriminate two species simultaneously binding to different sites on a protein, which limits the utility of SPR, for example, in the study of allosteric binders or bi-specific molecules. It is also impossible in principle to discriminate protein conformation changes from actual binding events. Here we demonstrate how Label-Enhanced SPR can be utilized to discriminate and quantitatively monitor the simultaneous binding of two different species - one dye-labeled and one unlabeled - on a standard, single-wavelength SPR instrument. This new technique increases the versatility of SPR technology by opening up application areas where the usefulness of the approach has previously been limited. Copyright © 2018 Elsevier Inc. All rights reserved.

Optical nanoantennas for multiband surface-enhanced infrared and raman spectroscopy

KAUST Repository

D'Andrea, Cristiano; Bochterle, Jö rg; Toma, Andrea; Huck, Christian W.; Neubrech, Frank; Messina, Elena; Fazio, Barbara; Maragó , Onofrio M.; Di Fabrizio, Enzo M.; Lamy De La Chapelle, Marc L.; Gucciardi, Pietro Giuseppe; Pucci, Annemarie

2013-01-01

In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm -1 energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantenna's surface is accomplished, with signal enhancement factors of 5 × 102 for SERS (electromagnetic enhancement) and up to 105 for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances. © 2013 American Chemical Society.

Manipulating individual dichlorotin phthalocyanine molecules on Cu(100) surface at room temperature by scanning tunneling microscopy

International Nuclear Information System (INIS)

Li, Chao; Xiang, Feifei; Wang, Zhongping; Liu, Xiaoqing; Jiang, Danfeng; Wang, Li; Wang, Guang; Zhang, Xueao; Chen, Wei

2014-01-01

Single molecule manipulations have been achieved on dichlorotin phthalocyanine(SnCl 2 Pc) molecules adsorbed on Cu (100) at room temperature. Scanning tunneling microscopy observations directly demonstrate that the individual SnCl 2 Pc molecules can be moved along the [100] direction on Cu(100) surface by employing a scanning tunneling microscope tip fixed at the special position of the molecules. The orientation of the molecule can be switched between two angles of ±28° with respect to the [011] surface direction in the same way. Dependences of the probability of molecular motion on the distances between the tip and the molecules reveal that the mechanism for such manipulation of a SnCl 2 Pc molecule is dominated by the repulsive interactions between the tip and the molecules. With the assistance of this manipulation process, a prototype molecular storage array with molecular orientation as information carrier and an artificial hydrogen bonded supramolecular structure have been constructed on the surface. (paper)

Single OR molecule and OR atomic circuit logic gates interconnected on a Si(100)H surface

International Nuclear Information System (INIS)

Ample, F; Joachim, C; Duchemin, I; Hliwa, M

2011-01-01

Electron transport calculations were carried out for three terminal OR logic gates constructed either with a single molecule or with a surface dangling bond circuit interconnected on a Si(100)H surface. The corresponding multi-electrode multi-channel scattering matrix (where the central three terminal junction OR gate is the scattering center) was calculated, taking into account the electronic structure of the supporting Si(100)H surface, the metallic interconnection nano-pads, the surface atomic wires and the molecule. Well interconnected, an optimized OR molecule can only run at a maximum of 10 nA output current intensity for a 0.5 V bias voltage. For the same voltage and with no molecule in the circuit, the output current of an OR surface atomic scale circuit can reach 4 μA.

NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Platinum plasmonic nanostructure arrays for massively parallel single-molecule detection based on enhanced fluorescence measurements

International Nuclear Information System (INIS)

Saito, Toshiro; Takahashi, Satoshi; Obara, Takayuki; Itabashi, Naoshi; Imai, Kazumichi

2011-01-01

We fabricated platinum bowtie nanostructure arrays producing fluorescence enhancement and evaluated their performance using two-photon photoluminescence and single-molecule fluorescence measurements. A comprehensive selection of suitable materials was explored by electromagnetic simulation and Pt was chosen as the plasmonic material for visible light excitation near 500 nm, which is preferable for multicolor dye-labeling applications like DNA sequencing. The observation of bright photoluminescence (λ = 500-600 nm) from each Pt nanostructure, induced by irradiation at 800 nm with a femtosecond laser pulse, clearly indicates that a highly enhanced local field is created near the Pt nanostructure. The attachment of a single dye molecule was attempted between the Pt triangles of each nanostructure by using selective immobilization chemistry. The fluorescence intensities of the single dye molecule localized on the nanostructures were measured. A highly enhanced fluorescence, which was increased by a factor of 30, was observed. The two-photon photoluminescence intensity and fluorescence intensity showed qualitatively consistent gap size dependence. However, the average fluorescence enhancement factor was rather repressed even in the nanostructure with the smallest gap size compared to the large growth of photoluminescence. The variation of the position of the dye molecule attached to the nanostructure may influence the wide distribution of the fluorescence enhancement factor and cause the rather small average value of the fluorescence enhancement factor.

Electrical properties of SAM-modified ITO surface using aromatic small molecules with double bond carboxylic acid groups for OLED applications

Energy Technology Data Exchange (ETDEWEB)

Can, Mustafa [Izmir Katip Celebi University, Faculty of Engineering, Department of Engineering Sciences, Çiğli, Izmir (Turkey); Havare, Ali Kemal [Toros University, Faculty of Engineering, Electric and Electronic Department, Mersin (Turkey); Aydın, Hasan; Yagmurcukardes, Nesli [Izmir Institute of Technology, Material Science and Engineering, Izmir (Turkey); Demic, Serafettin [Izmir Katip Celebi University, Faculty of Engineering, Department of Material Science and Engineering, Çiğli, Izmir (Turkey); Icli, Sıddık [Ege University, Solar Energy Institute, Izmir (Turkey); Okur, Salih, E-mail: salih.okur@ikc.edu.tr [Izmir Katip Celebi University, Faculty of Engineering, Department of Material Science and Engineering, Çiğli, Izmir (Turkey)

2014-09-30

Graphical abstract: - Highlights: • We report that the performance of OLED consist of aromatic small molecules with double bond carboxylic acid groups on ITO surface. • The OLED devices were tested in terms of electrical and optical characteristics. • The I–V results show that OLEDs with SAM-modified ITO surface have lower turn on voltages than OLED configurations without SAMs. - Abstract: 5-[(3-Methylphenyl)(phenyl)amino]isophthalic acid (5-MePIFA) and 5-(diphenyl)amino]isophthalic acid (5-DPIFA) organic molecules were synthesized to form self-assembled monolayer on indium tin oxide (ITO) anode to enhance hole transport from ITO to organic hole transport layers such as TPD. The modified surface was characterized by scanning tunneling microscopy (STM). The change in the surface potential was measured by Kelvin probe force microscopy (KPFM). Our Kelvin probe force microscopy (KPFM) measurements showed that the surface potentials increased more than 100 mV with reference to bare indium tin-oxide. The results show that the threshold voltage on OLEDs with modified ITO is lowered significantly compared to OLEDs with unmodified ITO. The hole mobility of TPD has been estimated using space–charge-limited current measurements (SCLC)

Electrical properties of SAM-modified ITO surface using aromatic small molecules with double bond carboxylic acid groups for OLED applications

International Nuclear Information System (INIS)

Can, Mustafa; Havare, Ali Kemal; Aydın, Hasan; Yagmurcukardes, Nesli; Demic, Serafettin; Icli, Sıddık; Okur, Salih

2014-01-01

Graphical abstract: - Highlights: • We report that the performance of OLED consist of aromatic small molecules with double bond carboxylic acid groups on ITO surface. • The OLED devices were tested in terms of electrical and optical characteristics. • The I–V results show that OLEDs with SAM-modified ITO surface have lower turn on voltages than OLED configurations without SAMs. - Abstract: 5-[(3-Methylphenyl)(phenyl)amino]isophthalic acid (5-MePIFA) and 5-(diphenyl)amino]isophthalic acid (5-DPIFA) organic molecules were synthesized to form self-assembled monolayer on indium tin oxide (ITO) anode to enhance hole transport from ITO to organic hole transport layers such as TPD. The modified surface was characterized by scanning tunneling microscopy (STM). The change in the surface potential was measured by Kelvin probe force microscopy (KPFM). Our Kelvin probe force microscopy (KPFM) measurements showed that the surface potentials increased more than 100 mV with reference to bare indium tin-oxide. The results show that the threshold voltage on OLEDs with modified ITO is lowered significantly compared to OLEDs with unmodified ITO. The hole mobility of TPD has been estimated using space–charge-limited current measurements (SCLC)

Perfect-absorption graphene metamaterials for surface-enhanced molecular fingerprint spectroscopy

Science.gov (United States)

Guo, Xiangdong; Hu, Hai; Liao, Baoxin; Zhu, Xing; Yang, Xiaoxia; Dai, Qing

2018-05-01

Graphene plasmon with extremely strong light confinement and tunable resonance frequency represents a promising surface-enhanced infrared absorption (SEIRA) sensing platform. However, plasmonic absorption is relatively weak (approximately 1%-9%) in monolayer graphene nanostructures, which would limit its sensitivity. Here, we theoretically propose a hybrid plasmon-metamaterial structure that can realize perfect absorption in graphene with a low carrier mobility of 1000 cm2 V-1 s-1. This structure combines a gold reflector and a gold grating to the graphene plasmon structures, which introduce interference effect and the lightning-rod effect, respectively, and largely enhance the coupling of light to graphene. The vibration signal of trace molecules can be enhanced up to 2000-fold at the hotspot of the perfect-absorption structure, enabling the SEIRA sensing to reach the molecular level. This hybrid metal-graphene structure provides a novel path to generate high sensitivity in nanoscale molecular recognition for numerous applications.

Surface functionalization of bioactive glasses with natural molecules of biological significance, Part I: Gallic acid as model molecule

Science.gov (United States)

Zhang, Xin; Ferraris, Sara; Prenesti, Enrico; Verné, Enrica

2013-12-01

Gallic acid (3,4,5-trihydroxybenzoic acid, GA) and its derivatives are a group of biomolecules (polyphenols) obtained from plants. They have effects which are potentially beneficial to heath, for example they are antioxidant, anticarcinogenic and antibacterial, as recently investigated in many fields such as medicine, food and plant sciences. The main drawbacks of these molecules are both low stability and bioavailability. In this research work the opportunity to graft GA to bioactive glasses is investigated, in order to deliver the undamaged biological molecule into the body, using the biomaterial surfaces as a localized carrier. GA was considered for functionalization since it is a good model molecule for polyphenols and presents several interesting biological activities, like antibacterial, antioxidant and anticarcinogenic properties. Two different silica based bioactive glasses (SCNA and CEL2), with different reactivity, were employed as substrates. UV photometry combined with the Folin&Ciocalteu reagent was adopted to test the concentration of GA in uptake solution after functionalization. This test verified how much GA consumption occurred with surface modification and it was also used on solid samples to test the presence of GA on functionalized glasses. XPS and SEM-EDS techniques were employed to characterize the modification of material surface properties and functional group composition before and after functionalization.

Enhancing SERS by Means of Supramolecular Charge Transfer

Science.gov (United States)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Laser ablation surface-enhanced Raman microspectroscopy.

Science.gov (United States)

Londero, Pablo S; Lombardi, John R; Leona, Marco

2013-06-04

Improved identification of trace organic compounds in complex matrixes is critical for a variety of fields such as material science, heritage science, and forensics. Surface-enhanced Raman scattering (SERS) is a vibrational spectroscopy technique that can attain single-molecule sensitivity and has been shown to complement mass spectrometry, but lacks widespread application without a robust method that utilizes the effect. We demonstrate a new, highly sensitive, and widely applicable approach to SERS analysis based on laser ablation in the presence of a tailored plasmonic substrate. We analyze several challenging compounds, including non-water-soluble pigments and dyed leather from an ancient Egyptian chariot, achieving sensitivity as high as 120 amol for a 1:1 signal-to-noise ratio and 5 μm spatial resolution. This represents orders of magnitude improvement in spatial resolution and sensitivity compared to those of other SERS approaches intended for widespread application, greatly increasing the applicability of SERS.

Internal state distributions of molecules scattering and desorbing from surfaces

International Nuclear Information System (INIS)

Auerbach, D.J.

1983-01-01

Attempts are made to interpret scattering experiments of NO molecules on Ag(111) where a (rotational) state-specific detector has been used. A model using an anisotropic potential is proposed to explain the observed incoming energy- and angle dependence. The so-called rotational rainbows are explained. It is concluded, that in this way information on intermolecular potentials and the transfer of translational to rotational energy in the dynamics of trapping and sticking of molecules on surfaces can be extracted. (G.Q.)

Hydrophobicity-driven self-assembly of protein and silver nanoparticles for protein detection using surface-enhanced Raman scattering.

Science.gov (United States)

Kahraman, Mehmet; Balz, Ben N; Wachsmann-Hogiu, Sebastian

2013-05-21

Surface-enhanced Raman scattering (SERS) is a promising analytical technique for the detection and characterization of biological molecules and structures. The role of hydrophobic and hydrophilic surfaces in the self-assembly of protein-metallic nanoparticle structures for label-free protein detection is demonstrated. Aggregation is driven by both the hydrophobicity of the surface as well as the charge of the proteins. The best conditions for obtaining a reproducible SERS signal that allows for sensitive, label-free protein detection are provided by the use of hydrophobic surfaces and 16 × 10(11) NPs per mL. A detection limit of approximately 0.5 μg mL(-1) is achieved regardless of the proteins' charge properties and size. The developed method is simple and can be used for reproducible and sensitive detection and characterization of a wide variety of biological molecules and various structures with different sizes and charge status.

Jump rates for surface diffusion of large molecules from first principles

Energy Technology Data Exchange (ETDEWEB)

Shea, Patrick, E-mail: patrick.shea@dal.ca; Kreuzer, Hans Jürgen [Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia B3H 3J5 (Canada)

2015-04-21

We apply a recently developed stochastic model for the surface diffusion of large molecules to calculate jump rates for 9,10-dithioanthracene on a Cu(111) surface. The necessary input parameters for the stochastic model are calculated from first principles using density functional theory (DFT). We find that the inclusion of van der Waals corrections to the DFT energies is critical to obtain good agreement with experimental results for the adsorption geometry and energy barrier for diffusion. The predictions for jump rates in our model are in excellent agreement with measured values and show a marked improvement over transition state theory (TST). We find that the jump rate prefactor is reduced by an order of magnitude from the TST estimate due to frictional damping resulting from energy exchange with surface phonons, as well as a rotational mode of the diffusing molecule.

Enhanced antibody recognition with a magneto-optic surface plasmon resonance (MO-SPR) sensor.

Science.gov (United States)

Manera, Maria Grazia; Ferreiro-Vila, Elías; Garcia-Martin, José Miguel; Garcia-Martin, Antonio; Rella, Roberto

2014-08-15

A comparison between sensing performance of traditional SPR (Surface Plasmon Resonance) and magneto-optic SPR (MOSPR) transducing techniques is presented in this work. MOSPR comes from an evolution of traditional SPR platform aiming at modulating Surface Plasmon wave by the application of an external magnetic field in transverse configuration. Previous work demonstrated that, when the Plasmon resonance is excited in these structures, the external magnetic field induces a modification of the coupling of the incident light with the Surface Plasmon Polaritons (SPP). Besides, these structures can lead to an enhancement in the magneto-optical (MO) activity when the SPP is excited. This phenomenon is exploited in this work to demonstrate the possibility to use the enhanced MO signal as proper transducer signal for investigating biomolecular interactions in liquid phase. To this purpose, the transducer surface was functionalized by thiol chemistry and used for recording the binding between Bovine Serum Albumin molecules immobilized onto the surface and its complementary target. Higher sensing performance in terms of sensitivity and lower limit of detection of the MOSPR biosensor with respect to traditional SPR sensors is demonstrated. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption behavior of sulfur-containing amino acid molecule on transition metal surface studied by S K-edge NEXAFS

International Nuclear Information System (INIS)

Yagi, S.; Matsumura, K.; Nakano, Y.; Ikenaga, E.; Sardar, S.A.; Syed, J.A.; Soda, K.; Hashimoto, E.; Tanaka, K.; Taniguchi, M.

2003-01-01

Adsorption behavior of a sulfur-containing amino acid L-cysteine molecule on transition metal surface have been investigated by S K-edge near-edge X-ray absorption fine structure. The L-cysteine molecule for first adsorption layer was found to dissociate on polycrystalline nickel surface, whereas molecularly adsorbed on copper surface at room temperature. Most of the L-cysteine molecules have been dissociated on nickel surface in annealing condition up to 353 K. On the other hand, the L-cysteine molecule did not dissociate on copper surface and the elongation of the S-C bonding occurred at 353 K

A Small-Molecule Screen for Enhanced Homing of Systemically Infused Cells

Directory of Open Access Journals (Sweden)

Oren Levy

2015-03-01

Full Text Available Poor homing of systemically infused cells to disease sites may limit the success of exogenous cell-based therapy. In this study, we screened 9,000 signal-transduction modulators to identify hits that increase mesenchymal stromal cell (MSC surface expression of homing ligands that bind to intercellular adhesion molecule 1 (ICAM-1, such as CD11a. Pretreatment of MSCs with Ro-31-8425, an identified hit from this screen, increased MSC firm adhesion to an ICAM-1-coated substrate in vitro and enabled targeted delivery of systemically administered MSCs to inflamed sites in vivo in a CD11a- (and other ICAM-1-binding domains-dependent manner. This resulted in a heightened anti-inflammatory response. This represents a new strategy for engineering cell homing to enhance therapeutic efficacy and validates CD11a and ICAM-1 as potential targets. Altogether, this multi-step screening process may significantly improve clinical outcomes of cell-based therapies.

A Classical Potential to Model the Adsorption of Biological Molecules on Oxidized Titanium Surfaces.

Science.gov (United States)

Schneider, Julian; Ciacchi, Lucio Colombi

2011-02-08

The behavior of titanium implants in physiological environments is governed by the thin oxide layer that forms spontaneously on the metal surface and mediates the interactions with adsorbate molecules. In order to study the adsorption of biomolecules on titanium in a realistic fashion, we first build up a model of an oxidized Ti surface in contact with liquid water by means of extensive first-principles molecular dynamics simulations. Taking the obtained structure as reference, we then develop a classical potential to model the Ti/TiOx/water interface. This is based on the mapping with Coulomb and Lennard-Jones potentials of the adsorption energy landscape of single water and ammonia molecules on the rutile TiO2(110) surface. The interactions with arbitrary organic molecules are obtained via standard combination rules to established biomolecular force fields. The transferability of our potential to the case of organic molecules adsorbing on the oxidized Ti surface is checked by comparing the classical potential energy surfaces of representative systems to quantum mechanical results at the level of density functional theory. Moreover, we calculate the heat of immersion of the TiO2 rutile surface and the detachment force of a single tyrosine residue from steered molecular dynamics simulations, finding good agreement with experimental reference data in both cases. As a first application, we study the adsorption behavior of the Arg-Gly-Asp (RGD) peptide on the oxidized titanium surface, focusing particularly on the calculation of the free energy of desorption.

Ag-ZnO nanostructure for ANTA explosive molecule detection

Energy Technology Data Exchange (ETDEWEB)

Shaik, Ummar Pasha [Advanced Center of Research in High Energy Materials, University of Hyderabad, Hyderabad 500046 (India); Sangani, L. D. Varma [Centre for Advanced Studies in Electronics Science and Technology, School of Physics, University of Hyderabad (India); Gaur, Anshu [Department of Industrial Engineering, University of Trento, Via Sommarive9, Trento (Italy); Mohiddon, Md. Ahamad, E-mail: ahamed.vza@gmail.com [National Institute of Technology Andhra Pradesh, Tadepalliguem 534101, AP, India Phone : (+) 91-40-23134382, FAX: (+) 91-40-23010227 (India); Krishna, M. Ghanashyam [Advanced Center of Research in High Energy Materials, University of Hyderabad, Hyderabad 500046 (India); Centre for Advanced Studies in Electronics Science and Technology, School of Physics, University of Hyderabad (India); National Institute of Technology Andhra Pradesh, Tadepalliguem 534101, AP, India Phone : (+) 91-40-23134382, FAX: (+) 91-40-23010227 (India)

2016-05-23

Ag/ZnO nanostructure for surface enhanced Raman scattering application in the detection of ANTA explosive molecule is demonstrated. A highly rough ZnO microstructure was achieved by rapid thermal annealing of metallic Zn film. Different thickness Ag nanostructures are decorated over these ZnO microstructures by ion beam sputtering technique. Surface enhanced Raman spectroscopic studies carried out over Ag/ZnO substrates have shown three orders higher enhancement compared to bare Ag nanostructure deposited on the same substrate. The reasons behind such huge enhancement are discussed based on the morphology of the sample.

Optical nanoantennas for multiband surface-enhanced infrared and raman spectroscopy

KAUST Repository

D'Andrea, Cristiano

2013-04-23

In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm -1 energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantenna\\'s surface is accomplished, with signal enhancement factors of 5 × 102 for SERS (electromagnetic enhancement) and up to 105 for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances. © 2013 American Chemical Society.

Surface-enhanced Raman scattering active gold nanoparticle/nanohole arrays fabricated through electron beam lithography

Science.gov (United States)

Wu, Tsunghsueh; Lin, Yang-Wei

2018-03-01

Effective surface-enhanced Raman scattering (SERS)-active substrates from gold nanoparticle and gold nanohole arrays were successfully fabricated through electron beam lithography with precise computer-aided control of the unit size and intergap distance. Their SERS performance was evaluated using 4-mercaptobenzoic acid (4-MBA). These gold arrays yielded strong SERS signals under 785 nm laser excitation. The enhancement factors for 4-MBA molecules on the prepared gold nanoparticle and nanohole arrays maxed at 1.08 × 107 and 8.61 × 106, respectively. The observed increase in SERS enhancement was attributed to the localized surface plasmon resonance (LSPR) wavelength shifting toward the near-infrared regime when the gold nanohole diameter increased, in agreement with the theoretical prediction in this study. The contribution of LSPR to the Raman enhancement from nanohole arrays deposited on fluorine-doped tin oxide glass was elucidated by comparing SERS and transmission spectra. This simple fabrication procedure, which entails employing electron beam lithography and the controllability of the intergap distance, suggests highly promising uses of nanohole arrays as functional components in sensing and photonic devices.

Observing single molecule chemical reactions on metal nanoparticles.

Energy Technology Data Exchange (ETDEWEB)

Emory, S. R. (Steven R.); Ambrose, W. Patrick; Goodwin, P. M. (Peter M); Keller, Richard A.

2001-01-01

We report the study of the photodecomposition of single Rhodamine 6G (R6G) dye molecules adsorbed on silver nanoparticles. The nanoparticles were immobilized and spatially isolated on polylysine-derivatized glass coverslips, and confocal laser microspectroscopy was used to obtain surface-enhanced Raman scattering (SERS) spectra from individual R6G molecules. The photodecomposition of these molecules was observed with 150-ms temporal resolution. The photoproduct was identified as graphitic carbon based on the appearance of broad SERS vibrational bands at 1592 cm{sup -1} and 1340 cm{sup -1} observed in both bulk and averaged single-molecule photoproduct spectra. In contrast, when observed at the single-molecule level, the photoproduct yielded sharp SERS spectra. The inhomogeneous broadening of the bulk SERS spectra is due to a variety of photoproducts in different surface orientations and is a characteristic of ensemble-averaged measurements of disordered systems. These single-molecule studies indicate a photodecomposition pathway by which the R6G molecule desorbs from the metal surface, an excited-state photoreaction occurs, and the R6G photoproduct(s) readsorbs to the surface. A SERS spectrum is obtained when either the intact R6G or the R6G photoproduct(s) are adsorbed on a SERS-active site. This work further illustrates the power of single-molecule spectroscopy (SMS) to reveal unique behaviors of single molecules that are not discernable with bulk measurements.

Influences of Au ion radiation on microstructure and surface-enhanced Raman scattering of nanoporous copper

Science.gov (United States)

Wang, Jing; Hu, Zhaoyi; Li, Rui; Liu, Xiongjun; Xu, Chuan; Wang, Hui; Wu, Yuan; Fu, Engang; Lu, Zhaoping

2018-05-01

In this work, effects of Au ion irradiation on microstructure and surface-enhanced Raman scattering (SERS) performance of nanoporous copper (NPC) were investigated. It is found that the microstructure of NPC could be tailored by the ion irradiation dose, i.e., the pore size decreases while the ligament size significantly coarsens with the increase of the irradiation dose. In addition, the SERS enhancement for rhodamine 6G molecules was improved by Au ions irradiation at an appropriate dose. The underlying mechanism of the increase of SERS enhancement resulted from ion irradiation was discussed. Our findings could provide a new way to tune nanoporosity of nanoporous metals and improve their SERS performance.

Dimensional scale effects on surface enhanced Raman scattering efficiency of self-assembled silver nanoparticle clusters

International Nuclear Information System (INIS)

Fasolato, C.; Domenici, F.; De Angelis, L.; Luongo, F.; Postorino, P.; Sennato, S.; Mura, F.; Costantini, F.; Bordi, F.

2014-01-01

A study of the Surface Enhanced Raman Scattering (SERS) from micrometric metallic nanoparticle aggregates is presented. The sample is obtained from the self-assembly on glass slides of micro-clusters of silver nanoparticles (60 and 100 nm diameter), functionalized with the organic molecule 4-aminothiophenol in water solution. For nanoparticle clusters at the micron scale, a maximum enhancement factor of 10 9 is estimated from the SERS over the Raman intensity ratio normalized to the single molecule contribution. Atomic force microscopy, correlated to spatially resolved Raman measurements, allows highlighting the connection between morphology and efficiency of the plasmonic system. The correlation between geometric features and SERS response of the metallic structures reveals a linear trend of the cluster maximum scattered intensity as a function of the surface area of the aggregate. On given clusters, the intensity turns out to be also influenced by the number of stacking planes of the aggregate, thus suggesting a plasmonic waveguide effect. The linear dependence results weakened for the largest area clusters, suggesting 30 μm 2 as the upper limit for exploiting the coherence over large scale of the plasmonic response.

Anchoring of organic molecules to a metal surface: HtBDC on Cu(110)

DEFF Research Database (Denmark)

Schunack, M.; Petersen, L.; Kuhnle, A.

2001-01-01

The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce...

Surface-enhanced Raman scattering on gold nanorod pairs with interconnection bars of different widths

KAUST Repository

Yue, Weisheng

2012-08-01

We demonstrate that surface-enhanced Raman scattering (SERS) enhancement could be tuned by adjusting the width of a connection bar at the bottom of a gold nanorod pair. Arrays of gold nanorod pairs with interconnection bars of different widths at the bottom of the interspace were fabricated by electron-beam lithography and used for the SERS study. Rhodamine 6G (R6G) was used as the probe molecule for the SERS. In addition to the large SERS enhancement observed in the nanostructured substrates, the SERS enhancement increases as the width of the connection bar increases. This result provides an important method for tuning SERS enhancement. Numerical simulations of electromagnetic properties on the nanostructures were performed with CST Microwave Studio, and the results correspond well with the experimental observations. © 2012 Elsevier B.V. All rights reserved.

Single Molecule Raman Detection of Enkephalin on Silver Colloidal Particles

DEFF Research Database (Denmark)

Kneipp, Katrin; Kneipp, Holger; Abdali, Salim

2004-01-01

the Raman signal the enkephalin molecules have been attached to silver colloidal cluster structures. The experiments demonstrate that the SERS signal of the strongly enhanced ring breathing vibration of phenylalanine at 1000 cm-1 can be used as “intrinsic marker” for detecting a single enkephalin molecule...... and for monitoring its diffusion on the surface of the silver colloidal cluster without using a specific label molecule....

Surface enhanced Raman spectroscopy platform based on graphene with one-year stability

Energy Technology Data Exchange (ETDEWEB)

Tite, Teddy [Univ Lyon, UJM-Saint-Etienne, CNRS, Laboratoire Hubert Curien UMR 5516, 18 rue Professeur Benoit Lauras, F-42000 Saint-Etienne (France); Barnier, Vincent [Ecole Nationale Supérieure des Mines, CNRS, Laboratoire Georges Friedel UMR 5307, 158 cours Fauriel, F-42023 Saint-Etienne (France); Donnet, Christophe, E-mail: Christophe.Donnet@univ-st-etienne.fr [Univ Lyon, UJM-Saint-Etienne, CNRS, Laboratoire Hubert Curien UMR 5516, 18 rue Professeur Benoit Lauras, F-42000 Saint-Etienne (France); Loir, Anne–Sophie; Reynaud, Stéphanie; Michalon, Jean–Yves; Vocanson, Francis; Garrelie, Florence [Univ Lyon, UJM-Saint-Etienne, CNRS, Laboratoire Hubert Curien UMR 5516, 18 rue Professeur Benoit Lauras, F-42000 Saint-Etienne (France)

2016-04-01

We report the synthesis, characterization and use of a robust surface enhanced Raman spectroscopy platform with a stable detection for up to one year of Rhodamine R6G at a concentration of 10{sup −6} M. The detection of aminothiophenol and methyl parathion, as active molecules of commercial insecticides, is further demonstrated at concentrations down to 10{sup −5}–10{sup −6} M. This platform is based on large scale textured few-layer (fl) graphene obtained without any need of graphene transfer. The synthesis route is based on diamond-like carbon films grown by pulsed laser deposition, deposited onto silicon substrates covered by a Ni layer prior to diamond-like carbon deposition. The formation of fl-graphene film, confirmed by Raman spectroscopy and mapping, is obtained by thermal annealing inducing the diffusion of Ni atoms and the concomitant formation of nickel silicide compounds, as identified by Raman and Auger electron spectroscopies. The textured fl-graphene films were decorated with gold nanoparticles to optimize the efficiency of the SERS device to detect organic molecules at low concentrations. - Highlights: • Synthesis of graphene film from amorphous carbon by pulsed laser deposition with nickel catalyst • Large scale textured graphene with nanoscale roughness obtained through nickel silicide formation • Films used for surface enhanced Raman spectroscopy detection of organophosphate compounds • Stability of the SERS platforms over up to one year.

Advances in single-molecule magnet surface patterning through microcontact printing

NARCIS (Netherlands)

Mannini, Matteo; Bonacchi, D.; Bonacchi, Daniele; Zobbi, Laura; Piras, Federica M.; Speets, E.A.; Caneschi, Andrea; Cornia, Andrea; Magnani, Agnese; Ravoo, B.J.; Reinhoudt, David; Sessoli, Roberta; Gatteschi, Dante

2005-01-01

We present an implementation of strategies to deposit single-molecule magnets (SMMs) using microcontact printing (uCP). We describe different approaches of CP to print stripes of a sulfur-functionalized dodecamanganese(III,IV) cluster on gold surfaces. Comparison by atomic force microscopy profile

Tip-Enhanced Nano-Spectroscopy, Imaging, and Control: From Single Molecules to van der Waals Materials

Science.gov (United States)

Park, Kyoung-Duck

Photon-induced phenomena in molecules and other materials play a significant role in device applications as well as understanding their physical properties. While a range of device applications using organic and inorganic molecules and soft and hard materials have led striking developments in modern technologies, using bulk systems has reached the limit in their functions, performance, and regarding application range. Recently, low-dimensional systems have emerged as appealing resources for the advanced technologies based on their significantly improved functions and properties. Hence, understanding light-matter interactions at their natural length scale is of fundamental significance, in addition to the next generation device applications. This thesis demonstrates a range of new functions and behaviors of low-dimensional materials revealed and controlled by the advanced tip-enhanced near-field spectroscopy and imaging techniques exceeding the current instrumental limits. To understand the behaviors of zero-dimensional (0D) molecular systems in interacting environments, we explore new regimes in tip-enhanced Raman spectroscopy (TERS) and scanning near-field optical microscopy (SNOM), revealing the fundamental nature of single-molecule dynamics and nanoscale spatial heterogeneity of biomolecules on the cell membranes. To gain insight into intramolecular properties and dynamic processes of single molecules, we use TERS at cryogenic temperatures. From temperature-dependent line narrowing and splitting, we investigate and quantify ultrafast vibrational dephasing, intramolecular coupling, and conformational heterogeneity. Through correlation analysis of fluctuations of individual modes, we observe rotational motion and spectral fluctuations of single-molecule. We extend single-molecule spectroscopy study into in situ nano-biomolecular imaging of cancer cells by developing in-liquid SNOM. We use a new mechanical resonance control, achieving a high-Q force sensing of the

Surface-enhanced Raman spectrum of Gly-Gly adsorbed on the silver colloidal surface

Science.gov (United States)

Xiaojuan, Yuan; Huaimin, Gu; Jiwei, Wu

2010-08-01

Raman and SERS spectra of homodipeptide Gly-Gly and Gly were recorded and compared in this paper, and band assignment for the functional groups contained in these molecules was analyzed in detail. Time-dependent and pH-dependent SERS spectra of Gly-Gly molecule adsorbed on nano-colloidal silver surface were also studied. The time-dependent SERS spectra of Gly-Gly are characterized by the increase in intensity of bands primarily representing the vibrational signatures emanating from the amino and amide moiety of Gly-Gly molecule. It is found that the adsorption style of Gly-Gly on the silver colloid changes as time goes on; at 5 min after adding the sample to the silver colloid, Gly-Gly adsorbs on silver surface firstly through the carboxylate, amino and amide groups, and then the carboxylate group is far away from the silver surface at 10 min to 3 days. The SERS variation of Gly-Gly with the change of pH suggests that the adsorption style is pH-dependent, the different adsorption behavior of the Gly-Gly occurs on silver surface at different pH values.

Differential Expression of Osteo-Modulatory Molecules in Periodontal Ligament Stem Cells in Response to Modified Titanium Surfaces

Directory of Open Access Journals (Sweden)

So Yeon Kim

2014-01-01

Full Text Available This study assessed differential gene expression of signaling molecules involved in osteogenic differentiation of periodontal ligament stem cells (PDLSCs subjected to different titanium (Ti surface types. PDLSCs were cultured on tissue culture polystyrene (TCPS, and four types of Ti discs (PT, SLA, hydrophilic PT (pmodPT, and hydrophilic SLA (modSLA with no osteoinductive factor and then osteogenic activity, including alkaline phosphatase (ALP activity, mRNA expression of runt-related gene 2, osterix, FOSB, FRA1, and protein levels of osteopontin and collagen type IA, were examined. The highest osteogenic activity appeared in PDLSCs cultured on SLA, compared with the TCPS and other Ti surfaces. The role of surface properties in affecting signaling molecules to modulate PDLSC behavior was determined by examining the regulation of Wnt pathways. mRNA expression of the canonical Wnt signaling molecules, Wnt3a and β-catenin, was higher on SLA and modSLA than on smooth surfaces, but gene expression of the calcium-dependent Wnt signaling molecules Wnt5a, calmodulin, and NFATc1 was increased significantly on PT and pmodPT. Moreover, integrin α2/β1, sonic hedgehog, and Notch signaling molecules were affected differently by each surface modification. In conclusion, surface roughness and hydrophilicity can affect differential Wnt pathways and signaling molecules, targeting the osteogenic differentiation of PDLSCs.

Adsorption and dissociation of oxygen molecules on Si(111)-(7×7) surface

International Nuclear Information System (INIS)

Niu, Chun-Yao; Wang, Jian-Tao

2013-01-01

The adsorption and dissociation of O 2 molecules on Si(111)-(7×7) surface have been studied by first-principles calculations. Our results show that all the O 2 molecular species adsorbed on Si(111)-(7×7) surface are unstable and dissociate into atomic species with a small energy barrier about 0.1 eV. The single O 2 molecule adsorption tends to form an ins×2 or a new metastable ins×2* structure on the Si adatom sites and the further coming O 2 molecules adsorb on those structures to produce an ad-ins×3 structure. The ad-ins×3 structure is indeed highly stable and kinetically limited for diving into the subsurface layer to form the ins×3-tri structure by a large barrier of 1.3 eV. Unlike the previous views, we find that all the ad-ins, ins×2, and ad-ins×3 structures show bright images, while the ins×2*, ins×3, and ins×3-tri structures show dark images. The proposed oxidation pathways and simulated scanning tunneling microscope images account well for the experimental results and resolve the long-standing confusion and issue about the adsorption and reaction of O 2 molecules on Si(111) surface

Degradation-by-design: Surface modification with functional substrates that enhance the enzymatic degradation of carbon nanotubes.

Science.gov (United States)

Sureshbabu, Adukamparai Rajukrishnan; Kurapati, Rajendra; Russier, Julie; Ménard-Moyon, Cécilia; Bartolini, Isacco; Meneghetti, Moreno; Kostarelos, Kostas; Bianco, Alberto

2015-12-01

Biodegradation of carbon-based nanomaterials has been pursued intensively in the last few years, as one of the most crucial issues for the design of safe, clinically relevant conjugates for biomedical applications. In this paper it is demonstrated that specific functional molecules can enhance the catalytic activity of horseradish peroxidase (HRP) and xanthine oxidase (XO) for the degradation of carbon nanotubes. Two different azido coumarins and one cathecol derivative are linked to multi-walled carbon nanotubes (MWCNTs). These molecules are good reducing substrates and strong redox mediators to enhance the catalytic activity of HRP. XO, known to metabolize various molecules mainly in the mammalian liver, including human, was instead used to test the biodegradability of MWCNTs modified with an azido purine. The products of the biodegradation process are characterized by transmission electron microscopy and Raman spectroscopy. The results indicate that coumarin and catechol moieties have enhanced the biodegradation of MWCNTs compared to oxidized nanotubes, likely due to the capacity of these substrates to better interact with and activate HRP. Although azido purine-MWCNTs are degraded less effectively by XO than oxidized nanotubes, the data uncover the importance of XO in the biodegradation of carbon-nanomaterials leading to their better surface engineering for biomedical applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface-enhanced Raman scattering based nonfluorescent probe for multiplex DNA detection.

Science.gov (United States)

Sun, Lan; Yu, Chenxu; Irudayaraj, Joseph

2007-06-01

To provide rapid and accurate detection of DNA markers in a straightforward, inexpensive, and multiplex format, an alternative surface-enhanced Raman scattering based probe was designed and fabricated to covalently attach both DNA probing sequence and nonfluorescent Raman tags to the surface of gold nanoparticles (DNA-AuP-RTag). The intensity of Raman signal of the probes could be controlled through the surface coverage of the nonfluorescent Raman tags (RTags). Detection sensitivity of these probes could be optimized by fine-tuning the amount of DNA molecules and RTags on the probes. Long-term stability of the DNA-AuP-RTag probes was found to be good (over 3 months). Excellent multiplexing capability of the DNA-AuP-RTag scheme was demonstrated by simultaneous identification of up to eight probes in a mixture. Detection of hybridization of single-stranded DNA to its complementary targets was successfully accomplished with a long-term goal to use nonfluorescent RTags in a Raman-based DNA microarray platform.

Electron-beam lithography of gold nanostructures for surface-enhanced Raman scattering

KAUST Repository

Yue, Weisheng

2012-10-26

The fabrication of nanostructured substrates with precisely controlled geometries and arrangements plays an important role in studies of surface-enhanced Raman scattering (SERS). Here, we present two processes based on electron-beam lithography to fabricate gold nanostructures for SERS. One process involves making use of metal lift-off and the other involves the use of the plasma etching. These two processes allow the successful fabrication of gold nanostructures with various kinds of geometrical shapes and different periodic arrangements. 4-mercaptopyridine (4-MPy) and Rhodamine 6G (R6G) molecules are used to probe SERS signals on the nanostructures. The SERS investigations on the nanostructured substrates demonstrate that the gold nanostructured substrates have resulted in large SERS enhancement, which is highly dependent on the geometrical shapes and arrangements of the gold nanostructures. © 2012 IOP Publishing Ltd.

Desorption dynamics of deuterium molecules from the Si(100)-(3x1) dideuteride surface.

Science.gov (United States)

Niida, T; Tsurumaki, H; Namiki, A

2006-01-14

We measured polar angle (theta)-resolved time-of-flight spectra of D2 molecules desorbing from the Si(100)-(3x1) dideuteride surface. The desorbing D2 molecules exhibit a considerable translational heating with mean desorption kinetic energies of approximately 0.25 eV, which is mostly independent of the desorption angles for 0 degreesdynamics of deuterium was discussed along the principle of detailed balance to predict their adsorption dynamics onto the monohydride Si surface.

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

Science.gov (United States)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

Single-Molecule Tribology: Force Microscopy Manipulation of a Porphyrin Derivative on a Copper Surface.

Science.gov (United States)

Pawlak, Rémy; Ouyang, Wengen; Filippov, Alexander E; Kalikhman-Razvozov, Lena; Kawai, Shigeki; Glatzel, Thilo; Gnecco, Enrico; Baratoff, Alexis; Zheng, Quanshui; Hod, Oded; Urbakh, Michael; Meyer, Ernst

2016-01-26

The low-temperature mechanical response of a single porphyrin molecule attached to the apex of an atomic force microscope (AFM) tip during vertical and lateral manipulations is studied. We find that approach-retraction cycles as well as surface scanning with the terminated tip result in atomic-scale friction patterns induced by the internal reorientations of the molecule. With a joint experimental and computational effort, we identify the dicyanophenyl side groups of the molecule interacting with the surface as the dominant factor determining the observed frictional behavior. To this end, we developed a generalized Prandtl-Tomlinson model parametrized using density functional theory calculations that includes the internal degrees of freedom of the side group with respect to the core and its interactions with the underlying surface. We demonstrate that the friction pattern results from the variations of the bond length and bond angles between the dicyanophenyl side group and the porphyrin backbone as well as those of the CN group facing the surface during the lateral and vertical motion of the AFM tip.

Surface enhanced raman spectroscopy on chip

DEFF Research Database (Denmark)

Hübner, Jörg; Anhøj, Thomas Aarøe; Zauner, Dan

2007-01-01

In this paper we report low resolution surface enhanced Raman spectra (SERS) conducted with a chip based spectrometer. The flat field spectrometer presented here is fabricated in SU-8 on silicon, showing a resolution of around 3 nm and a free spectral range of around 100 nm. The output facet...... is projected onto a CCD element and visualized by a computer. To enhance the otherwise rather weak Raman signal, a nanosurface is prepared and a sample solutions is impregnated on this surface. The surface enhanced Raman signal is picked up using a Raman probe and coupled into the spectrometer via an optical...... fiber. The obtained spectra show that chip based spectrometer together with the SERS active surface can be used as Raman sensor....

Sensitive and fast detection of fructose in complex media via symmetry breaking and signal amplification using surface-enhanced Raman spectroscopy.

Science.gov (United States)

Sun, Fang; Bai, Tao; Zhang, Lei; Ella-Menye, Jean-Rene; Liu, Sijun; Nowinski, Ann K; Jiang, Shaoyi; Yu, Qiuming

2014-03-04

A new strategy is proposed to sensitively and rapidly detect analytes with weak Raman signals in complex media using surface-enhanced Raman spectroscopy (SERS) via detecting the SERS signal changes of the immobilized probe molecules on SERS-active substrates upon binding of the analytes. In this work, 4-mercaptophenylboronic acid (4-MPBA) was selected as the probe molecule which was immobilized on the gold surface of a quasi-three-dimensional plasmonic nanostructure array (Q3D-PNA) SERS substrate to detect fructose. The molecule of 4-MPBA possesses three key functions: molecule recognition and reversible binding of the analyte via the boronic acid group, amplification of SERS signals by the phenyl group and thus shielding of the background noise of complex media, and immobilization on the surface of SERS-active substrates via the thiol group. Most importantly, the symmetry breaking of the 4-MPBA molecule upon fructose binding leads to the change of area ratio between totally symmetric 8a ring mode and nontotally symmetric 8b ring mode, which enables the detection. The detection curves were obtained in phosphate-buffered saline (PBS) and in undiluted artificial urine at clinically relevant concentrations, and the limit of detection of 0.05 mM was achieved.

Application of silver nanoparticles in the detection of SYBR Green I by surface enhanced Raman and surface-enhanced fluorescence

Science.gov (United States)

Guo, Wei; Wu, Jian; Wang, Chunyan; Zhang, Tian; Chen, Tao

2018-05-01

Silver nanomaterials have remarkable application in biomedical detection due to their unique surface plasmon resonance (SPR) characteristics. It can be used for surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). Current research elaborates a technique for improvement of SYBR Green I detection obtained from surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) by silver nanoparticles with the average size about 70 nm. Primarily, SYBR Green I is an important fluorescent dye used in polymerase chain reaction (PCR). It is found that both Raman and fluorescence can be used for detection of this dye. Furthermore, the enhanced efficiency of the Raman and fluorescence by SERS and SEF is observed in this study, the enhancement factor for Raman signals is 3.2 × 103, and the fluorescence intensity bincreased two times by SEF. The quantitative detection of SYBR Green I by SERS and SEF can be achieved. The present work can be used to improve the detection of SYBR Green I by SERS and SEF. It would also be employed for high-sensitive detection of other materials in the future.

Desorption dynamics of deuterium molecules from the Si(100)-(3×1) dideuteride surface

OpenAIRE

Niida, T; Tsurumaki, Hiroshi; Namiki, Akira

2006-01-01

We measured polar angle ()-resolved time-of-flight spectra of D2 molecules desorbing from the Si(100)-(3×1) dideuteride surface. The desorbing D2 molecules exhibit a considerable translational heating with mean desorption kinetic energies of 0.25 eV, which is mostly independent of the desorption angles for 0°30°. The observed desorption dynamics of deuterium was discussed along the principle of detailed balance to predict their adsorption dynamics onto the monohydride Si surface.

A Raman spectroscopy study on the effects of intermolecular hydrogen bonding on water molecules absorbed by borosilicate glass surface

Science.gov (United States)

Li, Fabing; Li, Zhanlong; Wang, Ying; Wang, Shenghan; Wang, Xiaojun; Sun, Chenglin; Men, Zhiwei

2018-05-01

The structural forms of water/deuterated water molecules located on the surface of borosilicate capillaries have been first investigated in this study on the basis of the Raman spectral data obtained at different temperatures and under atmospheric pressure for molecules in bulk and also for molecules absorbed by borosilicate glass surface. The strongest two fundamental bands locating at 3063 cm-1 (2438 cm-1) in the recorded Raman spectra are assigned here to the Osbnd H (Osbnd D) bond stretching vibrations and they are compared with the corresponding bands observed at 3124 cm-1 (2325 cm-1) in the Raman spectrum of ice Ih. Our spectroscopic observations have indicated that the structure of water and deuterated water molecules on borosilicate surface is similar to that of ice Ih (hexagonal phase of ice). These observations have also indicated that water molecules locate on the borosilicate surface so as to construct a bilayer structure and that strong and weak intermolecular hydrogen bonds are formed between water/deuterated molecules and silanol groups on borosilicate surface. In accordance with these findings, water and deuterated water molecules at the interface of capillary have a higher melting temperature.

Thermally generated metals for plasmonic coloring and surface-enhanced Raman sensing

Science.gov (United States)

Huang, Zhenping; Chen, Jian; Liu, Guiqiang; Wang, Yan; Liu, Yi; Tang, Li; Liu, Zhengqi

2018-03-01

Spectral coloring glass and its application on the surface-enhanced Raman scattering are demonstrated experimentally via a simple and moderate heat-treating of the top ultrathin gold film to create discrete nanoparticles, which can produce localized surface plasmon resonances and strong plasmonic near-field coupling effects. Ultrathin metal films with a wide range of thicknesses are investigated by different heat-treatment processes. The annealed metal films have been demonstrated with a series of spectral coloring responses. Moreover, the microscopy images of the metal film structures confirm the formation of distinct geometry features in these operation procedures. Densely packed nanoparticles are observed for the ultrathin metal film with the single-digit level of thickness. With increasing the film thickness over 10 nm, metallic clusters and porous morphologies can be obtained. Importantly, the metallic resonators can provide enhanced Raman scattering with the detection limit down to 10 - 7 molL - 1 of Rhodamine 6G molecules due to the excitation of plasmon resonances and strong near-field coupling effects. These features hold great potential for large-scale and low-cost production of colored glass and Raman substrate.

A fitting program for potential energy surfaces of bent triatomic molecules

International Nuclear Information System (INIS)

Searles, D.J.; Nagy-Felsobuki, E.I. von

1992-01-01

A program has been developed in order to fit analytical power series expansions (Dunham, Simon-Parr-Finlan, Ogilvie and their exponential variants) and Pade approximants to discrete ab initio potential energy surfaces of non-linear triatomic molecules. The program employs standard least-squares fitting techniques using the singular decomposition method in order to dampen the higher-order coefficients (if deemed necessary) without significantly degrading the fit. The program makes full use of the symmetry of a triatomic molecule and so addresses the D 3h , C 2v and C S cases. (orig.)

Interface formation between hydrocarbon ring molecules and III-V semiconductor surfaces

Energy Technology Data Exchange (ETDEWEB)

Passmann, Regina

2008-08-15

In this work a systematical study to investigate the adsorption structures of small hydrocarbon ring shaped molecules on III-V semiconductor surfaces with Photo-Emission Spectroscopy (PES), Reflectance Anisotropy Spectroscopy (RAS), Scanning Tunneling Microscopy (STM) as well as Low Electron Energy Diffraction (LEED) was performed. To investigate the influence of the surface structure in detail the surface dimer configuration to the adsorption process of organic molecules GaAs(001) surfaces, the c(4 x 4), the (2 x 4) and the (4 x 2) have been investigated as well as the adsorption of cyclopentene on the InP(001)(2 x 4) reconstructed surface. In the direct comparison it is shown that cyclopentene bonds to the InP(001)(2 x 4) surface via a cycloaddition like reaction. During this adsorption the double bond splits which is in contrast to the adsorption of cyclopentene on the GaAs(001) surfaces. Therefrom it is concluded that the surface geometry has an influence on the resulting adsorption structure. In order to investigate the influence of the intra-molecular double bonds, cyclopentene (one double bond), 1,4-cyclohexadiene (two double bonds) and benzene (three double bonds) were used for the characterization of the interface formation. With the investigations on the GaAs(001) reconstructed surfaces it was shown that a dependency of the bonding configuration on the intra-molecular double bonds exists. During the adsorption of cyclopentene no evidence was found that the double bond has to be involved in the interface formation while during the adsorption of 1,4-cyclohexadiene and benzene the double bonds are involved. Furthermore it was found that a bonding to As atoms of the surface is more likely than a bonding to Ga atoms. (orig.)

Interface formation between hydrocarbon ring molecules and III-V semiconductor surfaces

International Nuclear Information System (INIS)

Passmann, Regina

2008-01-01

In this work a systematical study to investigate the adsorption structures of small hydrocarbon ring shaped molecules on III-V semiconductor surfaces with Photo-Emission Spectroscopy (PES), Reflectance Anisotropy Spectroscopy (RAS), Scanning Tunneling Microscopy (STM) as well as Low Electron Energy Diffraction (LEED) was performed. To investigate the influence of the surface structure in detail the surface dimer configuration to the adsorption process of organic molecules GaAs(001) surfaces, the c(4 x 4), the (2 x 4) and the (4 x 2) have been investigated as well as the adsorption of cyclopentene on the InP(001)(2 x 4) reconstructed surface. In the direct comparison it is shown that cyclopentene bonds to the InP(001)(2 x 4) surface via a cycloaddition like reaction. During this adsorption the double bond splits which is in contrast to the adsorption of cyclopentene on the GaAs(001) surfaces. Therefrom it is concluded that the surface geometry has an influence on the resulting adsorption structure. In order to investigate the influence of the intra-molecular double bonds, cyclopentene (one double bond), 1,4-cyclohexadiene (two double bonds) and benzene (three double bonds) were used for the characterization of the interface formation. With the investigations on the GaAs(001) reconstructed surfaces it was shown that a dependency of the bonding configuration on the intra-molecular double bonds exists. During the adsorption of cyclopentene no evidence was found that the double bond has to be involved in the interface formation while during the adsorption of 1,4-cyclohexadiene and benzene the double bonds are involved. Furthermore it was found that a bonding to As atoms of the surface is more likely than a bonding to Ga atoms. (orig.)

Surface Plasmon Enhanced Phosphorescent Organic Light Emitting Diodes

International Nuclear Information System (INIS)

Bazan, Guillermo; Mikhailovsky, Alexander

2008-01-01

The objective of the proposed work was to develop the fundamental understanding and practical techniques for enhancement of Phosphorescent Organic Light Emitting Diodes (PhOLEDs) performance by utilizing radiative decay control technology. Briefly, the main technical goal is the acceleration of radiative recombination rate in organometallic triplet emitters by using the interaction with surface plasmon resonances in noble metal nanostructures. Increased photonic output will enable one to eliminate constraints imposed on PhOLED efficiency by triplet-triplet annihilation, triplet-polaron annihilation, and saturation of chromophores with long radiative decay times. Surface plasmon enhanced (SPE) PhOLEDs will operate more efficiently at high injection current densities and will be less prone to degradation mechanisms. Additionally, introduction of metal nanostructures into PhOLEDs may improve their performance due to the improvement of the charge transport through organic layers via multiple possible mechanisms ('electrical bridging' effects, doping-like phenomena, etc.). SPE PhOLED technology is particularly beneficial for solution-fabricated electrophosphorescent devices. Small transition moment of triplet emitters allows achieving a significant enhancement of the emission rate while keeping undesirable quenching processes introduced by the metal nanostructures at a reasonably low level. Plasmonic structures can be introduced easily into solution-fabricated PhOLEDs by blending and spin coating techniques and can be used for enhancement of performance in existing device architectures. This constitutes a significant benefit for a large scale fabrication of PhOLEDs, e.g. by roll-to-roll fabrication techniques. Besides multieexciton annihilation, the power efficacy of PhOLEDs is often limited by high operational bias voltages required for overcoming built-in potential barriers to injection and transport of electrical charges through a device. This problem is especially

Rapid and sensitive phenotypic marker detection on breast cancer cells using surface-enhanced Raman scattering (SERS) imaging.

Science.gov (United States)

Lee, Sangyeop; Chon, Hyangah; Lee, Jiyoung; Ko, Juhui; Chung, Bong Hyun; Lim, Dong Woo; Choo, Jaebum

2014-01-15

We report a surface-enhanced Raman scattering (SERS)-based cellular imaging technique to detect and quantify breast cancer phenotypic markers expressed on cell surfaces. This technique involves the synthesis of SERS nano tags consisting of silica-encapsulated hollow gold nanospheres (SEHGNs) conjugated with specific antibodies. Hollow gold nanospheres (HGNs) enhance SERS signal intensity of individual particles by localizing surface electromagnetic fields through pinholes in the hollow particle structures. This capacity to enhance imaging at the level of single molecules permits the use of HGNs to detect specific biological markers expressed in living cancer cells. In addition, silica encapsulation greatly enhances the stability of nanoparticles. Here we applied a SERS-based imaging technique using SEHGNs in the multiplex imaging of three breast cancer cell phenotypes. Expression of epidermal growth factor (EGF), ErbB2, and insulin-like growth factor-1 (IGF-1) receptors were assessed in the MDA-MB-468, KPL4 and SK-BR-3 human breast cancer cell lines. SERS imaging technology described here can be used to test the phenotype of a cancer cell and quantify proteins expressed on the cell surface simultaneously. Based on results, this technique may enable an earlier diagnosis of breast cancer than is currently possible and offer guidance in treatment. © 2013 Elsevier B.V. All rights reserved.

Improved density functional calculations for atoms, molecules and surfaces

International Nuclear Information System (INIS)

Fricke, B.; Anton, J.; Fritzsche, S.; Sarpe-Tudoran, C.

2005-01-01

The non-collinear and collinear descriptions within relativistic density functional theory is described. We present results of both non-collinear and collinear calculations for atoms, diatomic molecules, and some surface simulations. We find that the accuracy of our density functional calculations for the smaller systems is comparable to good quantum chemical calculations, and thus this method provides a sound basis for larger systems where no such comparison is possible. (author)

Dependence of energy per molecule on sputtering yields with reactive gas cluster ions

International Nuclear Information System (INIS)

Toyoda, Noriaki; Yamada, Isao

2010-01-01

Gas cluster ions show dense energy deposition on a target surface, which result in the enhancement of chemical reactions. In reactive sputtering with gas cluster ions, the energy per atom or molecule plays an important role. In this study, the average cluster size (N, the number of atoms or molecules in a cluster ion) was controlled; thereby the dependences of the energy per molecule on the sputtering yields of carbon by CO 2 cluster ions and that of Si by SF 6 /Ar mixed gas cluster ions were investigated. Large CO 2 cluster ions with energy per molecule of 1 eV showed high reactive sputtering yield of an amorphous carbon film. However, these ions did not cause the formation of large craters on a graphite surface. It is possible to achieve very low damage etching by controlling the energy per molecule of reactive cluster ions. Further, in the case of SF 6 /Ar mixed cluster ions, it was found that reactive sputtering was enhanced when a small amount of SF 6 gas (∼10%) was mixed with Ar. The reactive sputtering yield of Si by one SF 6 molecule linearly increased with the energy per molecule.

Heat transfer and forces on concave surfaces in free molecule flow.

Science.gov (United States)

Fan, C.

1971-01-01

A Monte Carlo modeling technique is described for mathematically simulating free molecular flows over a concave spherical surface and a concave cylindrical surface of finite length. The half-angle of the surfaces may vary from 0 to 90 degrees, and the incident flow may have an arbitrary speed ratio and an arbitrary angle of attack. Partial diffuse reflection and imperfect energy accommodation for molecules colliding with the surfaces are also considered. Results of heat transfer, drag and lift coefficients are presented for a variety of flow conditions. The present Monte Carlo results are shown to be in very good agreement with certain available theoretical solutions.

Resonance reactions and enhancement of weak interactions in collisions of cold molecules

International Nuclear Information System (INIS)

Flambaum, V. V.; Ginges, J. S. M.

2006-01-01

With the creation of ultracold atoms and molecules, a new type of chemistry - 'resonance' chemistry - emerges: chemical reactions can occur when the energy of colliding atoms and molecules matches a bound state of the combined molecule (Feshbach resonance). This chemistry is rather similar to reactions that take place in nuclei at low energies. In this paper we suggest some problems for future experimental and theoretical work related to the resonance chemistry of ultracold molecules. Molecular Bose-Einstein condensates are particularly interesting because in this system collisions and chemical reactions are extremely sensitive to weak fields; also, a preferred reaction channel may be enhanced due to a finite number of final states. The sensitivity to weak fields arises due to the high density of narrow compound resonances and the macroscopic number of molecules with kinetic energy E=0 (in the ground state of a mean-field potential). The high sensitivity to the magnetic field may be used to measure the distribution of energy intervals, widths, and magnetic moments of compound resonances and study the onset of quantum chaos. A difference in the production rate of right-handed and left-handed chiral molecules may be produced by external electric E and magnetic B fields and the finite width Γ of the resonance (correlation ΓE·B). The same effect may be produced by the parity-violating energy difference in chiral molecules

[In situ thin layer chromatography-fourier transform-surface-enhanced Raman spectrum study on ingredients of berberine].

Science.gov (United States)

Wang, Yuan; Guo, Zhan-sheng; Wang, Ying-feng; Wang, Song-ying; Ren, Gui-fen; Zhang, Xiang-lan; Han, Xiu-lan

2002-10-01

Surface Enhanced Raman Scattering (SERS) combined with Thin Layer Chromatography (TLC) has been used for studying characteristic spectrum of molecules in situ in micrograms samples. There are very few report for applying the SERS-TCL method in the study of the effective ingredients of Chinese traditional herbs. Coptis Chinensis France is an often-used clinic Chinese traditional medicine. Its main effective components include berberine and so on, which have antibiotic very wide and also have curative effect on improving the functions of heart vascular cycles. Therefore the concentrations of berberine are very important for the quality control of the medicine. In this work, the ethanol extract of Coptis Chinensis France was first separated by TLC, the SERS was then measure directly after dropping silver gel on the separated spots. The method can be used for the finger print analysis of the berberine. 3 microL of alcohol extract of Coptis Chinensis France with total alkaloids concentration of 1.0 mg.mL was placed on silicon GF254 TLC plate. The sample was separated by developing solvent of n bulanol-Acitic acid-H2O (7:2:1 V/V). The positions of berberine in the sample were confirmed by the standard alkaloid solutions. The Rf values for berberine are 0.29. The silver gel was used as surface enhanced substrate and placed on the separated berberine spots. FT-SERS was measured directly by a Nicolet FT-Raman 910 spectrometer. Berberine belong to isoquinoline alkaloids. His structure can be found in reference. The date of spectrum of berberine can be seen that the band at 1,396 cm-1 due to Ar-OCH3 deformation vibrations was greatly enhanced, indicating that the molecule was absorbed on silver gel strongly through lone-pair electron in Ar-OCH3. The ring stretching mode occurring around 1,548 cm-1 represents isoquinoline ring in the molecule. The band at 727 cm-1 due to CH (ring) deformation vibrations was also enhanced.

Improved surface-enhanced Raman scattering on arrays of gold quasi-3D nanoholes

KAUST Repository

Yue, Weisheng

2012-10-04

Arrays of gold quasi-3D nanoholes were proposed and fabricated as substrates for surface-enhanced Raman scattering (SERS). By detecting rhodamine 6G (R6G) molecules, the gold quasi-3D nanoholes demonstrated an SERS intensity that was 25-62 times higher than that of two-dimensional nanoholes with the same geometrical shapes and periodicities. The larger SERS enhancement of the quasi-3D nanoholes is attributed to the enhanced electromagnetic field on the top-layer nanohole, the bottom nanodiscs and the field coupling between the two layers. In addition, the investigation of the shape dependence of the SERS on the quasi-3D nanoholes demonstrated that the quadratic, circular, triangular and rhombic holes exhibited different SERS properties. Numerical simulations of the electromagnetic properties on the nanostructures were performed with CST Microwave Studio, and the results agree with the experimental observations. © 2012 IOP Publishing Ltd.

Measuring the force of single protein molecule detachment from surfaces with AFM.

Science.gov (United States)

Tsapikouni, Theodora S; Missirlis, Yannis F

2010-01-01

Atomic force microscopy (AFM) was used to measure the non-specific detachment force of single fibrinogen molecules from glass surfaces. The identification of single unbinding events was based on the characteristics of the parabolic curves, recorded during the stretching of protein molecules. Fibrinogen molecules were covalently bound to Si(3)N(4) AFM tips, previously modified with 3-aminopropyl-dimethyl-ethoxysilane, through a homobifunctional poly(ethylene glycol) linker bearing two hydroxysulfosuccinimide esters. The most probable detachment force was found to be 210 pN, when the tip was retracting with a velocity of 1400 nm/s, while the distribution of the detachment distances indicated that the fibrinogen chain can be elongated beyond the length of the physical conformation before detachment. The dependence of the most probable detachment force on the loading rate was examined and the dynamics of fibrinogen binding to the surface were found amenable to the simple expression of the Bell-Evans theory. The theory's expansion, however, by incorporating the concept of the rupture of parallel residue-surface bonds could only describe the detachment of fibrinogen for a small number of such bonds. Finally, the mathematical expression of the Worm-Like Chain model was used to fit the stretching curves before rupture and two interpretations are suggested for the description of the AFM curves with multiple detachment events.

Fabrication of large area nanoprism arrays and their application for surface enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Cui, B; Clime, L; Li, K; Veres, T

2008-01-01

This work demonstrates the fabrication of metallic nanoprism (triangular nanostructure) arrays using a low-cost and high-throughput process. In the method, the triangular structure is defined by the shadow of a pyramid during angle evaporation of a metal etching mask. The pyramids were created by nanoimprint lithography in polymethylmethacrylate (PMMA) using a mould having an inverse-pyramid-shaped hole array formed by KOH wet etching of silicon. Silver and gold nanoprism arrays with a period of 200 nm and an edge length of 100 nm have been fabricated and used as effective substrates for surface enhanced Raman spectroscopy (SERS) detection of rhodamine 6G (R6G) molecules. Numerical calculations confirmed the great enhancement of electric field near the sharp nanoprism corners, as well as the detrimental effect of the chromium adhesion layer on localized surface plasmon resonance. The current method can also be used to fabricate non-equilateral nanoprism and three-dimensional (3D) nanopyramid arrays, and it can be readily extended to other metals

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

Science.gov (United States)

Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

2015-01-01

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

Cell recognition molecule L1 promotes embryonic stem cell differentiation through the regulation of cell surface glycosylation

Energy Technology Data Exchange (ETDEWEB)

Li, Ying [Department of Biochemistry and Molecular Biology, Dalian Medical University, Dalian 116044 (China); Department of Clinical Laboratory, Second Affiliated Hospital of Dalian Medical University, Dalian 116023 (China); Huang, Xiaohua [Department of Biochemistry and Molecular Biology, Dalian Medical University, Dalian 116044 (China); Department of Clinical Biochemistry, College of Laboratory Medicine, Dalian Medical University, Dalian 116044 (China); An, Yue [Department of Clinical Laboratory, Second Affiliated Hospital of Dalian Medical University, Dalian 116023 (China); Ren, Feng [Department of Biochemistry and Molecular Biology, Dalian Medical University, Dalian 116044 (China); Yang, Zara Zhuyun; Zhu, Hongmei; Zhou, Lei [The Key Laboratory of Stem Cell and Regenerative Medicine, Institute of Molecular and Clinical Medicine, Kunming Medical University, Kunming 650228 (China); Department of Anatomy and Developmental Biology, Monash University, Clayton 3800 (Australia); He, Xiaowen; Schachner, Melitta [Keck Center for Collaborative Neuroscience and Department of Cell Biology and Neuroscience, Rutgers University, New Brunswick, NJ (United States); Xiao, Zhicheng, E-mail: zhicheng.xiao@monash.edu [The Key Laboratory of Stem Cell and Regenerative Medicine, Institute of Molecular and Clinical Medicine, Kunming Medical University, Kunming 650228 (China); Department of Anatomy and Developmental Biology, Monash University, Clayton 3800 (Australia); Ma, Keli, E-mail: makeli666@aliyun.com [Department of Biochemistry and Molecular Biology, Dalian Medical University, Dalian 116044 (China); Li, Yali, E-mail: yalilipaper@gmail.com [Department of Biochemistry and Molecular Biology, Dalian Medical University, Dalian 116044 (China); Department of Anatomy, National University of Singapore, Singapore 119078 (Singapore)

2013-10-25

Highlights: •Down-regulating FUT9 and ST3Gal4 expression blocks L1-induced neuronal differentiation of ESCs. •Up-regulating FUT9 and ST3Gal4 expression in L1-ESCs depends on the activation of PLCγ. •L1 promotes ESCs to differentiate into neuron through regulating cell surface glycosylation. -- Abstract: Cell recognition molecule L1 (CD171) plays an important role in neuronal survival, migration, differentiation, neurite outgrowth, myelination, synaptic plasticity and regeneration after injury. Our previous study has demonstrated that overexpressing L1 enhances cell survival and proliferation of mouse embryonic stem cells (ESCs) through promoting the expression of FUT9 and ST3Gal4, which upregulates cell surface sialylation and fucosylation. In the present study, we examined whether sialylation and fucosylation are involved in ESC differentiation through L1 signaling. RNA interference analysis showed that L1 enhanced differentiation of ESCs into neurons through the upregulation of FUT9 and ST3Gal4. Furthermore, blocking the phospholipase Cγ (PLCγ) signaling pathway with either a specific PLCγ inhibitor or knockdown PLCγ reduced the expression levels of both FUT9 and ST3Gal4 mRNAs and inhibited L1-mediated neuronal differentiation. These results demonstrate that L1 promotes neuronal differentiation from ESCs through the L1-mediated enhancement of FUT9 and ST3Gal4 expression.

Cell recognition molecule L1 promotes embryonic stem cell differentiation through the regulation of cell surface glycosylation

International Nuclear Information System (INIS)

Li, Ying; Huang, Xiaohua; An, Yue; Ren, Feng; Yang, Zara Zhuyun; Zhu, Hongmei; Zhou, Lei; He, Xiaowen; Schachner, Melitta; Xiao, Zhicheng; Ma, Keli; Li, Yali

2013-01-01

Highlights: •Down-regulating FUT9 and ST3Gal4 expression blocks L1-induced neuronal differentiation of ESCs. •Up-regulating FUT9 and ST3Gal4 expression in L1-ESCs depends on the activation of PLCγ. •L1 promotes ESCs to differentiate into neuron through regulating cell surface glycosylation. -- Abstract: Cell recognition molecule L1 (CD171) plays an important role in neuronal survival, migration, differentiation, neurite outgrowth, myelination, synaptic plasticity and regeneration after injury. Our previous study has demonstrated that overexpressing L1 enhances cell survival and proliferation of mouse embryonic stem cells (ESCs) through promoting the expression of FUT9 and ST3Gal4, which upregulates cell surface sialylation and fucosylation. In the present study, we examined whether sialylation and fucosylation are involved in ESC differentiation through L1 signaling. RNA interference analysis showed that L1 enhanced differentiation of ESCs into neurons through the upregulation of FUT9 and ST3Gal4. Furthermore, blocking the phospholipase Cγ (PLCγ) signaling pathway with either a specific PLCγ inhibitor or knockdown PLCγ reduced the expression levels of both FUT9 and ST3Gal4 mRNAs and inhibited L1-mediated neuronal differentiation. These results demonstrate that L1 promotes neuronal differentiation from ESCs through the L1-mediated enhancement of FUT9 and ST3Gal4 expression

Nanopolyaniline as immobilization template for signal enhancement of surface plasmon resonance biosensor - A preliminary study

Science.gov (United States)

Kamarun, Dzaraini; Abdul Azem, Nor Hazirah Kamel; Sarijo, Siti Halimah; Mohd, Ahmad Faiza; Abdullah @ Mohd Noor, Mashita

2012-07-01

A technique for the enhancement of Surface Plasmon Resonance (SPR) signal for sensing biomolecular interactions is described. Polyaniline (PANI) of particle size in the range of 1 to 15 nm was synthesized and used as the template for the immobilization of protein molecules. Biomolecular interactions of unbound and PANI-bound proteins with antibody molecules were SPR-monitored using a model system comprising of Bovine Serum Albumin (BSA) and anti BSA. A 7-fold increased in the signal was recorded from interactions of the PANI-bound BSA with anti BSA compared to the interactions of its unbound counterpart. This preliminary observation provides new avenue in immunosensor technology for improving the detection sensitivity of SPR biosensor; and thereby increasing the lower detection limit of biomolecules.

Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions

Energy Technology Data Exchange (ETDEWEB)

Bajo, Juan José [Departamento de Química-Física I, Universidad Complutense de Madrid, 28040 Madrid (Spain); Granucci, Giovanni, E-mail: giovanni.granucci@unipi.it; Persico, Maurizio [Università di Pisa, Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35, 56126 Pisa (Italy)

2014-01-28

We implemented a method for the treatment of field induced transitions in trajectory surface hopping simulations, in the framework of the local diabatization scheme, especially suited for on-the-fly dynamics. The method is applied to a simple one-dimensional model with an avoided crossing and compared with quantum wavepacket dynamics. The results show the importance of introducing a proper decoherence correction to surface hopping, in order to obtain meaningful results. Also the energy conservation policy of standard surface hopping must be revised: in fact, the quantum wavepacket energetics is well reproduced if energy absorption/emission is allowed for in the hops determined by radiation-molecule coupling. To our knowledge, this is the first time the issues of decoherence and energy conservation have been analyzed in depth to devise a mixed quantum-classical method for dynamics with molecule-field interactions.

Complementary surface charge for enhanced capacitive deionization

NARCIS (Netherlands)

Gao, X.; Porada, S.; Omosebi, A.; Liu, K.L.; Biesheuvel, P.M.; Landon, J.

2016-01-01

Commercially available activated carbon cloth electrodes are treated using nitric acid and ethylenediamine solutions, resulting in chemical surface charge enhanced carbon electrodes for capacitive deionization (CDI) applications. Surface charge enhanced electrodes are then configured in a CDI

A theoretical and experimental investigation of the interaction between gas molecules and cryogenic surfaces

International Nuclear Information System (INIS)

Varlam, M.; Steflea, D.; Chiriloaie, N.

1992-01-01

The cryo-pumping performance of a cryo-surface subjected to the impingement of low-pressure, thermal-velocity air flow is experimentally and theoretically investigated. Our purpose is to determine the angular dependence of capture coefficients for gas molecules incident on a cryogenic surface under conditions closely approximating those prevailing in cryo-pumped high vacuum chambers. The classical model for the interaction of gas atoms and the solid surface - the 'soft-tube' model - is developed and the basic assumption are examined. Starting from this theory we have calculated the capture coefficient of the Ag - N system and these values are discussed in terms of principal parameters considered. Despite the many simplifying assumptions, this model has the important attribute that it yields closed-form expressions for the capture coefficient of gas molecules. The molecular beam technique offers a direct experimental method for determining the capture coefficient for molecules with given angles of incidence by measuring the incident and reflected molecular fluxes. An experimental setup is also designed and the method for determining these coefficients is proposed. (Author)

Adhesion of Model Molecules to Metallic Surfaces, the Implications for Corrosion Protection

International Nuclear Information System (INIS)

De Wit, J. H. W.; Van den Brand, J.; De Wit, F. M.; Mol, J. M. C.

2008-01-01

The majority of the described experimental results deal with relatively pure aluminium. Variations were made in the pretreatment of the aluminum substrates and an investigation was performed on the resulting changes in oxide layer composition and chemistry. Subsequently, the bonding behavior of the surfaces was investigated by using model adhesion molecules. These molecules were chosen to represent the bonding functionality of an organic polymer. They were applied onto the pretreated surfaces as a monolayer and the bonding behavior was studied using infrared reflection absorption spectroscopy. A direct and clear relation was found between the hydroxyl fraction on the oxide surfaces and the amount of molecules that subsequently bonded to the surface. Moreover, it was found that most bonds between the oxide surface and organic functional groups are not stable in the presence of water. The best performance was obtained using molecules, which are capable of chemisorption with the oxide surface. Finally, it was found that freshly prepared relatively pure aluminum substrates, which are left in air, rapidly lose their bonding capacity towards organic functional groups. This can be attributed to the adsorption of contamination and water to the oxide surface. in addition the adhesion of a typical epoxy-coated aluminum system was investigated during exposure to water at different temperatures. The coating was found to quite rapidly lose its adhesion upon exposure to water. This rapid loss of adhesion corresponds well with the data where it was demonstrated that the studied epoxy coating only bonds through physisorptive hydrogen bonding, these bonds not being stable in the presence of water. After the initial loss the adhesion of the coating was however found to recover again and even exceeded the adhesion prior to exposure. The improvement could be ascribed to the growth of a thin oxyhydroxide layer on the aluminum substrate, which forms a new, water-stable and stronger bond

A simple approach for ultrasensitive detection of bisphenols by multiplexed surface-enhanced Raman scattering

Energy Technology Data Exchange (ETDEWEB)

De Bleye, C., E-mail: cdebleye@ulg.ac.be; Dumont, E.; Hubert, C.; Sacré, P.-Y.; Netchacovitch, L.; Chavez, P.-F.; Hubert, Ph.; Ziemons, E.

2015-08-12

Bisphenol A (BPA) is well known for its use in plastic manufacture and thermal paper production despite its risk of health toxicity as an endocrine disruptor in humans. Since the publication of new legislation regarding the use of BPA, manufacturers have begun to replace BPA with other phenolic molecules such as bisphenol F (BPF) and bisphenol B (BPB), but there are no guarantees regarding the health safety of these compounds at this time. In this context, a very simple, cheap and fast surface-enhanced Raman scattering (SERS) method was developed for the sensitive detection of these molecules in spiked tap water solutions. Silver nanoparticles were used as SERS substrates. An original strategy was employed to circumvent the issue of the affinity of bisphenols for metallic surfaces and the silver nanoparticles surface was functionalized using pyridine in order to improve again the sensitivity of the detection. Semi-quantitative detections were performed in tap water solutions at a concentrations range from 0.25 to 20 μg L{sup −1} for BPA and BPB and from 5 to 100 μg L{sup −1} for BPF. Moreover, a feasibility study for performing a multiplex-SERS detection of these molecules was also performed before successfully implementing the developed SERS method on real samples. - Highlights: • Development of a simple, fast and ultrasensitive SERS method to detect bisphenols. • Multiplexed-SERS detection of bisphenol A, bisphenol B and bisphenol F. • Implementation of the SERS developed method on real samples to detect bisphenols.

A simple approach for ultrasensitive detection of bisphenols by multiplexed surface-enhanced Raman scattering

International Nuclear Information System (INIS)

De Bleye, C.; Dumont, E.; Hubert, C.; Sacré, P.-Y.; Netchacovitch, L.; Chavez, P.-F.; Hubert, Ph.; Ziemons, E.

2015-01-01

Bisphenol A (BPA) is well known for its use in plastic manufacture and thermal paper production despite its risk of health toxicity as an endocrine disruptor in humans. Since the publication of new legislation regarding the use of BPA, manufacturers have begun to replace BPA with other phenolic molecules such as bisphenol F (BPF) and bisphenol B (BPB), but there are no guarantees regarding the health safety of these compounds at this time. In this context, a very simple, cheap and fast surface-enhanced Raman scattering (SERS) method was developed for the sensitive detection of these molecules in spiked tap water solutions. Silver nanoparticles were used as SERS substrates. An original strategy was employed to circumvent the issue of the affinity of bisphenols for metallic surfaces and the silver nanoparticles surface was functionalized using pyridine in order to improve again the sensitivity of the detection. Semi-quantitative detections were performed in tap water solutions at a concentrations range from 0.25 to 20 μg L −1 for BPA and BPB and from 5 to 100 μg L −1 for BPF. Moreover, a feasibility study for performing a multiplex-SERS detection of these molecules was also performed before successfully implementing the developed SERS method on real samples. - Highlights: • Development of a simple, fast and ultrasensitive SERS method to detect bisphenols. • Multiplexed-SERS detection of bisphenol A, bisphenol B and bisphenol F. • Implementation of the SERS developed method on real samples to detect bisphenols

Detection and aggregation of the antitumoral drug parietin in ethanol/water mixture and on plasmonic metal nanoparticles studied by surface-enhanced optical spectroscopy: Effect of pH and ethanol concentration

Science.gov (United States)

Lopez-Tobar, Eduardo; Verebova, Valeria; Blascakova, Ludmila; Jancura, Daniel; Fabriciova, Gabriela; Sanchez-Cortes, Santiago

2016-04-01

In the present paper, we have investigated the effect of ethanol in aqueous media, the pH and the presence of Ag nanoparticles (NPs) on the aggregation processes of the antitumoral anthraquinone parietin in aqueous media and on the metal surface. UV-visible absorption, fluorescence and Raman spectra of parietin were used for such purpose. The present study provides information about the deprotonation and molecular aggregation processes occurring in parietin under different environments: ethanol/water mixture and when adsorbed onto Ag nanoparticles. The effect of ethanol on the optical properties of parietin in alcohol-water mixtures was also investigated at different ethanol concentrations with the time. For the case of the adsorption and organization of parietin molecules on the surface of Ag NPs, special attention was paid to the use of surface-enhanced optical techniques, SEF (surface-enhanced fluorescence) and SERS (surface-enhanced Raman scattering), for the characterization of the parietin aggregates and the ionization of the molecule on the surface. In particular, we have studied the variation of the SEF signal with the pH, which depends on the molecular organization of the molecule on the surface. Furthermore, a detailed analysis of the SERS spectra at different pH was accomplished and the main Raman bands of the protonated, mono-deprotonated and di-deprotonated parietin were identified. Finally, the second ionization pK of parietin on metal NPs was deduced from the SERS spectra.

Hollow-Core Photonic Crystal Fibers for Surface-Enhanced Raman Scattering Probes

Directory of Open Access Journals (Sweden)

Xuan Yang

2011-01-01

Full Text Available Photonic crystal fiber (PCF sensors based on surface-enhanced Raman scattering (SERS have become increasingly attractive in chemical and biological detections due to the molecular specificity, high sensitivity, and flexibility. In this paper, we review the development of PCF SERS sensors with emphasis on our recent work on SERS sensors utilizing hollow-core photonic crystal fibers (HCPCFs. Specifically, we discuss and compare various HCPCF SERS sensors, including the liquid-filled HCPCF and liquid-core photonic crystal fibers (LCPCFs. We experimentally demonstrate and theoretically analyze the high sensitivity of the HCPCF SERS sensors. Various molecules including Rhodamine B, Rhodamine 6G, human insulin, and tryptophan have been tested to show the excellent performance of these fiber sensors.

Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

1992-01-01

The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules...

Strong plasmonic enhancement of single molecule photostability in silver dimer optical antennas

Directory of Open Access Journals (Sweden)

Kaminska Izabela

2018-02-01

Full Text Available Photobleaching is an effect terminating the photon output of fluorophores, limiting the duration of fluorescence-based experiments. Plasmonic nanoparticles (NPs can increase the overall fluorophore photostability through an enhancement of the radiative rate. In this work, we use the DNA origami technique to arrange a single fluorophore in the 12-nm gap of a silver NP dimer and study the number of emitted photons at the single molecule level. Our findings yielded a 30× enhancement in the average number of photons emitted before photobleaching. Numerical simulations are employed to rationalize our results. They reveal the effect of silver oxidation on decreasing the radiative rate enhancement.

Structure determination by photoelectron diffraction of small molecules on surfaces

International Nuclear Information System (INIS)

Booth, N.A.

1998-05-01

The synchrotron radiation based technique of Photoelectron Diffraction (PhD) has been applied to three adsorption systems. Structure determinations, are presented for each system which involve the adsorption of small molecules on the low index {110} plane of single crystal Cu and Ni substrates. For the NH 3 -Cu(110) system PhD was successful in determining a N-Cu bondlength of 2.05 ± 0.03 A as well as values for the anisotropic vibrational amplitudes of the N and an expansion of the 1st to 2nd Cu substrate layer spacing from the bulk value of 0.08 ± 0.08 A. The most significant and surprising structural parameter determined for this system was that the N atom occupies an asymmetric adsorption site. Rather than being situated in the expected high symmetry atop site the N atom was found to be offset parallel to the surface by 0.37 ± 0.12 A in the [001] azimuth. In studying the glycine-Cu(110) system the adsorption structure of an amino-acid has been quantified. The local adsorption geometries of all the atoms involved in the molecule to surface bond have been determined. The glycine molecule is found to be bonded to the surface via both its amino and carboxylate functional groups. The molecule straddles two [11-bar0] rows of the Cu substrate. The two O atoms are found to be in identical sites both approximately atop Cu atoms on the [11-bar0] rows offset parallel to the surface by 0.80 ± 0.05 A in the [001] azimuth, the O-Cu bondlength was found to be 2.03 ± 0.05 A. The N atom was also found to adsorb in an approximately atop geometry but offset parallel to the surface by 0.24 ± 0.10A in the [11-bar0] direction, the N-Cu bondlength was found to be 2.05± 0.05 A. PhD was unsuccessful in determining the positions of the two C atoms that form a bridge between the two functional groups bonded to the surface due to difficulties in separating the two inequivalent contributions to the final intensity modulation function. For the CN-Ni(110) system both PhD and Near Edge

Electronic properties and assambly of DNA-based molecules on gold surfaces

DEFF Research Database (Denmark)

Salvatore, Princia

, highly base specific voltammetric peak in the presence of spermidine ions. A capacitive origin was attributed to this peak, and a novel route to detection of hybridization and base pair mismatches proposed on the basis of the high sensitivity to base pair mismatches showed by such ON-based monolayers...... as widely employed as Au(111) surfaces). In particular, SERS offered a valuable and rapid way ofcharacterising interactions between the DNA-based molecules and the NP surface, with no need for complex sample preparation....

Spontaneous dissociation of a conjugated molecule on the Si(100) surface

DEFF Research Database (Denmark)

Lin, Rong; Galili, Michael; Quaade, Ulrich

2002-01-01

The adsorption mechanism of alpha-sexithiophene (alpha-6T) on the clean Si(100)-(2x1) surface has been investigated using scanning tunneling microscopy (STM) and first principles electronic structure calculations. We find that at submonolayer coverage, the alpha-6T molecules are not stable and di...

Cones fabricated by 3D nanoimprint lithography for highly sensitive surface enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Wu Wei; Hu Min; Ou Fungsuong; Li Zhiyong; Williams, R Stanley

2010-01-01

We demonstrated a cost-effective and deterministic method of patterning 3D cone arrays over a large area by using nanoimprint lithography (NIL). Cones with tip radius of less than 10 nm were successfully duplicated onto the UV-curable imprint resist materials from the silicon cone templates. Such cone structures were shown to be a versatile platform for developing reliable, highly sensitive surface enhanced Raman spectroscopy (SERS) substrates. In contrast to the silicon nanocones, the SERS substrates based on the Au coated cones made by the NIL offered significant improvement of the SERS signal. A further improvement of the SERS signal was observed when the polymer cones were imprinted onto a reflective metallic mirror surface. A sub-zeptomole detection sensitivity for a model molecule, trans-1,2-bis(4-pyridyl)-ethylene (BPE), on the Au coated NIL cone surfaces was achieved.

Microscale surface modifications for heat transfer enhancement.

Science.gov (United States)

Bostanci, Huseyin; Singh, Virendra; Kizito, John P; Rini, Daniel P; Seal, Sudipta; Chow, Louis C

2013-10-09

In this experimental study, two surface modification techniques were investigated for their effect on heat transfer enhancement. One of the methods employed the particle (grit) blasting to create microscale indentations, while the other used plasma spray coating to create microscale protrusions on Al 6061 (aluminum alloy 6061) samples. The test surfaces were characterized using scanning electron microscopy (SEM) and confocal scanning laser microscopy. Because of the surface modifications, the actual surface area was increased up to 2.8× compared to the projected base area, and the arithmetic mean roughness value (Ra) was determined to vary from 0.3 μm for the reference smooth surface to 19.5 μm for the modified surfaces. Selected samples with modified surfaces along with the reference smooth surface were then evaluated for their heat transfer performance in spray cooling tests. The cooling system had vapor-atomizing nozzles and used anhydrous ammonia as the coolant in order to achieve heat fluxes up to 500 W/cm(2) representing a thermal management setting for high power systems. Experimental results showed that the microscale surface modifications enhanced heat transfer coefficients up to 76% at 500 W/cm(2) compared to the smooth surface and demonstrated the benefits of these practical surface modification techniques to enhance two-phase heat transfer process.

Enhancing Single Molecule Imaging in Optofluidics and Microfluidics

Directory of Open Access Journals (Sweden)

Andreas E. Vasdekis

2011-08-01

Full Text Available Microfluidics and optofluidics have revolutionized high-throughput analysis and chemical synthesis over the past decade. Single molecule imaging has witnessed similar growth, due to its capacity to reveal heterogeneities at high spatial and temporal resolutions. However, both resolution types are dependent on the signal to noise ratio (SNR of the image. In this paper, we review how the SNR can be enhanced in optofluidics and microfluidics. Starting with optofluidics, we outline integrated photonic structures that increase the signal emitted by single chromophores and minimize the excitation volume. Turning then to microfluidics, we review the compatible functionalization strategies that reduce noise stemming from non-specific interactions and architectures that minimize bleaching and blinking.

Single-Molecule Detection in Nanogap-Embedded Plasmonic Gratings

Directory of Open Access Journals (Sweden)

Biyan Chen

2015-07-01

Full Text Available We introduce nanogap-embedded silver plasmonic gratings for single-molecule (SM visualization using an epifluorescence microscope. This silver plasmonic platform was fabricated by a cost-effective nano-imprint lithography technique, using an HD DVD template. DNA/ RNA duplex molecules tagged with Cy3/Cy5 fluorophores were immobilized on SiO 2 -capped silver gratings. Light was coupled to the gratings at particular wavelengths and incident angles to form surface plasmons. The SM fluorescence intensity of the fluorophores at the nanogaps showed approximately a 100-fold mean enhancement with respect to the fluorophores observed on quartz slides using an epifluorescence microscope. This high level of enhancement was due to the concentration of surface plasmons at the nanogaps. When nanogaps imaged with epifluorescence mode were compared to quartz imaged using total internal reflection fluorescence (TIRF microscopy, more than a 30-fold mean enhancement was obtained. Due to the SM fluorescence enhancement of plasmonic gratings and the correspondingly high emission intensity, the required laser power can be reduced, resulting in a prolonged detection time prior to photobleaching. This simple platform was able to perform SM studies with a low-cost epifluorescence apparatus, instead of the more expensive TIRF or confocal microscopes, which would enable SM analysis to take place in most scientific laboratories.

Suppression and enhancement of non-native molecules within biological systems

Energy Technology Data Exchange (ETDEWEB)

Jones, E.A. [Surface Analysis Research Centre, CEAS, School of Chemical Engineering and Analytical Science, University of Manchester, Manchester M60 1QD (United Kingdom)]. E-mail: e.jones@postgrad.manchester.ac.uk; Lockyer, N.P. [Surface Analysis Research Centre, CEAS, School of Chemical Engineering and Analytical Science, University of Manchester, Manchester M60 1QD (United Kingdom); Vickerman, J.C. [Surface Analysis Research Centre, CEAS, School of Chemical Engineering and Analytical Science, University of Manchester, Manchester M60 1QD (United Kingdom)

2006-07-30

With the aim of evaluating the potential of SIMS to provide molecular information from small molecules within biological systems, here we investigate the effect of different biological compounds as they act as matrices. The results highlight the fact that the chemical environment of a molecule can have a significant effect on its limit of detection. This has implications for the imaging of drugs and xenobiotics in tissue sections and other biological matrices. A 1:1 mixture of the organic acid 2,4,6-trihydroxyacetophenone and the dipeptide valine-valine demonstrates that almost complete suppression of the [M + H]{sup +} ion of one compound can be caused by the presence of a compound of higher proton affinity. The significance of this is highlighted when two similar drug molecules, atropine (a neutral molecule) and ipratropium bromide (a quaternary nitrogen containing salt) are mixed with brain homogenate. The atropine [M + H]{sup +} ion shows significant suppression whilst the [M - Br]{sup +} of ipratopium bromide is detected at an intensity that can be rationalised by its decreased surface concentration. By investigating the effect of two abundant tissue lipids, cholesterol and dipalmitoylphosphatidyl choline (DPPC), on the atropine [M + H]{sup +} signal detected in mixtures with these lipids we see that the DPPC has a strong suppressing effect, which may be attributed to gas phase proton transfer.

Surface-Enhanced Raman Spectroscopy

Indian Academy of Sciences (India)

Home; Journals; Resonance – Journal of Science Education; Volume 15; Issue 2. Surface-Enhanced Raman Spectroscopy - Recent Advancement of Raman Spectroscopy. Ujjal Kumar Sur. General Article Volume 15 Issue 2 February 2010 pp 154-164 ...

Control of magnetism in dilute magnetic semiconductor (Ga,Mn)As films by surface decoration of molecules

Science.gov (United States)

Wang, Hailong; Wang, Xiaolei; Xiong, Peng; Zhao, Jianhua

2016-03-01

The responses of magnetic moments to external stimuli such as magnetic-field, heat, light and electric-field have been utilized to manipulate the magnetism in magnetic semiconductors, with many of the novel ideas applied even to ferromagnetic metals. Here, we review a new experimental development on the control of magnetism in (Ga,Mn)As thin films by surface decoration of organic molecules: Molecules deposited on the surface of (Ga,Mn)As thin films are shown to be capable of significantly modulating their saturation magnetization and Curie temperature. These phenomena are shown to originate from the carrier-mediated ferromagnetism in (Ga,Mn)As and the surface molecules acting as acceptors or donors depending on their highest occupied molecular orbitals, resembling the charge transfer mechanism in a pn junction in which the equilibrium state is reached on the alignment of Fermi levels.

Control of magnetism in dilute magnetic semiconductor (Ga,MnAs films by surface decoration of molecules

Directory of Open Access Journals (Sweden)

Hailong eWang

2016-03-01

Full Text Available The responses of magnetic moments to external stimuli such as magnetic-field, heat, light and electric-field have been utilized to manipulate the magnetism in magnetic semiconductors, with many of the novel ideas applied even to ferromagnetic metals. Here, we review a new experimental development on the control of magnetism in (Ga,MnAs thin films by surface decoration of organic molecules: Molecules deposited on the surface of (Ga,MnAs thin films are shown to be capable of significantly modulating their saturation magnetization and Curie temperature. These phenomena are shown to originate from the carrier-mediated ferromagnetism in (Ga,MnAs and the surface molecules acting as acceptors or donors depending on their highest occupied molecular orbitals, resembling the charge transfer mechanism in a pn junction in which the equilibrium state is reached on the alignment of Fermi levels.

Surface-enhanced Raman difference between bombesin and its modified analogues on the colloidal and electrochemically roughen silver surfaces.

Science.gov (United States)

Podstawka, Edyta; Ozaki, Yukihiro

2008-10-01

In this article, surface-enhanced Raman scattering (SERS) spectra of bombesin (BN) and its six modified analogues ([D-Phe(12)]BN, [Tyr(4)]BN, [Tyr(4),D-Phe(12)]BN, [D-Phe(12),Leu(14)]BN, [Leu(13)-(R)-Leu(14)]BN, and [Lys(3)]BN) on a colloidal silver surface are reported and compared with SERS spectra of these species immobilized onto an ellectrochemically roughen silver electrode. Changes in enhancement and wavenumber of proper bands upon adsorption on different silver surfaces are consistent with BN and its analogues adsorption primarily through Trp(8). Slightly different adsorption states of these molecules are observed depending upon natural amino acids substitution. For example, the indole ring in all the peptides interacts with silver nanoparticles in a edge-on orientation. It is additionally coordinated to the silver through the N(1)--H bond for all the peptides, except [Phe(12)]BN. This is in contrary to the results obtained for the silver roughen electrode that show direct but not strong N(1)--H/Ag interaction for all peptides except [D-Phe(12),Leu(14)]BN and [Leu(13)-(R)-Leu(14)]BN. For BN only C==O is not involved in the chemical coordination with the colloidal surface. [Lys(3)]BN and BN also adsorb with the C--N bond of NH(2) group normal and horizontal, respectively, to the colloidal surface, whereas C--NH(2) in other peptides is tilted to this surface. Also, the Trp(8) --CH(2)-- moiety of only [Tyr(4)]BN, [Lys(3)]BN, and [Tyr(4),D-Phe(12)]BN coordinates to Ag, whereas the Phe(12) ring of [Phe(12)]BN, [Tyr(4),D-Phe(12)]BN, and [D-Phe(12),Leu(14)]BN assists in the peptides binding only on the colloidal silver. (c) 2008 Wiley Periodicals, Inc.

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes.

Science.gov (United States)

Abdelhamid, Hani Nasser

2018-03-01

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks. Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

Single NdPc2 molecules on surfaces. Adsorption, interaction, and molecular magnetism

International Nuclear Information System (INIS)

Fahrendorf, Sarah

2013-01-01

They have huge potential for application in molecular-spin-transistors, molecular-spinvalves, and molecular quantum computing. SMMs are characterized by high spin ground states with zero-field splitting leading to high relaxation barriers and long relaxation times. A relevant class of molecules are the lanthanide double-decker phthalocyanines (LaPc 2 ) with only one metal atom sandwiched between two organic phthalocyanine (Pc) ligands. For envisaged spintronic applications it is important to understand the interaction between the molecules and the substrate and its influence on the electronic and magnetic properties. The subject of this thesis is the investigation of the adsorbed neodymium double-decker phthalocyanine (NdPc 2 ) by means of low temperature scanning tunneling microscopy and spectroscopy (STM and STS). The molecules are deposited by sublimation onto different substrates. It is observed that a large fraction of the double-decker molecules decomposes during deposition. The decomposition probability strongly depends on the chosen substrate. Therefore it is concluded that the substrate modifies the electronic structure of the molecule leading to a stabilization or destabilization of the molecular entity. Charge transfer from the surface to the molecule is identified as a potential stabilizing mechanism. The electronic and magnetic properties are investigated in detail for adsorbed NdPc 2 molecules on Cu(100). The results of the experimental study are compared to state-of-the-art density functional theory calculations performed by our colleagues from the Peter Gruenberg Institute (PGI-1) at the Forschungszentrum Juelich. Interestingly, the lower Pc ring of the molecule hybridizes intensely with the substrate leading to strong chemisorption of the molecule, while the upper Pc ring keeps its molecular type electronic states, which can be energetically shifted by an external electric field. Importantly, it is possible to get direct access to the spin

Recent Progress on Plasmon-Enhanced Fluorescence

Directory of Open Access Journals (Sweden)

Dong Jun

2015-12-01

Full Text Available The optically generated collective electron density waves on metal–dielectric boundaries known as surface plasmons have been of great scientific interest since their discovery. Being electromagnetic waves on gold or silver nanoparticle’s surface, localised surface plasmons (LSP can strongly enhance the electromagnetic field. These strong electromagnetic fields near the metal surfaces have been used in various applications like surface enhanced spectroscopy (SES, plasmonic lithography, plasmonic trapping of particles, and plasmonic catalysis. Resonant coupling of LSPs to fluorophore can strongly enhance the emission intensity, the angular distribution, and the polarisation of the emitted radiation and even the speed of radiative decay, which is so-called plasmon enhanced fluorescence (PEF. As a result, more and more reports on surface-enhanced fluorescence have appeared, such as SPASER-s, plasmon assisted lasing, single molecule fluorescence measurements, surface plasmoncoupled emission (SPCE in biological sensing, optical orbit designs etc. In this review, we focus on recent advanced reports on plasmon-enhanced fluorescence (PEF. First, the mechanism of PEF and early results of enhanced fluorescence observed by metal nanostructure will be introduced. Then, the enhanced substrates, including periodical and nonperiodical nanostructure, will be discussed and the most important factor of the spacer between molecule and surface and wavelength dependence on PEF is demonstrated. Finally, the recent progress of tipenhanced fluorescence and PEF from the rare-earth doped up-conversion (UC and down-conversion (DC nanoparticles (NPs are also commented upon. This review provides an introduction to fundamentals of PEF, illustrates the current progress in the design of metallic nanostructures for efficient fluorescence signal amplification that utilises propagating and localised surface plasmons.

Measuring the surface-enhanced Raman scattering enhancement factors of hot spots formed between an individual Ag nanowire and a single Ag nanocube

International Nuclear Information System (INIS)

Camargo, Pedro H C; Cobley, Claire M; Rycenga, Matthew; Xia Younan

2009-01-01

This paper describes a systematic study of the surface-enhanced Raman scattering (SERS) activity of hot spots formed between a Ag nanowire and a Ag nanocube with sharp corners. We investigated two distinct dimer structures: (i) a nanocube having one side face nearly touching the side face of a nanowire, and (ii) a nanocube having one edge nearly touching the side face of a nanowire. The field enhancements for the dimers displayed a strong dependence on laser polarization, and the strongest SERS intensities were observed for polarization along the hot-spot axis. Moreover, the detected SERS intensities were dependent on the hot-spot structure, i.e., the relative orientation of the Ag nanocube with respect to the nanowire's side face. When the dimer had a face-to-face configuration, the enhancement factor EF dimer was 1.4 x 10 7 . This corresponds to 22-fold and 24-fold increases compared to those for individual Ag nanowires and nanocubes, respectively. Conversely, when the dimer had an edge-to-face configuration, EF dimer was 4.3 x 10 6 . These results demonstrated that the number of probe molecules adsorbed at the hot spot played an important role in determining the detected SERS intensities. EF dimer was maximized when the dimer configuration allowed for a larger number of probe molecules to be trapped within the hot-spot region.

Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

Science.gov (United States)

Barho, Franziska B.; Gonzalez-Posada, Fernando; Milla, Maria-Jose; Bomers, Mario; Cerutti, Laurent; Tournié, Eric; Taliercio, Thierry

2017-11-01

Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surface-enhanced infrared absorption (SEIRA) spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangular-shaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR) with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR.

Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

Directory of Open Access Journals (Sweden)

Barho Franziska B.

2017-11-01

Full Text Available Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surface-enhanced infrared absorption (SEIRA spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangular-shaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR.

Analysis of functional organic molecules at noble metal surfaces by means of vibrational spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Leyssner, Felix

2011-10-24

The goal of this work is to optimize the efficiency of photoinduced molecular switching processes on surfaces via controlled variations of the adsorption and electronic properties of the switch. We investigated the influence of external stimuli, i.e. photons and thermal activation, on surface bound molecular switches undergoing trans/cis-isomerizations and ring-opening/closing-reactions, respectively. High resolution electron energy loss spectroscopy (HREELS) and sum-frequency generation (SFG) spectroscopy have been used as the main tools to investigate the adsorption behavior and the molecular switching properties. Two basic concepts of coupling the molecular switch to the surface have been studied: (i) physisorbed or weakly chemisorbed systems deposited on noble metal surfaces under UHV conditions and (ii) molecular switches bound covalently via anchor groups. In the HREELS study following concept (i), we investigated the adsorption geometry and isomerization behavior of various molecular switches on metal substrates which are able to undergo a photoinduced trans/cis-isomerization in solution. We investigated three isoelectronic molecules on Au where we systematically changed the photochemically active group from the diazo-group in an azobenzene-derivative (on Cu(111)) to the imine-group, and the vinylene-group, respectively. Finding the photoisomerization quenched for all systems we observed considerable differences in their thermal isomerization behavior. Comparable we find the photoinduced ring-opening/closing-reaction of spiropyran quenched on Au(111) but a thermally induced ring-opening reaction resulting in the open form being strongly stabilized by the metal. SFG spectroscopy is employed to investigate the reversible, photoinduced trans/cis-isomerization of an azobenzene-functionalized self-assembled monolayer (SAM) on gold using a tripodal linker system. In consequence of the decoupling provided by the tripodal linker, the switching behavior of the

Porous Silicon Covered with Silver Nanoparticles as Surface-Enhanced Raman Scattering (SERS) Substrate for Ultra-Low Concentration Detection.

Science.gov (United States)

Kosović, Marin; Balarin, Maja; Ivanda, Mile; Đerek, Vedran; Marciuš, Marijan; Ristić, Mira; Gamulin, Ozren

2015-12-01

Microporous and macro-mesoporous silicon templates for surface-enhanced Raman scattering (SERS) substrates were produced by anodization of low doped p-type silicon wafers. By immersion plating in AgNO3, the templates were covered with silver metallic film consisting of different silver nanostructures. Scanning electron microscopy (SEM) micrographs of these SERS substrates showed diverse morphology with significant difference in an average size and size distribution of silver nanoparticles. Ultraviolet-visible-near-infrared (UV-Vis-NIR) reflection spectroscopy showed plasmonic absorption at 398 and 469 nm, which is in accordance with the SEM findings. The activity of the SERS substrates was tested using rhodamine 6G (R6G) dye molecules and 514.5 nm laser excitation. Contrary to the microporous silicon template, the SERS substrate prepared from macro-mesoporous silicon template showed significantly broader size distribution of irregular silver nanoparticles as well as localized surface plasmon resonance closer to excitation laser wavelength. Such silver morphology has high SERS sensitivity that enables ultralow concentration detection of R6G dye molecules up to 10(-15) M. To our knowledge, this is the lowest concentration detected of R6G dye molecules on porous silicon-based SERS substrates, which might even indicate possible single molecule detection.

The theory of surface-enhanced Raman scattering on semiconductor nanoparticles; toward the optimization of SERS sensors.

Science.gov (United States)

Lombardi, John R

2017-12-04

We present an expression for the lowest order nonzero contribution to the surface-enhanced Raman spectrum obtained from a system of a molecule adsorbed on a semiconductor nanoparticle. Herzberg-Teller vibronic coupling of the zero-order Born-Oppenheimer states results in an expression which may be regarded as an extension of the Albrecht A-, B-, and C-terms to SERS substrates. We show that the SERS enhancement is caused by combinations of several types of resonances in the combined system, namely, surface, exciton, charge-transfer, and molecular resonances. These resonances are coupled by terms in the numerator, which provide selection rules that enable various tests of the theory and predict the relative intensities of the Raman lines. Furthermore, by considering interactions of the various contributions to the SERS enhancement, we are able to develop ways to optimize the enhancement factor by tailoring the semiconductor nanostructure, thereby adjusting the locations of the various contributing resonances. This provides a procedure by which molecular sensors can be constructed and optimized. We provide several experimental examples on substrates such as monolayer MoS 2 and GaN nanorods.

Surface-enhanced Raman spectroscopy substrate based on Ag-coated self-assembled polystyrene spheres

Science.gov (United States)

Mikac, Lara; Ivanda, Mile; Gotić, Marijan; Janicki, Vesna; Zorc, Hrvoje; Janči, Tibor; Vidaček, Sanja

2017-10-01

The silver (Ag) films were deposited on the monodispersed polystyrene spheres that were drop-coated on hydrophilic glass substrates in order to form a self-assembled 2D monolayer. Thus prepared Ag films over polystyrene nanospheres (AgFONs) were used to record the surface-enhanced Raman scattering (SERS) spectra of rhodamine 6G (R6G) and pyridine (λex = 514.5 nm). AgFONs were prepared by depositing 120, 180 and 240 nm thick Ag layer on the 1000 nm polystyrene spheres and 80, 120, 160 and 200 nm thick Ag layer on the 350 nm spheres as well as on their mixture (350 + 1000 nm). The silver was deposited by electron beam evaporation technique. The best enhancement of the Raman signal for both test molecules was obtained using 180 nm Ag film deposited on the 1000 nm spheres and using 80 nm Ag film deposited on the 350 nm polystyrene spheres. The lowest detectable concentrations of R6G and pyridine were 10-9 mol L-1 and 1.2 × 10-3 mol L-1, respectively. This study has shown that AgFONs could be regarded as good and reproducible SERS substrate for analytical detection of various organic molecules.

Chiral surface waves for enhanced circular dichroism

Science.gov (United States)

Pellegrini, Giovanni; Finazzi, Marco; Celebrano, Michele; Duò, Lamberto; Biagioni, Paolo

2017-06-01

We present a novel chiral sensing platform that combines a one-dimensional photonic crystal design with a birefringent surface defect. The platform sustains simultaneous transverse electric and transverse magnetic surface modes, which are exploited to generate chiral surface waves. The present design provides homogeneous and superchiral fields of both handednesses over arbitrarily large areas in a wide spectral range, resulting in the enhancement of the circular dichroism signal by more than two orders of magnitude, thus paving the road toward the successful combination of surface-enhanced spectroscopies and electromagnetic superchirality.

Surface-enhanced chiroptical spectroscopy with superchiral surface waves.

Science.gov (United States)

Pellegrini, Giovanni; Finazzi, Marco; Celebrano, Michele; Duò, Lamberto; Biagioni, Paolo

2018-07-01

We study the chiroptical properties of one-dimensional photonic crystals supporting superchiral surface waves by introducing a simple formalism based on the Fresnel reflection matrix. We show that the proposed framework provides useful insights on the behavior of all the relevant chiroptical quantities, allowing for a deeper understanding of surface-enhanced chiral sensing platforms based on one-dimensional photonic crystals. Finally, we analyze and discuss the limitations of such platforms as the surface concentration of the target chiral analytes is gradually increased. © 2018 Wiley Periodicals, Inc.

Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

Science.gov (United States)

He, Xin; Kim, Seong H

2018-02-20

Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy

KAUST Repository

Cai, Qiran

2015-01-01

Atomically thin boron nitride (BN) nanosheets have been found to be excellent substrates for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets using a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depend on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrates as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of the analyte. The Au/BN substrates can be reused by heating in air to remove the adsorbed analyte without loss of SERS enhancement. This journal is © the Owner Societies 2015.

Surface-Enhanced Raman Scattering Nanoparticles as Optical Labels for Imaging Cell Surface Proteins

Science.gov (United States)

MacLaughlin, Christina M.

Assaying the expression of cell surface proteins has widespread application for characterizing cell type, developmental stage, and monitoring disease transformation. Immunophenotyping is conducted by treating cells with labelled targeting moieties that have high affinity for relevant surface protein(s). The sensitivity and specificity of immunophenotyping is defined by the choice of contrast agent and therefore, the number of resolvable signals that can be used to simultaneously label cells. Narrow band width surface-enhanced Raman scattering (SERS) nanoparticles are proposed as optical labels for multiplexed immunophenotying. Two types of surface coatings were investigated to passivate the gold nanoparticles, incorporate SERS functionality, and to facilitate attachment of targeting antibodies. Thiolated poly(ethylene glycol) forms dative bonds with the gold surface and is compatible with multiple physisorbed Raman-active reporter molecules. Ternary lipid bilayers are used to encapsulate the gold nanoparticles particles, and incorporate three different classes of Raman reporters. TEM, UV-Visible absorbance spectroscopy, DLS, and electrophoretic light scattering were used characterize the particle coating. Colourimetric protein assay, and secondary antibody labelling were used to quantify the antibody conjugation. Three different in vitromodels were used to investigate the binding efficacy and specificity of SERS labels for their biomarker targets. Primary human CLL cells, LY10 B lymphoma, and A549 adenocarcinoma lines were targeted. Dark field imaging was used to visualize the colocalization of SERS labels with cells, and evidence of receptor clustering was obtained based on colour shifts of the particles' Rayleigh scattering. Widefield, and spatially-resolved Raman spectra were used to detect labels singly, and in combination from labelled cells. Fluorescence flow cytometry was used to test the particles' binding specificity, and SERS from labelled cells was also

SEM visualization of glycosylated surface molecules using lectin-coated microspheres

Science.gov (United States)

Duke, J.; Janer, L.; Campbell, M.

1985-01-01

There are several techniques currently used to localize glycosylated surface molecules by scanning electron microscopy (Grinnell, 1980; Molday, 1976; Linthicum and Sell, 1975; Nicolson, 1974; Lo Buglio, et al, 1972). A simple and rapid method, using a modification of Grinnell's technique is reported here. Essentially, microspheres coated with Concavalin A are used to bind to glycosylated regions of the palatal shelf epithelium and are visualized in the scanning electron microscope (SEM).

Surface enhanced Raman spectroscopy detection of biomolecules using EBL fabricated nanostructured substrates.

Science.gov (United States)

Peters, Robert F; Gutierrez-Rivera, Luis; Dew, Steven K; Stepanova, Maria

2015-03-20

Fabrication and characterization of conjugate nano-biological systems interfacing metallic nanostructures on solid supports with immobilized biomolecules is reported. The entire sequence of relevant experimental steps is described, involving the fabrication of nanostructured substrates using electron beam lithography, immobilization of biomolecules on the substrates, and their characterization utilizing surface-enhanced Raman spectroscopy (SERS). Three different designs of nano-biological systems are employed, including protein A, glucose binding protein, and a dopamine binding DNA aptamer. In the latter two cases, the binding of respective ligands, D-glucose and dopamine, is also included. The three kinds of biomolecules are immobilized on nanostructured substrates by different methods, and the results of SERS imaging are reported. The capabilities of SERS to detect vibrational modes from surface-immobilized proteins, as well as to capture the protein-ligand and aptamer-ligand binding are demonstrated. The results also illustrate the influence of the surface nanostructure geometry, biomolecules immobilization strategy, Raman activity of the molecules and presence or absence of the ligand binding on the SERS spectra acquired.

Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

Energy Technology Data Exchange (ETDEWEB)

Ogletree, D.F.

1986-11-01

LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2..sqrt..3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (..sqrt..3 x ..sqrt..3) reconstruction on the (111) face of the ..cap alpha..-CuAl alloy has been determined.

Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

International Nuclear Information System (INIS)

Ogletree, D.F.

1986-11-01

LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2√3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (√3 x √3) reconstruction on the (111) face of the α-CuAl alloy has been determined

A new route to produce efficient surface-enhanced Raman spectroscopy substrates: gold-decorated CdSe nanowires

Energy Technology Data Exchange (ETDEWEB)

Das, Gobind; Chakraborty, Ritun; Gopalakrishnan, Anisha [Italian Institute of Technology, Nanostructure Division (Italy); Baranov, Dmitry [University of Colorado at Boulder, Department of Chemistry and Biochemistry (United States); Di Fabrizio, Enzo [King Abdullah University Science and Technology (KAUST), PSE and BESE Divisions (Saudi Arabia); Krahne, Roman, E-mail: roman.krahne@iit.it [Italian Institute of Technology, Nanostructure Division (Italy)

2013-05-15

Surface-enhanced Raman spectroscopy is a popular tool for the detection of extremely small quantities of target molecules. Au nanoparticles have been very successful in this respect due to local enhancement of the light intensity caused by their plasmon resonance. Furthermore, Au nanoparticles are biocompatible, and target substances can be easily attached to their surface. Here, we demonstrate that Au-decorated CdSe nanowires when employed as SERS substrates lead to an enhancement as large as 10{sup 5} with respect to the flat Au surfaces. In the case of hybrid metal-CdSe nanowires, the Au nucleates preferably on lattice defects at the lateral facets of the nanowires, which leads to a homogeneous distribution of Au nanoparticles on the nanowire, and to an efficient quenching of the nanowire luminescence. Moreover, the size of the Au nanoparticles can be well controlled via the AuCl{sub 3} concentration in the fabrication process. We demonstrate the effectiveness of our SERS substrates with two target substances, namely, cresyl-violet and rhodamine-6G. Au-decorated nanowires can be easily fabricated in large quantities at low cost by wet-chemical synthesis. Furthermore, their deposition onto various substrates, as well as the functionalization of these wires with the target substances, is as straightforward as with the traditional markers.

On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

Energy Technology Data Exchange (ETDEWEB)

Gao, Yi, E-mail: yig057@ucsd.edu; Galperin, Michael, E-mail: migalperin@ucsd.edu [Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093 (United States); Nitzan, Abraham, E-mail: nitzan@post.tau.ac.il [Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA and School of Chemistry, Tel Aviv University, Tel Aviv 69978 (Israel)

2016-06-28

Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases when the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.

Polarization Dependence of Surface Enhanced Raman Scattering on a Single Dielectric Nanowire

Directory of Open Access Journals (Sweden)

Hua Qi

2012-01-01

Full Text Available Our measurements of surface enhanced Raman scattering (SERS on Ga2O3 dielectric nanowires (NWs core/silver composites indicate that the SERS enhancement is highly dependent on the polarization direction of the incident laser light. The polarization dependence of the SERS signal with respect to the direction of a single NW was studied by changing the incident light angle. Further investigations demonstrate that the SERS intensity is not only dependent on the direction and wavelength of the incident light, but also on the species of the SERS active molecule. The largest signals were observed on an NW when the incident 514.5 nm light was polarized perpendicular to the length of the NW, while the opposite phenomenon was observed at the wavelength of 785 nm. Our theoretical simulations of the polarization dependence at 514.5 nm and 785 nm are in good agreement with the experimental results.

A high-yield, one-step synthesis of surfactant-free gold nanostars and numerical study for single-molecule SERS application

Energy Technology Data Exchange (ETDEWEB)

Chatterjee, S.; Ringane, A. B.; Arya, A.; Das, G. M.; Dantham, V. R., E-mail: dantham@iitp.ac.in; Laha, R. [Indian Institute of Technology Patna, Department of Physics (India); Hussian, S. [Indian Institute of Technology Patna, Department of Chemistry (India)

2016-08-15

We report a high-yield synthesis of star-shaped gold nanostructures in one step, using a new surfactant-free wet chemistry method. Compared to the existing reports, these nanostars were found to have longer and sharper spikes anchored uniformly on the surface of the spherical core, allowing at least a few hot spots irrespective of the incident light polarization. The average experimental values of core radius and spike length were found to be 88.5 and 72 nm, respectively. Using these values in numerical simulations, the local electric field enhancement (η) and localized surface plasmon resonance (LSPR) spectrum were obtained. Moreover, the single-molecule surface-enhanced Raman scattering (SERS) enhancement factor was found to vary from 10{sup 10} to 10{sup 13} depending on the excitation wavelengths. Our theoretical calculations suggest that these nanostructures can be used to fabricate efficient SERS-based biosensors for the detection of single molecules in real time and for predicting structural information of single molecules.

[Three-dimensional vertically aligned CNTs coated by Ag nanoparticles for surface-enhanced Raman scattering].

Science.gov (United States)

Zhang, Xiao-Lei; Zhang, Jie; Fan, Tuo; Ren, Wen-Jie; Lai, Chun-Hong

2014-09-01

In order to make surface-enhanced Raman scattering (SERS) substrates contained more "hot spots" in a three-dimensional (3D) focal volume, and can be adsorbed more probe molecules and metal nanoparticles, to obtain stronger Raman spectral signal, a new structure based on vertically aligned carbon nanotubes (CNTs) coated by Ag nanoparticles for surface Raman enhancement is presented. The vertically aligned CNTs are synthesized by chemical vapor deposition (CVD). A silver film is first deposited on the vertically aligned CNTs by magnetron sputtering. The samples are then annealed at different temperature to cause the different size silver nanoparticles to coat on the surface and sidewalls of vertically aligned CNTs. The result of scanning electron microscopy(SEM) shows that Ag nanoparticles are attached onto the sidewalls and tips of the vertically aligned CNTs, as the annealing temperature is different , pitch size, morphology and space between the silver nanoparticles is vary. Rhodamine 6G is served as the probe analyte. Raman spectrum measurement indicates that: the higher the concentration of R6G, the stronger the Raman intensity, but R6G concentration increase with the enhanced Raman intensity varies nonlinearly; when annealing temperature is 450 °C, the average size of silver nanoparticles is about 100 to 120 nm, while annealing temperature is 400 °C, the average size is about 70 nm, and the Raman intensity of 450 °C is superior to the annealing temperature that of 400 °C and 350 °C.

Energy transfer between surface-immobilized light-harvesting chlorophyll a/b complex (LHCII) studied by surface plasmon field-enhanced fluorescence spectroscopy (SPFS).

Science.gov (United States)

Lauterbach, Rolf; Liu, Jing; Knoll, Wolfgang; Paulsen, Harald

2010-11-16

The major light-harvesting chlorophyll a/b complex (LHCII) of the photosynthetic apparatus in green plants can be viewed as a protein scaffold binding and positioning a large number of pigment molecules that combines rapid and efficient excitation energy transfer with effective protection of its pigments from photobleaching. These properties make LHCII potentially interesting as a light harvester (or a model thereof) in photoelectronic applications. Most of such applications would require the LHCII to be immobilized on a solid surface. In a previous study we showed the immobilization of recombinant LHCII on functionalized gold surfaces via a 6-histidine tag (His tag) in the protein moiety. In this work the occurrence and efficiency of Förster energy transfer between immobilized LHCII on a functionalized surface have been analyzed by surface plasmon field-enhanced fluorescence spectroscopy (SPFS). A near-infrared dye was attached to some but not all of the LHC complexes, serving as an energy acceptor to chlorophylls. Analysis of the energy transfer from chlorophylls to this acceptor dye yielded information about the extent of intercomplex energy transfer between immobilized LHCII.

Organic molecules as tools to control the growth, surface structure, and redox activity of colloidal quantum dots.

Science.gov (United States)

Weiss, Emily A

2013-11-19

Account, I describe the varied roles of organic molecules in controlling the structure and properties of colloidal quantum dots. Molecules serve as surfactant that determines the mechanism and rate of nucleation and growth and the final size and surface structure of a quantum dot. Anionic surfactant in the reaction mixture allows precise control over the size of the quantum dot core but also drives cation enrichment and structural disordering of the quantum dot surface. Molecules serve as chemisorbed ligands that dictate the energetic distribution of surface states. These states can then serve as thermodynamic traps for excitonic charge carriers or couple to delocalized states of the quantum dot core to change the confinement energy of excitonic carriers. Ligands, therefore, in some cases, dramatically shift the ground state absorption and photoluminescence spectra of quantum dots. Molecules also act as protective layers that determine the probability of redox processes between quantum dots and other molecules. How much the ligand shell insulates the quantum dot from electron exchange with a molecular redox partner depends less on the length or degree of conjugation of the native ligand and more on the density and packing structure of the adlayer and the size and adsorption mode of the molecular redox partner. Control of quantum dot properties in these examples demonstrates that nanoscale interfaces, while complex, can be rationally designed to enhance or specify the functionality of a nanostructured system.

Adsorption of metal-phthalocyanine molecules onto the Si(111) surface passivated by δ doping: Ab initio calculations

Science.gov (United States)

Veiga, R. G. A.; Miwa, R. H.; McLean, A. B.

2016-03-01

We report first-principles calculations of the energetic stability and electronic properties of metal-phthalocyanine (MPc) molecules (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn) adsorbed on the δ -doped Si(111)-B (√{3 }×√{3 }) reconstructed surface. (i) It can be seen that CrPc, MnPc, FePc, and CoPc are chemically anchored to the topmost Si atom. (ii) Contrastingly, the binding of the NiPc, CuPc, and ZnPc molecules to the Si (111 ) -B (√{3 }×√{3 }) surface is exclusively ruled by van der Waals interactions, the main implication being that these molecules may diffuse and rearrange to form clusters and/or self-organized structures on this surface. The electronic structure calculations reveal that in point (i), owing to the formation of the metal-Si covalent bond, the net magnetic moment of the molecule is quenched by 1 μB , remaining unchanged in point (ii). In particular, the magnetic moment of CuPc (1 μB ) is preserved after adsorption. Finally, we verify that the formation of ZnPc, CuPc, and NiPc molecular (self-assembled) arrangements on the Si(111)-B (√{3 }×√{3 } ) surface is energetically favorable, in good agreement with recent experimental findings.

Synthesis of 2.5 nm colloidal iridium nanoparticles with strong surface enhanced Raman scattering activity

International Nuclear Information System (INIS)

Cui, Malin; Zhao, Yuan; Wang, Chan; Song, Qijun

2016-01-01

Colloidal iridium nanoparticles (IrNPs) were synthesized through an environmentally friendly approach by using trisodium citrate as the capping molecule in an aqueous medium. The resulting colloidal IrNPs have a typical diameter of 2.5 nm and display absorption bands at 250, 400 and 600 nm. They possess uniform morphology, good dispersibility, excellent stability in water, and exhibit strong surface enhanced Raman scattering (SERS) activity with an enhancement factor (EF) of 3.5 × 10 5 at the 1512 cm -1 peak when using Rhodamine 6G as the probe molecule. The excellent SERS performance of the IrNPs was exemplarily applied to the determination of the industrial colorant Sudan Red I. The peak intensity of the Raman band at 1236 cm -1 is linearly related to the concentration of Sudan Red I which can be determined by SERS in the 2 nM to 8 μM concentration range with a limit of detection as low as 0.6 nM. In our perception, this strong SERS activity of the IrNPs has a large potential in the SERS-based quantitation of various chemical substances. (author)

Surface-enhanced Raman spectroscopy: nonlocal limitations

DEFF Research Database (Denmark)

Toscano, Giuseppe; Raza, Søren; Xiao, Sanshui

2012-01-01

for our understanding of surface-enhanced Raman spectroscopy (SERS). The intrinsic length scale of the electron gas serves to smear out assumed field singularities, leaving the SERS enhancement factor finite, even for geometries with infinitely sharp features. For silver nanogroove structures, mimicked...

Nonlinear optical techniques for surface studies

International Nuclear Information System (INIS)

Shen, Y.R.

1981-09-01

Recent effort in developing nonlinear optical techniques for surface studies is reviewed. Emphasis is on monolayer detection of adsorbed molecules on surfaces. It is shown that surface coherent antiStokes Raman scattering (CARS) with picosecond pulses has the sensitivity of detecting submonolayer of molecules. On the other hand, second harmonic or sum-frequency generation is also sensitive enough to detect molecular monolayers. Surface-enhanced nonlinear optical effects on some rough metal surfaces have been observed. This facilitates the detection of molecular monolayers on such surfaces, and makes the study of molecular adsorption at a liquid-metal interface feasible. Advantages and disadvantages of the nonlinear optical techniques for surface studies are discussed

Metallic nanocone array photonic substrate for high-uniformity surface deposition and optical detection of small molecules

International Nuclear Information System (INIS)

Coppe, Jean-Philippe; Xu Zhida; Chen Yi; Logan Liu, G

2011-01-01

Molecular probe arrays printed on solid surfaces such as DNA, peptide, and protein microarrays are widely used in chemical and biomedical applications especially genomic and proteomic studies (Pollack et al 1999 Nat. Genet. 23 41-6, Houseman et al 2002 Nat. Biotechnol. 20 270-4, Sauer et al 2005 Nat. Rev. Genet. 6 465-76) as well as surface imaging and spectroscopy (Mori et al 2008 Anal. Biochem. 375 223-31, Liu et al 2006 Nat. Nanotechnol. 1 47-52, Liu 2010 IEEE J. Sel. Top. Quantum Electron. 16 662-71). Unfortunately the printed molecular spots on solid surfaces often suffer low distribution uniformity due to the lingering 'coffee stain' (Deegan et al 1997 Nature 389 827-9) problem of molecular accumulations and blotches, especially around the edge of deposition spots caused by solvent evaporation and convection processes. Here we present, without any surface chemistry modification, a unique solid surface of high-aspect-ratio silver-coated silicon nanocone arrays that allows highly uniform molecular deposition and thus subsequent uniform optical imaging and spectroscopic molecular detection. Both fluorescent Rhodamine dye molecules and unlabeled oligopeptides are printed on the metallic nanocone photonic substrate surface as circular spot arrays. In comparison with the printed results on ordinary glass slides and silver-coated glass slides, not only high printing density but uniform molecular distribution in every deposited spot is achieved. The high-uniformity and repeatability of molecular depositions on the 'coffee stain'-free nanocone surface is confirmed by laser scanning fluorescence imaging and surface enhanced Raman imaging experiments. The physical mechanism for the uniform molecular deposition is attributed to the superhydrophobicity and localized pinned liquid-solid-air interface on the silver-coated silicon nanocone surface. The unique surface properties of the presented nanocone surface enabled high-density, high-uniformity probe spotting beneficial

Toward single-molecule detection with sensors based on propagating surface plasmons

Czech Academy of Sciences Publication Activity Database

Kvasnička, Pavel; Chadt, Karel; Vala, Milan; Bocková, Markéta; Homola, Jiří

2012-01-01

Roč. 37, č. 2 (2012), s. 163-165 ISSN 0146-9592 R&D Projects: GA AV ČR KAN200670701; GA MŠk OC09058; GA MŠk(CZ) LH11102 Institutional research plan: CEZ:AV0Z20670512 Keywords : optical biosenzor * single molecule * surface plasmon microscopy Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 3.385, year: 2012

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

Science.gov (United States)

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Surface chemical reactions induced by molecules electronically-excited in the gas

DEFF Research Database (Denmark)

Petrunin, Victor V.

2011-01-01

and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

Development of a miRNA surface-enhanced Raman scattering assay using benchtop and handheld Raman systems

Science.gov (United States)

Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Cote, Gerard

2018-01-01

DNA-functionalized nanoparticles, when paired with surface-enhanced Raman spectroscopy (SERS), can rapidly detect microRNA. However, widespread use of this approach is hindered by drawbacks associated with large and expensive benchtop Raman microscopes. MicroRNA-17 (miRNA-17) has emerged as a potential epigenetic indicator of preeclampsia, a condition that occurs during pregnancy. Biomarker detection using an SERS point-of-care device could enable prompt diagnosis and prevention as early as the first trimester. Recently, strides have been made in developing portable Raman systems for field applications. An SERS assay for miRNA-17 was assessed and translated from traditional benchtop Raman microscopes to a handheld system. Three different photoactive molecules were compared as potential Raman reporter molecules: a chromophore, malachite green isothiocyanate (MGITC), a fluorophore, tetramethylrhodamine isothiocyanate, and a polarizable small molecule 5,5-dithio-bis-(2-nitrobenzoic acid) (DTNB). For the benchtop Raman microscope, the DTNB-labeled assay yielded the greatest sensitivity under 532-nm laser excitation, but the MGITC-labeled assay prevailed at 785 nm. Conversely, DTNB was preferable for the miniaturized 785-nm Raman system. This comparison showed significant SERS enhancement variation in response to 1-nM miRNA-17, implying that the sensitivity of the assay may be more heavily dependent on the excitation wavelength, instrumentation, and Raman reporter chosen than on the plasmonic coupling from DNA/miRNA-mediated nanoparticle assemblies.

Advances in single-molecule magnet surface patterning through microcontact printing.

Science.gov (United States)

Mannini, Matteo; Bonacchi, Daniele; Zobbi, Laura; Piras, Federica M; Speets, Emiel A; Caneschi, Andrea; Cornia, Andrea; Magnani, Agnese; Ravoo, Bart Jan; Reinhoudt, David N; Sessoli, Roberta; Gatteschi, Dante

2005-07-01

We present an implementation of strategies to deposit single-molecule magnets (SMMs) using microcontact printing microCP). We describe different approaches of microCP to print stripes of a sulfur-functionalized dodecamanganese (III, IV) cluster on gold surfaces. Comparison by atomic force microscopy profile analysis of the patterned structures confirms the formation of a chemically stable single layer of SMMs. Images based on chemical contrast, obtained by time-of-flight secondary ion mass spectrometry, confirm the patterned structure.

Effect of surface density silver nanoplate films toward surface-enhanced Raman scattering enhancement for bisphenol A detection

Science.gov (United States)

Bakar, N. A.; Salleh, M. M.; Umar, A. A.; Shapter, J. G.

2018-03-01

This paper reports a study on surface-enhanced Raman scattering (SERS) phenomenon of triangular silver nanoplate (NP) films towards bisphenol A (BPA) detection. The NP films were prepared using self-assembly technique with four different immersion times; 1 hour, 2 hours, 5 hours, and 8 hours. The SERS measurement was studied by observing the changes in Raman spectra of BPA after BPA absorbed on the NP films. It was found that the Raman intensity of BPA peaks was enhanced by using the prepared SERS substrates. This is clearly indicated that these SERS silver substrates are suitable to sense industrial chemical and potentially used as SERS detector. However, the rate of SERS enhancement is depended on the distribution of NP on the substrate surface.

Single NdPc{sub 2} molecules on surfaces. Adsorption, interaction, and molecular magnetism

Energy Technology Data Exchange (ETDEWEB)

Fahrendorf, Sarah

2013-01-24

They have huge potential for application in molecular-spin-transistors, molecular-spinvalves, and molecular quantum computing. SMMs are characterized by high spin ground states with zero-field splitting leading to high relaxation barriers and long relaxation times. A relevant class of molecules are the lanthanide double-decker phthalocyanines (LaPc{sub 2}) with only one metal atom sandwiched between two organic phthalocyanine (Pc) ligands. For envisaged spintronic applications it is important to understand the interaction between the molecules and the substrate and its influence on the electronic and magnetic properties. The subject of this thesis is the investigation of the adsorbed neodymium double-decker phthalocyanine (NdPc{sub 2}) by means of low temperature scanning tunneling microscopy and spectroscopy (STM and STS). The molecules are deposited by sublimation onto different substrates. It is observed that a large fraction of the double-decker molecules decomposes during deposition. The decomposition probability strongly depends on the chosen substrate. Therefore it is concluded that the substrate modifies the electronic structure of the molecule leading to a stabilization or destabilization of the molecular entity. Charge transfer from the surface to the molecule is identified as a potential stabilizing mechanism. The electronic and magnetic properties are investigated in detail for adsorbed NdPc{sub 2} molecules on Cu(100). The results of the experimental study are compared to state-of-the-art density functional theory calculations performed by our colleagues from the Peter Gruenberg Institute (PGI-1) at the Forschungszentrum Juelich. Interestingly, the lower Pc ring of the molecule hybridizes intensely with the substrate leading to strong chemisorption of the molecule, while the upper Pc ring keeps its molecular type electronic states, which can be energetically shifted by an external electric field. Importantly, it is possible to get direct access to the

Enhancing sensitivity of SERRS nanoprobes by modifying heptamethine cyanine-based reporter molecules

Directory of Open Access Journals (Sweden)

Yunfei Zhang

2016-07-01

Full Text Available Surface enhanced resonance Raman scattering (SERRS is a physical phenomenon that occurs when the energy of incident light is close to that of electronic excitation of reporter molecules (RMs attached on substrates. SERRS has showed great promise in healthcare applications such as tumor diagnosis, image-guided tumor surgery and real-time evaluation of therapeutic response due to its ultra-sensitivity, manipulating convenience and easy accessibility. As the most widely used organic near-infrared (NIR fluorophore, heptamethine cyanines possess the electronic excitation energy that is close to the plasmon absorption energy of the gold nano-scaffolds, which results in the extraordinary enhancement of the SERRS signal. However, the effect of heptamethine cyanine structure and the gold nanoparticle morphology to the SERRS intensity are barely investigated. This work developed a series of SERRS nanoprobes in which two heptamethine cyanine derivatives (IR783 and IR780 were used as the RM and three gold nanoparticles (nanorod, nanosphere and nanostar were used as the substrates. Interestingly, even though IR780 and IR783 possess very similar chemical structure, SERRS signal produced by IR780 was determined as 14 times higher than that of IR783 when the RM concentration was 6.5 × 10−6M. In contrast, less than 4.0 fold SERRS signal intensity increase was measured by changing the substrate morphologies. Above experimental results indicate that finely tuning the chemical structure of the heptamethine cyanine could be a feasible way to develop robust SERRS probes to visualize tumor or guide tumor resection with high sensitivity and target to background ratio.

Study of Surface Enhanced Raman Scattering of Alizarin and Crystal Violet Dyes

Science.gov (United States)

Gopal, Ram; Swarnkar, Raj Kumar

2010-06-01

Surface enhanced Raman scattering (SERS) plays a vital role in analytical chemistry to characterize ultra trace quantity of organic compounds and biological samples. Two mechanisms have been considered to explain the SERS effect. The main contribution arises from a huge enhancement of the local electromagnetic field close to surface roughness of the metal structures, due to the excitation of a localized surface plasmon, while a further enhancement can be observed for molecules adsorbed onto specific sites when resonant charge transfer occurs. SERS signals have been observed from adsorbates on many metallic surfaces like Ag, Au, Ni, Cu etc. Additionally, metal oxide nanoparticles also show SERS signals It has now been established that SERS of analyte material is highly dependent on the type of substrate involved. Many types of nanostructures like nanofilms, nanorods, nanospheres etc. show highly efficient SERS signals. In particular, there are two routes available for the synthesis of these nanomaterials: the chemical route and the physical route. Chemical route involves many types of reducing agents and capping agents which can interfere in origin and measurement of these signals. The physical route avoids these anomalies and therefore it is suitable for the study of SERS phenomenon. Pulsed laser ablation in liquid medium is an excellent top down technique to produce colloidal solution of nanoparticles with desired shape and size having surface free from chemical contamination, which is essential requirement for surface application of nanoparticles. The present work deals with the study of SERS of Crystal violet dye and Alizarin group dye on Cu@ Cu_2O and Ag colloidal nanoparticles synthesized by pulsed laser ablation. M. Fleishchmann, P. J. Hendra, and A. J. McQuillian Chem. Phys. Lett., 26, 163, 1974. U. Wenning, B. Pettinger, and H. Wetzel Chem. Phys. Lett., 70, 49, 1980. S. C. Singh, R. K. Swarnkar, P. Ankit, M. C. Chattopadhyaya, and R. Gopal AIP Conf. Proc

Excitation enhancement and extraction enhancement with photonic crystals

Science.gov (United States)

Shapira, Ofer; Soljacic, Marin; Zhen, Bo; Chua, Song-Liang; Lee, Jeongwon; Joannopoulos, John

2015-03-03

Disclosed herein is a system for stimulating emission from at least one an emitter, such as a quantum dot or organic molecule, on the surface of a photonic crystal comprising a patterned dielectric substrate. Embodiments of this system include a laser or other source that illuminates the emitter and the photonic crystal, which is characterized by an energy band structure exhibiting a Fano resonance, from a first angle so as to stimulate the emission from the emitter at a second angle. The coupling between the photonic crystal and the emitter may result in spectral and angular enhancement of the emission through excitation and extraction enhancement. These enhancement mechanisms also reduce the emitter's lasing threshold. For instance, these enhancement mechanisms enable lasing of a 100 nm thick layer of diluted organic molecules solution with reduced threshold intensity. This reduction in lasing threshold enables more efficient organic light emitting devices and more sensitive molecular sensing.

Physisorption of three amine terminated molecules (TMBDA, BDA, TFBDA) on the Au(111) Surface: The Role of van der Waals Interaction

Science.gov (United States)

Aminpour, Maral; Le, Duy; Rahman, Talat S.

2012-02-01

Recently, the electronic properties and alignment of tetramethyl-1,4-benzenediamine (TMBDA), 1,4-benzenediamine (BDA) and tetrafluro-1,4-benzenediamine (TFBDA) molecules were studied experimentally. Discrepancies were found for both the binding energy and the molecule tilt angle with respect to the surface, when results were compared with density functional theory calculations [1]. We have included the effect of vdW interactions both between the molecules and the Au(111) surface and find binding energies which are in very good agreement with experiments. We also find that at low coverages each of these molecules would adsorb almost parallel to the surface. N-Au bond lengths and charge redistribution on adsorption of the molecules are also analyzed. Our calculations are based on DFT using vdW-DF exchange correlation functionals. For BDA (since we are aware of experimental data), we show that for higher coverage, inclusion of intermolecular van der Waals interaction leads to tilting of the molecules with respect to the surface and formation of line structures. Our results demonstrate the central role played by intermolecular interaction in pattern formation on this surface.[4pt] [1] M. Dell'Angela et al, Nano Lett. 2010, 10, 2470; M. Kamenetska et al, J. Phys. Chem. C, 2011, 115, 12625

Diamond surface functionalization with biomimicry – Amine surface tether and thiol moiety for electrochemical sensors

Energy Technology Data Exchange (ETDEWEB)

Sund, James B., E-mail: jim@jamessund.com [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Causey, Corey P. [Departments of Chemistry and Biochemistry, Duke University, Durham, NC (United States); Wolter, Scott D. [Department of Physics, Elon University, Elon, NC 27244 (United States); Parker, Charles B., E-mail: charles.parker@duke.edu [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Stoner, Brian R. [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States); Research Triangle Institute (RTI) International, Research Triangle Park, NC (United States); Toone, Eric J. [Departments of Chemistry and Biochemistry, Duke University, Durham, NC (United States); Glass, Jeffrey T. [Department of Electrical and Computer Engineering, Duke University, Durham, NC (United States)

2014-05-01

Highlights: • Diamond surfaces were functionalized with organic molecules using a novel approach. • Used biomimicry to select a molecule to bind NO, similar to the human body. • Molecular orbital theory predicted the molecule-analyte oxidation behavior. • A thiol moiety was attached to an amine surface tether on the diamond surface. • XPS analysis verified each surface functionalization step. - Abstract: The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen–oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

Diamond surface functionalization with biomimicry – Amine surface tether and thiol moiety for electrochemical sensors

International Nuclear Information System (INIS)

Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

2014-01-01

Highlights: • Diamond surfaces were functionalized with organic molecules using a novel approach. • Used biomimicry to select a molecule to bind NO, similar to the human body. • Molecular orbital theory predicted the molecule-analyte oxidation behavior. • A thiol moiety was attached to an amine surface tether on the diamond surface. • XPS analysis verified each surface functionalization step. - Abstract: The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen–oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis

Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

International Nuclear Information System (INIS)

Chang, Yung-Ting; Liu, Shun-Wei; Yuan, Chih-Hsien; Lee, Chih-Chien; Ho, Yu-Hsuan; Wei, Pei-Kuen; Chen, Kuan-Yu; Lee, Yi-Ting; Wu, Min-Fei; Chen, Chin-Ti; Wu, Chih-I

2013-01-01

Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7 cd/A and maximum power efficiency of 8.39 lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7 cd/A and 8.39 lm/W to 23 cd/A and 13.2 lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts

Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

Energy Technology Data Exchange (ETDEWEB)

Chang, Yung-Ting [Institute of Chemistry, Academia Sinica, Taipei, Taiwan 11529, Taiwan (China); Department of Electrical Engineering, Graduate Institute of Photonics and Optoelectronics, National Taiwan University, Taipei, Taiwan 10617, Taiwan (China); Liu, Shun-Wei [Department of Electronic Engineering, Mingchi University of Technology, New Taipei, Taiwan 24301, Taiwan (China); Yuan, Chih-Hsien; Lee, Chih-Chien [Department of Electronic Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan 10607, Taiwan (China); Ho, Yu-Hsuan; Wei, Pei-Kuen [Research Center for Applied Science Academia Sinica, Taipei, Taiwan 11527, Taiwan (China); Chen, Kuan-Yu [Chilin Technology Co., LTD, Tainan City, Taiwan 71758, Taiwan (China); Lee, Yi-Ting; Wu, Min-Fei; Chen, Chin-Ti, E-mail: cchen@chem.sinica.edu.tw, E-mail: chihiwu@cc.ee.ntu.edu.tw [Institute of Chemistry, Academia Sinica, Taipei, Taiwan 11529, Taiwan (China); Wu, Chih-I, E-mail: cchen@chem.sinica.edu.tw, E-mail: chihiwu@cc.ee.ntu.edu.tw [Department of Electrical Engineering, Graduate Institute of Photonics and Optoelectronics, National Taiwan University, Taipei, Taiwan 10617, Taiwan (China)

2013-11-07

Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7 cd/A and maximum power efficiency of 8.39 lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7 cd/A and 8.39 lm/W to 23 cd/A and 13.2 lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts.

Surface-enhanced molecularly imprinted electrochemiluminescence sensor based on Ru@SiO2 for ultrasensitive detection of fumonisin B1.

Science.gov (United States)

Zhang, Wei; Xiong, Huiwen; Chen, Miaomiao; Zhang, Xiuhua; Wang, Shengfu

2017-10-15

A novel molecularly imprinted electrochemiluminescence (MIP-ECL) sensor based on Ru(bpy) 3 2+ -doped silica nanoparticles (Ru@SiO 2 NPs) is developed for highly sensitive detection of fumonisin B 1 (FB 1 ). Gold-nanoparticles (AuNPs), Ru@SiO 2 NPs with chitosan (CS) composites and a molecularly imprinted polymer (MIP) are assembled on a glassy carbon electrode (GCE) to fabricate an ECL platform step by step. AuNPs could greatly promote the ECL intensity and improve the analytical sensitivity according to the localized surface plasmon resonance (LSPR) and the electrochemical effect. In this surface-enhanced electrochemiluminescence (SEECL) system, AuNPs work as the LSPR source to improve the ECL intensity and Ru@SiO 2 NPs are used as ECL luminophores. In the phosphate buffer solution (PBS), the evident anodic ECL of Ru@SiO 2 on the above working electrode is observed in the presence of the template molecule fumonisin B 1 (FB 1 ), which could act as the coreactant of Ru@SiO 2 NPs due to the amino group of FB 1 . When the template molecules were eluted from the MIP, little coreactant was left, resulting in an apparent decrease of ECL signal. After the MIP-ECL sensor was incubated in FB 1 solution, the template molecules rebound to the MIP surface, leading to the enhancement of ECL signal again. On the basis of these results, a facile MIP-ECL sensor has been successfully fabricated, which exhibited a linear range from 0.001 to 100ngmL -1 with a detection limit of 0.35pgmL -1 for FB 1 . Moreover, the proposed MIP-ECL sensor displayed an excellent application in real samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular selectivity of graphene-enhanced Raman scattering.

Science.gov (United States)

Huang, Shengxi; Ling, Xi; Liang, Liangbo; Song, Yi; Fang, Wenjing; Zhang, Jin; Kong, Jing; Meunier, Vincent; Dresselhaus, Mildred S

2015-05-13

Graphene-enhanced Raman scattering (GERS) is a recently discovered Raman enhancement phenomenon that uses graphene as the substrate for Raman enhancement and can produce clean and reproducible Raman signals of molecules with increased signal intensity. Compared to conventional Raman enhancement techniques, such as surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS), in which the Raman enhancement is essentially due to the electromagnetic mechanism, GERS mainly relies on a chemical mechanism and therefore shows unique molecular selectivity. In this paper, we report graphene-enhanced Raman scattering of a variety of different molecules with different molecular properties. We report a strong molecular selectivity for the GERS effect with enhancement factors varying by as much as 2 orders of magnitude for different molecules. Selection rules are discussed with reference to two main features of the molecule, namely its molecular energy levels and molecular structures. In particular, the enhancement factor involving molecular energy levels requires the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies to be within a suitable range with respect to graphene's Fermi level, and this enhancement effect can be explained by the time-dependent perturbation theory of Raman scattering. The enhancement factor involving the choice of molecular structures indicates that molecular symmetry and substituents similar to that of the graphene structure are found to be favorable for GERS enhancement. The effectiveness of these factors can be explained by group theory and the charge-transfer interaction between molecules and graphene. Both factors, involving the molecular energy levels and structural symmetry of the molecules, suggest that a remarkable GERS enhancement requires strong molecule-graphene coupling and thus effective charge transfer between the molecules and graphene. These conclusions are further

Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

International Nuclear Information System (INIS)

Yesildag, Ali; Ekinci, Duygu

2010-01-01

In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

Three-dimensional nanoporous MoS2 framework decorated with Au nanoparticles for surface-enhanced Raman scattering

Science.gov (United States)

Sheng, Yingqiang; Jiang, Shouzhen; Yang, Cheng; Liu, Mei; Liu, Aihua; Zhang, Chao; Li, Zhen; Huo, Yanyan; Wang, Minghong; Man, Baoyuan

2017-08-01

The three-dimensional (3D) MoS2 decorated with Au nanoparticles (Au NPs) hybrids (3D MoS2-Au NPs) for surface-enhanced Raman scattering (SERS) sensing was demonstrated in this paper. SEM, Raman spectroscopy, TEM, SAED, EDX and XRD were performed to characterize 3D MoS2-Au NPs hybrids. Rhodamine 6G (R6G), fluorescein and gallic acid molecules were used as the probe for the SERS detection of the 3D MoS2-Au NPs hybrids. In addition, we modeled the enhancement of the electric field of MoS2-Au NPs hybrids using Finite-difference time-domain (FDTD) analysis, which can further give assistance to the mechanism understanding of the SERS activity.

A new route to produce efficient surface-enhanced Raman spectroscopy substrates: Gold-decorated CdSe nanowires

KAUST Repository

Das, Gobind

2013-04-13

Surface-enhanced Raman spectroscopy is a popular tool for the detection of extremely small quantities of target molecules. Au nanoparticles have been very successful in this respect due to local enhancement of the light intensity caused by their plasmon resonance. Furthermore, Au nanoparticles are biocompatible, and target substances can be easily attached to their surface. Here, we demonstrate that Au-decorated CdSe nanowires when employed as SERS substrates lead to an enhancement as large as 105 with respect to the flat Au surfaces. In the case of hybrid metal-CdSe nanowires, the Au nucleates preferably on lattice defects at the lateral facets of the nanowires, which leads to a homogeneous distribution of Au nanoparticles on the nanowire, and to an efficient quenching of the nanowire luminescence. Moreover, the size of the Au nanoparticles can be well controlled via the AuCl3 concentration in the fabrication process. We demonstrate the effectiveness of our SERS substrates with two target substances, namely, cresyl-violet and rhodamine-6G. Au-decorated nanowires can be easily fabricated in large quantities at low cost by wet-chemical synthesis. Furthermore, their deposition onto various substrates, as well as the functionalization of these wires with the target substances, is as straightforward as with the traditional markers. © 2013 Springer Science+Business Media Dordrecht.

A new route to produce efficient surface-enhanced Raman spectroscopy substrates: Gold-decorated CdSe nanowires

KAUST Repository

Das, Gobind; Chakraborty, Ritun; Gopalakrishnan, Anisha; Baranov, Dmitry; Di Fabrizio, Enzo M.; Krahne, Roman

2013-01-01

Surface-enhanced Raman spectroscopy is a popular tool for the detection of extremely small quantities of target molecules. Au nanoparticles have been very successful in this respect due to local enhancement of the light intensity caused by their plasmon resonance. Furthermore, Au nanoparticles are biocompatible, and target substances can be easily attached to their surface. Here, we demonstrate that Au-decorated CdSe nanowires when employed as SERS substrates lead to an enhancement as large as 105 with respect to the flat Au surfaces. In the case of hybrid metal-CdSe nanowires, the Au nucleates preferably on lattice defects at the lateral facets of the nanowires, which leads to a homogeneous distribution of Au nanoparticles on the nanowire, and to an efficient quenching of the nanowire luminescence. Moreover, the size of the Au nanoparticles can be well controlled via the AuCl3 concentration in the fabrication process. We demonstrate the effectiveness of our SERS substrates with two target substances, namely, cresyl-violet and rhodamine-6G. Au-decorated nanowires can be easily fabricated in large quantities at low cost by wet-chemical synthesis. Furthermore, their deposition onto various substrates, as well as the functionalization of these wires with the target substances, is as straightforward as with the traditional markers. © 2013 Springer Science+Business Media Dordrecht.

On determination of the dynamics of hydrocarbon molecules on catalyst's surfaces by means of neutron scattering

International Nuclear Information System (INIS)

Stockmeyer, R.

1976-01-01

The intensity distribution of slow neutrons scattered by adsorbed hydrocarbon molecules contains information on the dynamics of the molecules. In this paper the scattering law for incoherently scattering molecules is derived taking into account the very different mobility perpendicular and parallel to the surface. In contrast to the well known scattering law of threedimensionally diffusing particles the scattering law for twodimensional diffusion diverges logarithmically at zero energy transfer. Conclusions relevant to the interpretation of neutron scattering data are discussed. (orig.) [de

Pulsed laser deposition of Ag nanoparticles on titanium hydroxide/oxide nanobelt arrays for highly sensitive surface-enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Jing, Yuting; Wang, Huanwen; Zhao, Jie; Yi, Huan; Wang, Xuefeng

2015-01-01

Highlights: • Silver nanoparticles (NPs) were deposited on Ti(OH) 4 nanobelt by pulsed laser deposition (PLD). • The highest enhancement factor of 10 6 and a maximum relative standard deviation (RSD) of 0.18. • Ag 2 O play important role for the high sensitivity Raman phenomenon. • Charge transfer from Ag NPs is also responsible for the enhancement ability. - Abstract: Surface-enhanced Raman scattering (SERS) substrate of Ti(OH) 4 nanobelt arrays (NBAs) was synthesized by a hydrothermal reaction, on which silver nanoparticles (NPs) were deposited by pulsed laser deposition (PLD). Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) revealed the effective high specific surface area with silver NPs decorated on three-dimensional NBAs. Using rhodamine 6G (R6G) as an analyte molecule, the highest enhancement factor of 10 6 and a maximum relative standard deviation (RSD) of 0.18 were obtained. It has been found that the specific morphology of these composite nanobelt arrays and the formation of Ag 2 O play important role for the high sensitivity Raman phenomenon. In addition, the surface plasmon resonance wavelength of Ag decorated Ti(OH) 4 NBAs and the charge transfer from Ag NPs are also responsible for the enhancement ability. For comparison SERS was investigated with silver particles decorated on TiO 2 NBAs, which is much less active

Interface properties of organic molecules on metal surfaces; Grenzflaecheneigenschaften organischer Molekuele auf Metalloberflaechen

Energy Technology Data Exchange (ETDEWEB)

Karacuban, Hatice

2010-01-28

In this work, the growth of the archetype molecules CuPc and PTCDA was investigated on Cu(111). PTCDA was also studied on NaCl/Cu(111). The main experiments were carried out with a scanning tunneling microscope. Structural analysis of CuPc on Cu (111) is only possible at low temperatures, since at room temperature the molecules exhibit a high surface mobility. For the investigation of these structures and especially to enable scanning tunneling spectroscopy, a low-temperature scanning tunneling microscope was developed. Using this home built STM the experiments could be carried out at about 10 K. After the adsorption of CuPc on Cu (111) a substrate-induced symmetry reduction of the molecules can be observed in scanning tunneling microscopy. When the occupied states of the molecules are imaged, a switching between two distinct levels is found. These modifications are determined by the adsorption geometry of the molecules. Based on high resolution STM data, an on-top adsorption geometry of the CuPc-molecules on Cu (111)-substrate can be deducted. At low temperatures, two new superstructures of PTCDA on Cu(111) are observed. The molecules within these superstructures are tilted with respect to the substrate. Intermolecular interactions may be the crucial factor for the realignment of the molecules. If PTCDA molecules are adsorbed on a NaCl/Cu (111) substrate, at room temperature, also two new superstructures on the copper substrate were found. They indicate the formation of a metall-organic-complex. On top of the NaCl layer the molecules exclusively grow at polar NaCl step edges. This is an indication for electrostatic interaction between the PTCDA molecules and the NaCl layer. When the molecule density is further increased, a Vollmer-Weber growth sets in. If both molecules PTCDA and CuPc are present on the sample at the same time, local spectroscopy provides information on the metal-organic interface in direct comparison. The STS-results of CuPc/PTCDA on Cu (111

Chemometric evaluation of temperature-dependent surface-enhanced Raman spectra of riboflavin: What is the best multivariate approach to describe the effect of temperature?

Science.gov (United States)

Kokaislová, Alžběta; Kalhousová, Milena; Gráfová, Michaela; Matějka, Pavel

2014-10-01

Riboflavin is an essential nutrient involved in energetic metabolism. It is used as a pharmacologically active substance in treatment of several diseases. From analytical point of view, riboflavin can be used as an active part of sensors for substances with affinity to riboflavin molecules. In biological environment, metal substrates coated with riboflavin are exposed to temperatures that are different from room temperature. Hence, it is important to describe the influence of temperature on adsorbed molecules of riboflavin, especially on orientation of molecules towards the metal surface and on stability of adsorbed molecular layer. Surface-enhanced Raman scattering (SERS) spectroscopy is a useful tool for investigation of architecture of molecular layers adsorbed on metal surfaces because the spectral features in SERS spectra change with varying orientation of molecules towards the metal surface, as well as with changes in mutual interactions among adsorbed molecules. In this study, riboflavin was adsorbed on electrochemically prepared massive silver substrates that were exposed to temperature changes according to four different temperature programs. Raman spectra measured at different temperatures were compared considering positions of spectral bands, their intensities, bandwidths and variability of all these parameters. It was found out that increase of substrate temperature up to 50 °C does not lead to any observable decomposition of riboflavin molecules, but the changes of band intensity ratios within individual spectra are apparent. To distinguish sources of variability beside changes in band intensities and widths, Principal Component Analysis (PCA) was applied. Discriminant Analysis (DA) was used to explore if the SERS spectra can be separated according to temperature. The results of Partial Least Squares (PLS) regression demonstrate the possibility to predict the sample temperature using SERS spectral features. Results of all performed experiments and

Measurement of the surface-enhanced coherent anti-Stokes Raman scattering (SECARS) due to the 1574 cm(-1) surface-enhanced Raman scattering (SERS) mode of benzenethiol using low-power (CW diode lasers.

Science.gov (United States)

Aggarwal, Roshan L; Farrar, Lewis W; Greeneltch, Nathan G; Van Duyne, Richard P; Polla, Dennis L

2013-02-01

The surface-enhanced coherent anti-Stokes Raman scattering (SECARS) from a self-assembled monolayer (SAM) of benzenethiol on a silver-coated surface-enhanced Raman scattering (SERS) substrate has been measured for the 1574 cm(-1) SERS mode. A value of 9.6 ± 1.7×10(-14) W was determined for the resonant component of the SECARS signal using 17.8 mW of 784.9 nm pump laser power and 7.1 mW of 895.5 nm Stokes laser power; the pump and Stokes lasers were polarized parallel to each other but perpendicular to the grooves of the diffraction grating in the spectrometer. The measured value of resonant component of the SECARS signal is in agreement with the calculated value of 9.3×10(-14) W using the measured value of 8.7 ± 0.5 cm(-1) for the SERS linewidth Γ (full width at half-maximum) and the value of 5.7 ± 1.4×10(-7) for the product of the Raman cross section σSERS and the surface concentration Ns of the benzenethiol SAM. The xxxx component of the resonant part of the third-order nonlinear optical susceptibility |3 χxxxx((3)R)| for the 1574 cm(-1) SERS mode has been determined to be 4.3 ± 1.1×10(-5) cm·g(-1)·s(2). The SERS enhancement factor for the 1574 cm(-1) mode was determined to be 3.6 ± 0.9×10(7) using the value of 1.8×10(15) molecules/cm(2) for Ns.

On the enhancement of the back-to-back two-electron-one photon ionization in molecules

Science.gov (United States)

Amusia, Miron; Drukarev, Eugene

2014-05-01

Recently, the long ago predicted quasi-free mechanism of two-electron photoionization was detected already at relatively low energy photoionization in He. It was observed that some pairs of electrons are leaving the target atom back-to-back, i.e. in opposite direction with almost the same energy. They have opposite spin directions. The cross-section of this process depends upon the probability for a pair of electrons to be close to each other before meeting the incoming photon. Such probability is greatly enhanced in molecules with covalent bonding, like H2. In this and similar molecules the electrons spend an essential part of time being between nuclei and thus screening them from each other. We demonstrate that indeed the back-to-back contribution is much bigger in H2 than in He. We analyze qualitatively some other situations that lead to relative growth of back-to-back contribution. Atoms with electrons with bigger principal quantum numbers have bigger back-to-back contributions. An external pressure applied to molecules forces electrons to be closer to each other. As a result for them the back-to-back contribution can be controllable enhanced.

Enhanced fluorescence of a molecular dipole near metal nanoparticle

International Nuclear Information System (INIS)

Pustovit, Vitaliy N.

2010-01-01

We study theoretically radiative and nonradiative decay of a single molecule near small gold nanoparticle. The local field enhancement leads to an increased radiative decay rate while the energy transfer from molecule to optically inactive electronic states in nanoparticle results in a decrease in the fluorescence quantum efficiency for small molecule-nanoparticle distances. We performed a DFT-TDLDA calculation of both the enhancement and the quenching for small nanometersized gold nanoparticles. We found that in close proximity to the surface, the nonradiative decay rate is dominated by generation of electron-hole pairs out of the Fermi sea resulting in a significantly lower quantum efficiency as compared to that obtained from electromagnetic calculations. For large distances, the efficiency is maximal for molecule polarized normal to the surface, whereas for small distances it is maximal for parallel orientation.

Enhanced fluorescence of a molecular dipole near metal nanoparticle

Energy Technology Data Exchange (ETDEWEB)

Pustovit, Vitaliy N., E-mail: pustovit@ccmsi.u [Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, General Naumov Street 17, 03164 Kyiv-164 (Ukraine)

2010-01-15

We study theoretically radiative and nonradiative decay of a single molecule near small gold nanoparticle. The local field enhancement leads to an increased radiative decay rate while the energy transfer from molecule to optically inactive electronic states in nanoparticle results in a decrease in the fluorescence quantum efficiency for small molecule-nanoparticle distances. We performed a DFT-TDLDA calculation of both the enhancement and the quenching for small nanometersized gold nanoparticles. We found that in close proximity to the surface, the nonradiative decay rate is dominated by generation of electron-hole pairs out of the Fermi sea resulting in a significantly lower quantum efficiency as compared to that obtained from electromagnetic calculations. For large distances, the efficiency is maximal for molecule polarized normal to the surface, whereas for small distances it is maximal for parallel orientation.

Self-assembled vertically aligned Au nanorod arrays for surface-enhanced Raman scattering (SERS) detection of Cannabinol

Science.gov (United States)

Milliken, Sarah; Fraser, Jeff; Poirier, Shawn; Hulse, John; Tay, Li-Lin

2018-05-01

Self-assembled multi-layered vertically aligned gold nanorod (AuNR) arrays have been fabricated by a simple preparation process that requires a balance between the particle concentration and the ionic strength of the solvent. An experimentally determined critical AuNR concentration of 2.0 nM and 50 mM NaCl produces well-ordered vertically aligned hexagonally close-packed AuNR arrays. We demonstrate surface treatment via UV Ozone cleaning of such samples to allow introduction of analyte molecules (benzenethiol and cannabinol) for effective surface enhanced Raman scattering detection. This is the first demonstration of the SERS analysis of cannabinol. This approach demonstrates a cost-effective, high-yield and simple fabrication route to SERS sensors with application in the screening for the cannabinoids.

Electrochemical surface-enhanced Raman scattering measurement on ligand capped PbS quantum dots at gap of Au nanodimer

Science.gov (United States)

Li, Xiaowei; Minamimoto, Hiro; Murakoshi, Kei

2018-05-01

The vibrational characteristics of ligand-capped lead sulfide (PbS) quantum dots (QDs) were clarified via electrochemical surface-enhanced Raman spectroscopy (EC-SERS) using a hybridized system of gold (Au) nanodimers and PbS QDs under electrochemical potential control. Enhanced electromagnetic field caused by the coupling of QDs with plasmonic Au nanodimers allowed the characteristic behavior of the ligand oleic acid (OA) on the PbS QD surface to be detected under electrochemical potential control. Binding modes between the QDs and OA molecules were characterized using synchronous two-dimensional correlation spectra at distinct electrochemical potentials, confirming that the bidentate bridging mode was probably the most stable mode even under relatively negative potential polarization. Changes in binding modes and molecular orientations resulted in fluctuations in EC-SERS spectra. The present observations strongly recommend the validity of the QD-plasmonic nanostructure coupled system for sensitive molecular detection via EC-SERS.

A surface-enhanced Raman study of N-methylquinolinium tricyanoquinodimethanide adsorbed on Ag nanospheres: Determination of molecular orientation and order

Science.gov (United States)

Fletcher, Melissa C.; Alexson, Dimitri M.; Prokes, Sharka M.; Glembocki, Orest J.; Vivoni, Alberto; Hosten, Charles M.

2015-08-01

Quinolinium tricyanoquinodimethanides are among the most promising molecules for electronic applications. Disorder can be detrimental to the desired electronic properties of a monolayer, and as such, a reliable method to characterize a monolayer without destroying or creating defects is paramount to determining potential applications. Here, the normal and surface-enhanced Raman scattering spectra of N-methylquinolinium tricyanoquinodimethanide (CH3Q-3CNQ) on silver coated nanosurfaces have been obtained and analyzed. Theoretical treatment of CH3Q-3CNQ was performed. Optimization and frequency search was conducted using the B3LYP functional with the 6-31G(d) basis set. A complete list of frequencies and assignments for the molecules are presented. The spectroscopic evidence points to the fact that a monolayer of CH3Q-3CNQ can be formed through the self-assembly process, and the SERS data indicate that the monolayer attaches to the silver surface through the nitrile groups.

Tamm-Horsfall Glycoprotein Enhances PMN Phagocytosis by Binding to Cell Surface-Expressed Lactoferrin and Cathepsin G That Activates MAP Kinase Pathway

Directory of Open Access Journals (Sweden)

Chia-Li Yu

2011-03-01

Full Text Available The molecular basis of polymorphonuclear neutrophil (PMN phagocytosis-enhancing activity (PEA by human purified urinary Tamm-Horsfall glyco- protein (THP has not been elucidated. In this study, we found human THP bound to lactoferrin (LF and cathepsin G (CG expressed on the surface of PMN, identified by a proteomic study with MALDI-TOF- LC/LC/mass spectrometric analysis. Pre-incubation of 10% SDS-PAGE electrophoresed PMN lysates with monoclonal anti-LF or anti-CG antibody reduced the binding with THP. To elucidate the signaling pathway of THP on PMN activation, we found THP enhanced ERK1/2 phosphorylation, reduced p38 MAP kinase phosphorylation, but had no effect on DNA binding of the five NF-kB family members in PMN. To further clarify whether the carbohydrate-side chains or protein-core structure in THP molecule is responsible for THP-PEA, THP was cleaved by different degrading enzymes with carbohydrate specificity (neuraminidase and β-galactosidase, protein specificity (V8 protease and proteinase K or glycoconjugate specificity (carboxylpeptidase Y and O-sialoglycoprotein endopeptidase. We clearly demonstrated that the intact protein-core structure in THP molecule was more important for THP-PEA than carbohydrate-side chains. Putting these results together, we conclude that THP adheres to surface-expressed LF and CG on PMN and transduces signaling via the MAP kinase pathway to enhance PMN phagocytosis.

Production of molecules on a surface under plasma exposure: example of NO on pyrex

International Nuclear Information System (INIS)

Marinov, D; Guaitella, O; Rousseau, A; Ionikh, Y

2010-01-01

We propose a new experimental approach to the study of surface-catalysed nitric oxide production under plasma exposure. Stable nitrogen species are grafted to the surface of a pyrex discharge tube during N 2 plasma pretreatment. These species are trapped by surface active sites and on being exposed to O 2 plasma, they initiate the production of NO molecules, which are detected using tunable diode laser absorption spectroscopy. Supposing that nitrogen species are adsorbed N atoms, we estimate the initial surface coverage as [N ads ] = 3 x 10 13 cm -2 . This gives an assessment of the lower boundary of the density of surface active sites.

The specificity of targeted vaccines for APC surface molecules influences the immune response phenotype.

Directory of Open Access Journals (Sweden)

Gunnveig Grødeland

Full Text Available Different diseases require different immune responses for efficient protection. Thus, prophylactic vaccines should prime the immune system for the particular type of response needed for protection against a given infectious agent. We have here tested fusion DNA vaccines which encode proteins that bivalently target influenza hemagglutinins (HA to different surface molecules on antigen presenting cells (APC. We demonstrate that targeting to MHC class II molecules predominantly induced an antibody/Th2 response, whereas targeting to CCR1/3/5 predominantly induced a CD8(+/Th1 T cell response. With respect to antibodies, the polarizing effect was even more pronounced upon intramuscular (i.m delivery as compared to intradermal (i.d. vaccination. Despite these differences in induced immune responses, both vaccines protected against a viral challenge with influenza H1N1. Substitution of HA with ovalbumin (OVA demonstrated that polarization of immune responses, as a consequence of APC targeting specificity, could be extended to other antigens. Taken together, the results demonstrate that vaccination can be tailor-made to induce a particular phenotype of adaptive immune responses by specifically targeting different surface molecules on APCs.

Surface-Enhanced Infrared Absorption of o-Nitroaniline on Nickel Nanoparticles Synthesized by Electrochemical Deposition

Directory of Open Access Journals (Sweden)

Yufang Niu

2014-01-01

Full Text Available Nickel nanoparticles were electrochemically deposited on indium-tin oxide (ITO coated glass plate in a modified Watt’s electrolyte. The surface-enhanced infrared absorption (SEIRA effect of the nanoparticles was evaluated by attenuated total reflection spectroscopy (ATR-FTIR using o-nitroaniline as a probe molecule. Electrodeposition parameters such as deposition time, pH value, and the type of surfactants were investigated. The morphology and the microstructure of the deposits were characterized by the field emission scanning electron microscope (FESEM and the atomic force microscope (AFM, respectively. The results indicate that the optimum parameters were potential of 1.3 V, time of 30 s, and pH of 8.92 in the solution of 0.3756 mol/L diethanolamine, 0.1 mol/L nickel sulfate, 0.01 mol/L nickel chloride, and 0.05 mol/L boric acid. The FESEM observation shows that the morphology of nickel nanoparticles with best enhancement effect is spherical and narrowly distributed particles with the average size of 50 nm. SEIRA enhancement factor is about 68.

In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal and Surface Complexation Using Soft X-Ray

International Nuclear Information System (INIS)

Myneni, Satish C.

2008-01-01

Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

Site-Selection in Single-Molecule Junction for Highly Reproducible Molecular Electronics.

Science.gov (United States)

Kaneko, Satoshi; Murai, Daigo; Marqués-González, Santiago; Nakamura, Hisao; Komoto, Yuki; Fujii, Shintaro; Nishino, Tomoaki; Ikeda, Katsuyoshi; Tsukagoshi, Kazuhito; Kiguchi, Manabu

2016-02-03

Adsorption sites of molecules critically determine the electric/photonic properties and the stability of heterogeneous molecule-metal interfaces. Then, selectivity of adsorption site is essential for development of the fields including organic electronics, catalysis, and biology. However, due to current technical limitations, site-selectivity, i.e., precise determination of the molecular adsorption site, remains a major challenge because of difficulty in precise selection of meaningful one among the sites. We have succeeded the single site-selection at a single-molecule junction by performing newly developed hybrid technique: simultaneous characterization of surface enhanced Raman scattering (SERS) and current-voltage (I-V) measurements. The I-V response of 1,4-benzenedithiol junctions reveals the existence of three metastable states arising from different adsorption sites. Notably, correlated SERS measurements show selectivity toward one of the adsorption sites: "bridge sites". This site-selectivity represents an essential step toward the reliable integration of individual molecules on metallic surfaces. Furthermore, the hybrid spectro-electric technique reveals the dependence of the SERS intensity on the strength of the molecule-metal interaction, showing the interdependence between the optical and electronic properties in single-molecule junctions.

Development of a miRNA surface-enhanced Raman scattering assay using benchtop and handheld Raman systems.

Science.gov (United States)

Schechinger, Monika; Marks, Haley; Locke, Andrea; Choudhury, Mahua; Cote, Gerard

2018-01-01

DNA-functionalized nanoparticles, when paired with surface-enhanced Raman spectroscopy (SERS), can rapidly detect microRNA. However, widespread use of this approach is hindered by drawbacks associated with large and expensive benchtop Raman microscopes. MicroRNA-17 (miRNA-17) has emerged as a potential epigenetic indicator of preeclampsia, a condition that occurs during pregnancy. Biomarker detection using an SERS point-of-care device could enable prompt diagnosis and prevention as early as the first trimester. Recently, strides have been made in developing portable Raman systems for field applications. An SERS assay for miRNA-17 was assessed and translated from traditional benchtop Raman microscopes to a handheld system. Three different photoactive molecules were compared as potential Raman reporter molecules: a chromophore, malachite green isothiocyanate (MGITC), a fluorophore, tetramethylrhodamine isothiocyanate, and a polarizable small molecule 5,5-dithio-bis-(2-nitrobenzoic acid) (DTNB). For the benchtop Raman microscope, the DTNB-labeled assay yielded the greatest sensitivity under 532-nm laser excitation, but the MGITC-labeled assay prevailed at 785 nm. Conversely, DTNB was preferable for the miniaturized 785-nm Raman system. This comparison showed significant SERS enhancement variation in response to 1-nM miRNA-17, implying that the sensitivity of the assay may be more heavily dependent on the excitation wavelength, instrumentation, and Raman reporter chosen than on the plasmonic coupling from DNA/miRNA-mediated nanoparticle assemblies. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

A procedure to analyze surface profiles of the protein molecules visualized by quick-freeze deep-etch replica electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Kimori, Yoshitaka [Division of Biomolecular Imaging, Institute of Medical Science, The University of Tokyo, Minato-ku, Tokyo 108-8639 (Japan); Department of Bioscience and Bioinformatics, Kyushu Institute of Technology, Iizuka, Fukuoka 820-8502 (Japan); Oguchi, Yosuke [Department of Electric Engineering, Kogakuin University, Hachioji, Tokyo 192-0015 (Japan); Ichise, Norihiko [Department of Visual Communication, Komazawa Women' s University, Inagi, Tokyo 206-8511 (Japan); Baba, Norio [Department of Electric Engineering, Kogakuin University, Hachioji, Tokyo 192-0015 (Japan); Katayama, Eisaku [Division of Biomolecular Imaging, Institute of Medical Science, The University of Tokyo, Minato-ku, Tokyo 108-8639 (Japan)]. E-mail: ekatayam@ims.u-tokyo.ac.jp

2007-01-15

Quick-freeze deep-etch replica electron microscopy gives high contrast snapshots of individual protein molecules under physiological conditions in vitro or in situ. The images show delicate internal pattern, possibly reflecting the rotary-shadowed surface profile of the molecule. As a step to build the new system for the 'Structural analysis of single molecules', we propose a procedure to quantitatively characterize the structural property of individual molecules; e.g. conformational type and precise view-angle of the molecules, if the crystallographic structure of the target molecule is available. This paper presents a framework to determine the observed face of the protein molecule by analyzing the surface profile of individual molecules visualized in freeze-replica specimens. A comprehensive set of rotary-shadowed views of the protein molecule was artificially generated from the available atomic coordinates using light-rendering software. Exploiting new mathematical morphology-based image filter, characteristic features were extracted from each image and stored as template. Similar features were extracted from the true replica image and the most likely projection angle and the conformation of the observed particle were determined by quantitative comparison with a set of archived images. The performance and the robustness of the procedure were examined with myosin head structure in defined configuration for actual application.

A procedure to analyze surface profiles of the protein molecules visualized by quick-freeze deep-etch replica electron microscopy

International Nuclear Information System (INIS)

Kimori, Yoshitaka; Oguchi, Yosuke; Ichise, Norihiko; Baba, Norio; Katayama, Eisaku

2007-01-01

Quick-freeze deep-etch replica electron microscopy gives high contrast snapshots of individual protein molecules under physiological conditions in vitro or in situ. The images show delicate internal pattern, possibly reflecting the rotary-shadowed surface profile of the molecule. As a step to build the new system for the 'Structural analysis of single molecules', we propose a procedure to quantitatively characterize the structural property of individual molecules; e.g. conformational type and precise view-angle of the molecules, if the crystallographic structure of the target molecule is available. This paper presents a framework to determine the observed face of the protein molecule by analyzing the surface profile of individual molecules visualized in freeze-replica specimens. A comprehensive set of rotary-shadowed views of the protein molecule was artificially generated from the available atomic coordinates using light-rendering software. Exploiting new mathematical morphology-based image filter, characteristic features were extracted from each image and stored as template. Similar features were extracted from the true replica image and the most likely projection angle and the conformation of the observed particle were determined by quantitative comparison with a set of archived images. The performance and the robustness of the procedure were examined with myosin head structure in defined configuration for actual application

Using Force to Probe Single-Molecule Receptor-Cytoskeletal Anchoring Beneath the Surface of a Living Cell

DEFF Research Database (Denmark)

Evans, Evan; Kinoshita, Koji

2007-01-01

-cytoskeletal unbinding increased exponentially with the level of force, suggesting disruption at a site of single-molecule interaction. Since many important enzymes and signaling molecules are closely associated with a membrane receptor-cytoskeletal linkage, pulling on a receptor could alter interactions among its......The ligation of cell surface receptors often communicates a signal that initiates a cytoplasmic chemical cascade to implement an important cell function. Less well understood is how physical stress applied to a cell surface adhesive bond propagates throughout the cytostructure to catalyze...... or trigger important steps in these chemical processes. Probing the nanoscale impact of pulling on cell surface bonds, we discovered that receptors frequently detach prematurely from the interior cytostructure prior to failure of the exterior adhesive bond [Evans, E., Heinrich, V., Leung, A., and Kinoshita...

Molecules in stars

International Nuclear Information System (INIS)

Tsuji, T.

1986-01-01

Recently, research related to molecules in stars has rapidly expanded because of progress in related fields. For this reason, it is almost impossible to cover all the topics related to molecules in stars. Thus, here the authors focus their attention on molecules in the atmospheres of cool stars and do not cover in any detail topics related to circumstellar molecules originating from expanding envelopes located far from the stellar surface. However, the authors do discuss molecules in quasi-static circumstellar envelopes (a recently discovered new component of circumstellar envelopes) located near the stellar surface, since molecular lines originating from such envelopes show little velocity shift relative to photospheric lines, and hence they directly affect the interpretation and analysis of stellar spectra

Predicting supramolecular self-assembly on reconstructed metal surfaces

Science.gov (United States)

Roussel, Thomas J.; Barrena, Esther; Ocal, Carmen; Faraudo, Jordi

2014-06-01

The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule interactions are enhanced in a way that long-range order is promoted. Also, the presence of a distortion in a reconstructed surface pattern not only induces the presence of long-range order but also is able to drive the organization of DIP into two coexisting homochiral domains, in quantitative agreement with STM experiments. On the other hand, only short range order is obtained in other reconstructions of the Au(111) surface. The simulation strategy opens interesting perspectives to tune the supramolecular structure by simulation design and surface engineering if choosing the right molecular building blocks and stabilising the chosen reconstruction pattern.The prediction of supramolecular self-assembly onto solid surfaces is still challenging in many situations of interest for nanoscience. In particular, no previous simulation approach has been capable to simulate large self-assembly patterns of organic molecules over reconstructed surfaces (which have periodicities over large distances) due to the large number of surface atoms and adsorbing molecules involved. Using a novel simulation technique, we report here large scale simulations of the self-assembly patterns of an organic molecule (DIP) over different reconstructions of the Au(111) surface. We show that on particular reconstructions, the molecule-molecule

Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

Energy Technology Data Exchange (ETDEWEB)

Yesildag, Ali [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey); Ekinci, Duygu, E-mail: dekin@atauni.edu.t [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey)

2010-09-30

In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN){sub 6}{sup 3-} and Ru(NH{sub 3}){sub 6}{sup 3+} by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

Synthesis of Silicalite Membrane with an Aluminum-Containing Surface for Controlled Modification of Zeolitic Pore Entries for Enhanced Gas Separation

Directory of Open Access Journals (Sweden)

Shaowei Yang

2018-02-01

Full Text Available The separation of small molecule gases by membrane technologies can help performance enhancement and process intensification for emerging advanced fossil energy systems with CO2 capture capacity. This paper reports the demonstration of controlled modification of zeolitic channel size for the MFI-type zeolite membranes to enhance the separation of small molecule gases such as O2 and N2. Pure-silica MFI-type zeolite membranes were synthesized on porous α-alumina disc substrates with and without an aluminum-containing thin skin on the outer surface of zeolite membrane. The membranes were subsequently modified by on-stream catalytic cracking deposition (CCD of molecular silica to reduce the effective openings of the zeolitic channels. Such a pore modification caused the transition of gas permeation from the N2-selective gaseous diffusion mechanism in the pristine membrane to the O2-selective activated diffusion mechanism in the modified membrane. The experimental results indicated that the pore modification could be effectively limited within the aluminum-containing surface of the MFI zeolite membrane to minimize the mass transport resistance for O2 permeation while maintaining its selectivity. The implications of pore modification on the size-exclusion-enabled gas selectivity were discussed based on the kinetic molecular theory. In light of the theoretical analysis, experimental investigation was performed to further enhance the membrane separation selectivity by chemical liquid deposition of silica into the undesirable intercrystalline spaces.

Au nanoparticle arrays with tunable particle gaps by template-assisted electroless deposition for high performance surface-enhanced Raman scattering

International Nuclear Information System (INIS)

Mu Cheng; Xu Dongsheng; Zhang Jianping

2010-01-01

Surface-enhanced Raman spectroscopy (SERS) with enormous enhancements has shown great potential in ultrasensitive detection technologies, but the fabrication of large-scale, controllable and reproducible substrates with high SERS activity is a major challenge. Here, we report the preparation of Au nanoparticle arrays for SERS-active substrates with tunable particle sizes and interparticle gaps, and the enhancement factor of the SERS signal obtained from 4-mercaptopyridine probe molecules was as high as 10 7 . The experimental data points show the increase of enhancement factor as a function of the ratio of diameter to interparticle gap, which can be explained by the averaged electromagnetic field enhancement model. Furthermore, we demonstrated that this type of substrate merits its high uniformity, high reproducibility and excellent long-term stability. As the fabrication protocol of such a SERS substrate is simple and inexpensive, this substrate may anticipate a wide range of applications in SERS-based sensors.

A small-molecule/cytokine combination enhances hematopoietic stem cell proliferation via inhibition of cell differentiation.

Science.gov (United States)

Wang, Lan; Guan, Xin; Wang, Huihui; Shen, Bin; Zhang, Yu; Ren, Zhihua; Ma, Yupo; Ding, Xinxin; Jiang, Yongping

2017-07-18

Accumulated evidence supports the potent stimulating effects of multiple small molecules on the expansion of hematopoietic stem cells (HSCs) which are important for the therapy of various hematological disorders. Here, we report a novel, optimized formula, named the SC cocktail, which contains a combination of three such small molecules and four cytokines. Small-molecule candidates were individually screened and then combined at their optimal concentration with the presence of cytokines to achieve maximum capacity for stimulating the human CD34 + cell expansion ex vivo. The extent of cell expansion and the immunophenotype of expanded cells were assessed through flow cytometry. The functional preservation of HSC stemness was confirmed by additional cell and molecular assays in vitro. Subsequently, the expanded cells were transplanted into sublethally irradiated NOD/SCID mice for the assessment of human cell viability and engraftment potential in vivo. Furthermore, the expression of several genes in the cell proliferation and differentiation pathways was analyzed through quantitative polymerase chain reaction (qPCR) during the process of CD34 + cell expansion. The SC cocktail supported the retention of the immunophenotype of hematopoietic stem/progenitor cells remarkably well, by yielding purities of 86.6 ± 11.2% for CD34 + cells and 76.2 ± 10.5% for CD34 + CD38 - cells, respectively, for a 7-day culture. On day 7, the enhancement of expansion of CD34 + cells and CD34 + CD38 - cells reached a maxima of 28.0 ± 5.5-fold and 27.9 ± 4.3-fold, respectively. The SC cocktail-expanded CD34 + cells preserved the characteristics of HSCs by effectively inhibiting their differentiation in vitro and retained the multilineage differentiation potential in primary and secondary in vivo murine xenotransplantation trials. Further gene expression analysis suggested that the small-molecule combination strengthened the ability of the cytokines to enhance the Notch

Improving surface-enhanced Raman scattering effect using gold-coated hierarchical polystyrene bead substrates modified with postgrowth microwave treatment.

Science.gov (United States)

Yuen, Clement; Zheng, Wei; Huang, Zhiwei

2008-01-01

We report a novel postgrowth microwave heating implementation by selectively modifying hierarchical polystyrene (PS) bead substrates coated with gold (Au) films to effectively improve the surface-enhanced Raman scattering (SERS) effect on the analytes. The SERS signal of probe molecule rhodamine 6G (Rh 6G) on the microwave-treated Au-PS substrates can be improved by 10-fold, while the detection limit of Rh 6G in concentration can be enhanced by two orders of magnitude compared to the as-growth substrates. The high-quality SERS spectrum of saliva can also be acquired using the modified substrates, demonstrating the potential for the realization of the high-performance SERS substrates for biomedical applications.

The Adsorption Geometry and Electronic Structure of Organic Dye Molecule on TiO2(101 Surface from First Principles Calculations

Directory of Open Access Journals (Sweden)

Niu Mang

2017-01-01

Full Text Available Using density functional theory (DFT, we have investigated the structural and electronic properties of dye-sensitized solar cells (DSSCs comprised of I-doped anatase TiO2(101 surface sensitized with NKX-2554 dye. The calculation results indicate that the cyanoacrylic acid anchoring group in NKX-2554 has a strong binding to the TiO2(101 surface. The dissociative and bidentate bridging type was found to be the most favorable adsorption configuration. On the other hand, the incorporations of I dopant can reduce the band gap of TiO2 photoanode and improve the of NKX-2554 dye, which can improve the visible-light absorption of anatase TiO2 and can also facilitate the electron injection from the dye molecule to the TiO2 substrate. As a result, the I doping can significantly enhance the incident photon-to-current conversion efficiency (IPCE of DSSCs.

Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

Energy Technology Data Exchange (ETDEWEB)

Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

1999-11-08

Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO₂ were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO₂, large photoelectrocatalytic effect for the reduction of CO₂ was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO₂ in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

Density functional study the interaction of oxygen molecule with defect sites of graphene

Energy Technology Data Exchange (ETDEWEB)

Qi Xuejun [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Guo Xin, E-mail: guoxin@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Wuhan 430074 (China); Zheng Chuguang [State Key Laboratory of Coal Combustion, Wuhan 430074 (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer The defect sites existed on the graphite surface create active sites and enhance the reactivity of carbonaceous material. Black-Right-Pointing-Pointer Oxygen molecule more favor chemisorbed on the graphene surface contains defect sites than the perfect surface. Black-Right-Pointing-Pointer The single active oxygen atom adsorbed on the defect surfaces, it completely insert into the surface. - Abstract: The present article reports a theoretical study of oxygen interacted with graphene surface containing defect sites on the atomic level by employing the density functional theory combined with the graphene cluster model. It was founded that oxygen molecule prefers to be chemisorbed on the graphene surface containing defect sites compared to the perfect surface. The adsorption energy of O{sub 2} on the double defect site is about 2.5 times as large as that on the perfect graphene surface. Moreover, the oxygen molecule interacts with S-W defect site gives rise to stable epoxy structure, which pulling the carbon atom outward from the original site in the direction perpendicular to the surface. If the oxygen molecule is adsorbed on the single vacancy site, two C-O bonds are formed on the graphene surface. However, when the oxygen molecule is chemisorbed on the double vacancy site, the oxygen atoms substitute the missing carbon atom's position in the carbon plane and form a hexagonal structure on the graphene network. The results indicate that single active oxygen atom approaches the defect site, it's completely adsorbed in the plane and high energy is released. In all cases, the interaction of an oxygen atom with defect surface involves an exothermic process. The defect site creates active sites on the surface of graphene and produces catalytic effects during the process of oxidation of carbonaceous materials.

Magnetic Fe{sub 3}O{sub 4}-Au core-shell nanostructures for surface enhanced Raman scattering

Energy Technology Data Exchange (ETDEWEB)

Wheeler, D.A.; Adams, S.A.; Zhang, J.Z. [Department of Chemistry and Biochemistry, University of California, Santa Cruz, Santa Cruz, CA 95064 (United States); Lopez-Luke, T. [Department of Chemistry and Biochemistry, University of California, Santa Cruz, Santa Cruz, CA 95064 (United States); Cento de Investigaciones en Optica, A.P. 1-948 Leon, Gto. 37150 (Mexico); Torres-Castro, A. [Universidad Autonoma de Nuevo Leon, A.P. 126-F, Monterrey, NL, 66450 (Mexico)

2012-11-15

The synthesis, structural and optical characterization, and application of superparamagnetic and water-dispersed Fe{sub 3}O{sub 4}-Au core-shell nanoparticles for surface enhanced Raman scattering (SERS) is reported. The structure of the nanoparticles was determined by scanning transmission electron microscopy (STEM) and high-resolution transmission electron microscopy (HRTEM). STEM images of the Fe{sub 3}O{sub 4}-Au core-shell nanoparticles reveal an average diameter of 120 nm and a high degree of surface roughness. The nanoparticles, which display superparamagnetic properties due to the core Fe{sub 3}O{sub 4} material, exhibit a visible surface plasmon resonance (SPR) peaked at 580 nm due to the outer gold shell. The nanoparticles are used as a substrate for surface enhanced Raman scattering (SERS) with rhodamine 6G (R6G) as a Raman reporter molecule. The SERS enhancement factor is estimated to be on the order of 10{sup 6}, which is {proportional_to} 2 times larger than that of conventional gold nanoparticles (AuNPs) under similar conditions. Significantly, magnetically-induced aggregation of the Fe{sub 3}O{sub 4}-Au core-shell nanoparticles substantially enhanced SERS activity compared to non-magnetically-aggregated Fe{sub 3}O{sub 4}-Au nanoparticles. This is attributed to both increased scattering from the aggregates as well as ''hot spots'' due to more junction sites in the magnetically-induced aggregates. The magnetic properties of the Fe{sub 3}O{sub 4} core, coupled with the optical properties of the Au shell, make the Fe{sub 3}O{sub 4}-Au nanoparticles unique for various potential applications including biological sensing and therapy. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Mobility of chemisorbed molecules and surface regeneration of active centers during dehydration of isopropanol on aluminium oxide and aluminosilicate

International Nuclear Information System (INIS)

Makhlis, L.A.; Vasserberg, V.Eh.

1976-01-01

By a differential isotope method involving 14 C the authors have investigated the surface mobility of chemisorbed molecules of isopropanol during its dehydration in an adsorption layer on aluminium oxide and aluminosilicate. The chemisorbed alcohol molecules possess marked surface mobility which plays a decisive part in the mechanism of surface regeneration of the active catalyst centers in the process of dehydration. The cessation of the reaction long before the adsorbed alcohol is completely used up is explained by the hypothesis that there is local overpopulation of the active sectors by water formed by the reaction; this hinders further surface regeneration and repetition of the elementary events of dehydration

Cell factory-derived bioactive molecules with polymeric cryogel scaffold enhance the repair of subchondral cartilage defect in rabbits.

Science.gov (United States)

Gupta, Ankur; Bhat, Sumrita; Chaudhari, Bhushan P; Gupta, Kailash C; Tägil, Magnus; Zheng, Ming Hao; Kumar, Ashok; Lidgren, Lars

2017-06-01

We have explored the potential of cell factory-derived bioactive molecules, isolated from conditioned media of primary goat chondrocytes, for the repair of subchondral cartilage defects. Enzyme-linked immunosorbent assay (ELISA) confirms the presence of transforming growth factor-β1 in an isolated protein fraction (12.56 ± 1.15 ng/mg protein fraction). These bioactive molecules were used alone or with chitosan-agarose-gelatin cryogel scaffolds, with and without chondrocytes, to check whether combined approaches further enhance cartilage repair. To evaluate this, an in vivo study was conducted on New Zealand rabbits in which a subchondral defect (4.5 mm wide × 4.5 mm deep) was surgically created. Starting after the operation, bioactive molecules were injected at the defect site at regular intervals of 14 days. Histopathological analysis showed that rabbits treated with bioactive molecules alone had cartilage regeneration after 4 weeks. However, rabbits treated with bioactive molecules along with scaffolds, with or without cells, showed cartilage formation after 3 weeks; 6 weeks after surgery, the cartilage regenerated in rabbits treated with either bioactive molecules alone or in combinations showed morphological similarities to native cartilage. No systemic cytotoxicity or inflammatory response was induced by any of the treatments. Further, ELISA was done to determine systemic toxicity, which showed no difference in concentration of tumour necrosis factor-α in blood serum, before or after surgery. In conclusion, intra-articular injection with bioactive molecules alone may be used for the repair of subchondral cartilage defects, and bioactive molecules along with chondrocyte-seeded scaffolds further enhance the repair. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Small Molecule-BIO Accelerates and Enhances Marrow-Derived Mesenchymal Stem Cell in Vitro Chondrogenesis

Directory of Open Access Journals (Sweden)

Mohamadreza Baghaban Eslaminejad

2014-03-01

Full Text Available Background: Hyaline cartilage defects exhibit a major challenge in the field of orthopedic surgery owing to its limited repair capacity. On the other hand, mesenchymal stem cells (MSCs are regarded as potent cells with a property of cartilage regeneration. We aimed to optimize marrow-derived MSC chondrogenic culture using a small bioactive molecule referred to as BIO. Methods: MSCs from the marrow of NMRI mice were extracted, culture-expanded, and characterized. Micro-mass culture was then established for chondrogenic differentiation (control group. The cultures of MSC in chondrogenic medium supplemented with 0.01, 0.05, 0.1, and 1 µM BIO were taken as the experimental groups. Cartilage differentiation was examined by both histological sections and real-time PCR for Sox9, aggrecan, and collagen II at different time points. Moreover, the involvement of the Wnt pathway was investigated. Results: Based on histological sections, there was seemingly more intense metachromatic matrix produced in the cultures with 0.01 µM BIO. In this experimental group, cartilage-specific genes tended to be upregulated at day 14 compared to day 21 of the control group, indicating the accelerating effect of BIO on cartilage differentiation. Overall, there was statistically a significant increase (P=0.01 in the expression level of cartilage-specific genes in cultures with 0.01 µM BIO (enhancing effects. These upregulations appeared to be mediated through the Wnt pathway evident from the significant upregulation of T-cell factor and beta-catenin molecules (P=0.01. Conclusion: Taken together, BIO at 0.01 µM could accelerate and enhance in vitro chondrogenesis of mouse marrow-derived MSCs. Please cite this article as: Baghaban Eslaminejad MR, Fallah N. Small Molecule-BIO Accelerates and Enhances Marrow-Derived Mesenchymal Stem Cell in Vitro Chondrogenesis. Iran J Med Sci. 2014;39(2:107-116.

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

Science.gov (United States)

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

Nanospectroscopy of thiacyanine dye molecules adsorbed on silver nanoparticle clusters

Science.gov (United States)

Ralević, Uroš; Isić, Goran; Anicijević, Dragana Vasić; Laban, Bojana; Bogdanović, Una; Lazović, Vladimir M.; Vodnik, Vesna; Gajić, Radoš

2018-03-01

The adsorption of thiacyanine dye molecules on citrate-stabilized silver nanoparticle clusters drop-cast onto freshly cleaved mica or highly oriented pyrolytic graphite surfaces is examined using colocalized surface-enhanced Raman spectroscopy and atomic force microscopy. The incidence of dye Raman signatures in photoluminescence hotspots identified around nanoparticle clusters is considered for both citrate- and borate-capped silver nanoparticles and found to be substantially lower in the former case, suggesting that the citrate anions impede the efficient dye adsorption. Rigorous numerical simulations of light scattering on random nanoparticle clusters are used for estimating the electromagnetic enhancement and elucidating the hotspot formation mechanism. The majority of the enhanced Raman signal, estimated to be more than 90%, is found to originate from the nanogaps between adjacent nanoparticles in the cluster, regardless of the cluster size and geometry.

Decoration of carbon nano surfaces with hydrogen and hydrogen rich molecules

International Nuclear Information System (INIS)

Zöttl, S.

2013-01-01

The use of helium nano droplets as a matrix to investigate different atomic and molecular samples is a well established experimental technique. The unique properties of helium allow for different analytical methods and at the same time provide a stable ambient temperature. Cluster growth inside helium nano droplets can be accomplished by repeatedly doping the droplets with sample particles in a controlled environment. The experimental work represented in this thesis was performed using helium nano droplets to create clusters of fullerenes like C 60 and C 70 . The adsorption properties of these fullerene clusters regarding hydrogen and hydrogen rich molecules have been subject to investigation. The observed results suggest that curved carbon nano surfaces offer higher storage densities than planar graphite surfaces. The use of C 60 as a model carbon nano structure provides a well understood molecule for testing and evaluating computational methods to calculate surface properties of various carbon nano materials. The cost effective storage of hydrogen for mobile applications plays a key role in the development of alternatives to fossil fuels. For that reason, the application of carbon nano materials to store hydrogen by adsorption has attracted much scientific attention lately. The insights gained in the presented thesis contribute to the collective efforts and deliver more refined tools to estimate the adsorption properties of future carbon nano materials. In addition to the aforementioned, a time-of-flight mass spectrometer for educational purpose has been designed and constructed in the framework of my PhD thesis. The instrument is successfully used in various lab courses and information on the setup can be found in the Appendix of this work. (author) [de

Surface functionalization of 3D glass-ceramic porous scaffolds for enhanced mineralization in vitro

Science.gov (United States)

Ferraris, Sara; Vitale-Brovarone, Chiara; Bretcanu, Oana; Cassinelli, Clara; Vernè, Enrica

2013-04-01

Bone reconstruction after tissue loosening due to traumatic, pathological or surgical causes is in increasing demand. 3D scaffolds are a widely studied solution for supporting new bone growth. Bioactive glass-ceramic porous materials can offer a three-dimensional structure that is able to chemically bond to bone. The ability to surface modify these devices by grafting biologically active molecules represents a challenge, with the aim of stimulating physiological bone regeneration with both inorganic and organic signals. In this research work glass ceramic scaffolds with very high mechanical properties and moderate bioactivity have been functionalized with the enzyme alkaline phosphatase (ALP). The material surface was activated in order to expose hydroxyl groups. The activated surface was further grafted with ALP both via silanization and also via direct grafting to the surface active hydroxyl groups. Enzymatic activity of grafted samples were measured by means of UV-vis spectroscopy before and after ultrasonic washing in TRIS-HCl buffer solution. In vitro inorganic bioactivity was investigated by soaking the scaffolds after the different steps of functionalization in a simulated body fluid (SBF). SEM observations allowed the monitoring of the scaffold morphology and surface chemical composition after soaking in SBF. The presence of ALP enhanced the in vitro inorganic bioactivity of the tested material.

Preparation of theoretical scanning tunneling microscope images of adsorbed molecules: a theoretical study of benzene on the Cu(110) surface

International Nuclear Information System (INIS)

Shapter, J.G.; Rogers, B.L.; Ford, M.J.

2003-01-01

Full text: Since its development in 1982, the Scanning Tunneling Microscope (STM) has developed into a powerful tool for the study of surfaces and adsorbates. However, the utility of the technique can be further enhanced through the development of techniques for generating theoretical STM images. This is particularly true when studying molecules adsorbed on a substrate, as the results are often interpreted superficially due to an inadequate understanding of the orbital overlap probed in the experiment. A method of preparing theoretical scanning tunneling microscope (STM) images using comparatively inexpensive desktop computers and the commercially available CRYSTAL98 package is presented through a study of benzene adsorbed on the Cu(110) surface. Density Functional Theory (DFT) and Hartree-Fock (HF) methods are used to model clean Cu(110) slabs of various thicknesses and to simulate the adsorption of benzene onto these slabs. Eight possible orientations of benzene on the Cu(110) surface are proposed, and the optimum orientation according to the calculations is presented. Theoretical STM images of the Cu(110) surface and benzene adsorbed on the Cu(110) surface are compared with experimental STM images of the system from a published study. Significant differences are observed and are examined in detail

The Nanofabrication and Application of Substrates for Surface-Enhanced Raman Scattering

Directory of Open Access Journals (Sweden)

Xian Zhang

2012-01-01

Full Text Available Surface-enhanced Raman scattering (SERS was discovered in 1974 and impacted Raman spectroscopy and surface science. Although SERS has not been developed to be an applicable detection tool so far, nanotechnology has promoted its development in recent decades. The traditional SERS substrates, such as silver electrode, metal island film, and silver colloid, cannot be applied because of their enhancement factor or stability, but newly developed substrates, such as electrochemical deposition surface, Ag porous film, and surface-confined colloids, have better sensitivity and stability. Surface enhanced Raman scattering is applied in other fields such as detection of chemical pollutant, biomolecules, DNA, bacteria, and so forth. In this paper, the development of nanofabrication and application of surface-enhanced Ramans scattering substrate are discussed.

Laser-induced construction of multi-branched CuS nanodendrites with excellent surface-enhanced Raman scattering spectroscopy in repeated applications.

Science.gov (United States)

Li, Shuang; Zhang, Hua; Xu, Linlin; Chen, Ming

2017-07-10

We report on the successful fabrication of multi-branched CuS nanodendrites with average branch length of about 20 nm by laser ablation of bulk Cu target in thioacetamide (TAA) solution. During the nucleation of Cu and S species, the accurate anisotropic growth should be attributed to an ultra-rapid acid etching process by laser-induced TAA hydrolyzing reaction. Interestingly, the semiconductor CuS nanodendrites provide pronounced surface enhanced Raman scattering (SERS) properties with noble-metal comparable activity and a detection limit as low as ~10 -10 M, approaching the requirement (~nM) for single molecule detection. More importantly, after SERS analysis, the crystal violet (CV) probe molecules can be effectively removed from the substrate by 1064nm laser irradiation-induced moderate thermal treatment. Therefore, the unique and distinctive advantage is that the as-prepared CuS nanodendrites exhibit excellent reusability for 60 cycles of repeated SERS analyses. The low-cost CuS semiconductor nanodendrites with enhanced SERS properties should be established as a prominent SERS-based ultrasensitive probe in the repeated applications.

Surface-enhanced Raman Scattering Study of the Binding Modes of a Dibenzotetraaza[14]annulene Derivative with DNA/RNA Polynucleotides

OpenAIRE

Miljanić, Snežana; Dijanošić, Adriana; Kalac, Matea; Radić Stojković, Marijana; Piantanida, Ivo; Pawlica, Dariusz; Eilmes, Julita

2012-01-01

Binding modes of a dibenzotetraaza14annulene (DBTAA) derivative with synthetic nucleic acids were studied using surface-enhanced Raman spectroscopy (SERS). Changes in SERS intensity and appearance of new bands in spectra were attributed to different complexes formed between the DBTAA molecules and DNA/RNA polynucleotides. A decrease in intensity pointed to intercalation as the dominant binding mode of the annulene derivative with poly dGdC-poly dGdC and poly rA-poly rU, whereas new bands in...

Tapping mode AFM study on the surface dynamics of a single glucose oxidase molecule on a Au(1 1 1) surface in water with implication for a surface-induced unfolding pathway

International Nuclear Information System (INIS)

Otsuka, Ichiro; Yaoita, Masashi; Higano, Michi; Nagashima, Seiiichi; Kataoka, Ryoichi

2004-01-01

We have investigated a surface-induced unfolding dynamics of a single glucose oxidase (GO) molecule on Au(1 1 1) in air-saturated water, using tapping mode atomic force microscopy (TMAFM). We followed the unfolding process by measuring the maximum height of a well-isolated GO molecule on a terrace near a step-edge of the surface as a function of contact time. We find three linear portions with two intersections in a power-law fit to the selected values of the observed heights. The kinetic TMAFM result implies that there exist at least two distinct dynamic regimes in the unfolding

Radiation-Induced Correlation between Molecules Nearby Metallic Antenna Array

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Yoshiki Osaka

2015-01-01

Full Text Available We theoretically investigate optical absorption of molecules embedded nearby metallic antennas by using discrete dipole approximation method. It is found that the spectral peak of the absorption is shifted due to the radiation-induced correlation between the molecules. The most distinguishing feature of our work is to show that the shift is largely enhanced even when the individual molecules couple with localized surface plasmons near the different antennas. Specifically, we first consider the case that two sets of dimeric gold blocks with a spacing of a few nanometers are arranged and reveal that the intensity and spectral peak of the optical absorption strongly depend on the position of the molecules. In addition, when the dimeric blocks and the molecules are periodically arranged, the peak shift is found to increase up to ~1.2 meV (300 GHz. Because the radiation-induced correlation is essential for collective photon emission, our result implies the possibility of plasmon-assisted superfluorescence in designed antenna-molecule complex systems.

Determination of surface concentrations of individual molecule-layers used in nanoscale biosensors by in situ ATR-FTIR spectroscopy

KAUST Repository

Punzet, Manuel; Baurecht, Dieter; Varga, Franz; Karlic, Heidrun; Heitzinger, Clemens

2012-01-01

formation of typical functionalization protocols and to determine the respective molecule surface concentrations. BSA, anti-TNF-α and anti-PSA antibodies were bound via 3-(trimethoxy)butylsilyl aldehyde linkers to silicon-oxide surfaces in order

Theoretical studies of molecule surface scattering: Rotationally inelastic diffraction and dissociative dynamics of H2 on metals

International Nuclear Information System (INIS)

Cruz Pol, A.J.

1993-01-01

The interaction of H 2 and its isotopes with metal surfaces has been the subject of many investigations. The scattering experiments provide data such as the final rotational state distribution, sticking coefficients, kinetic energy distribution, and diffraction data. In the first study of this thesis the author implemented a model for looking at the rotationally inelastic diffraction probabilities for H 2 , HD, and D 2 , as a function of surface temperature. The surface is treated in a quantum mechanical fashion using a recently developed formalism. The center of mass translational motion is treated semiclassically using Gaussian wave packets, and the rotations are described quantum mechanically. The phonon summed rotation-diffraction probabilities as well as the probability distribution for a scattering molecule exchanging an amount of energy ΔE with the surface were computed. In the second and third study of this thesis the author implemented a mixed quantum-classical model to compute the probability for dissociation and rotational excitation for H 2 , HD, and D 2 scattered from Ni(100) dimensionally in dynamics simulations. Of the six degrees of freedom for the dissociative adsorption of a diatomic molecule on a static surface, the author treats Z,d the center of mass distance above the surface plan, r, the internuclear separation, θ, the polar orientation angle, quantum mechanically. The remaining three degrees of freedom, X and Y, the center of mass position on the surface plane, and oe, the azimuthal orientation angle, are treated classically. Probabilities for dissociation and ro-vibrational excitation are computed as a function of incident translational energy. Two sudden approximations are tested, in which either the center of mass translation parallel to the surface or the azimuthal orientation of the molecule are frozen. Comparisons are made between low and high dimensionality results and with fully classical results

Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

DEFF Research Database (Denmark)

Abild-Pedersen, Frank; Greeley, Jeffrey Philip; Studt, Felix

2007-01-01

Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorp...

Synthesis of Au Nanostars and Their Application as Surface Enhanced Raman Scattering-Activity Tags Inside Living Cells.

Science.gov (United States)

Cao, Xiaowei; Shi, Chaowen; Lu, Wenbo; Zhao, Hang; Wang, Man; Tong, Wei; Dong, Jian; Han, Xiaodong; Qian, Weiping

2015-07-01

This work presents the synthesis and characterization of Au nanostars (AuNSs) and demonstrates their application as surface enhanced Raman scattering (SERS)-activity tags for cellular imaging and sensing. Nile blue A (NBA) and bovine serum albumin (BSA) were used as Raman reporter molecules and capping materials, respectively. The SERS-activity tags were tested on human lung adenocarcinoma cell (A549) and alveolar type II cell (AT II) and found to present a low level of cytotoxicity and high chemical stability. These SERS-activity tags not only can be applied in multiplexed cellular imaging, including dark field imaging, transmission electron microscopy (TEM) and SERS imaging, but also can be used for cellular sensing. The SERS spectra clearly identified cellular important components such as proteins, nucleic acids, lipids, and carbohydrates. This study also shows that endocytosis is the main channel of tags internalized in cells. The AuNSs exhibiting strong surface enhanced Raman effects are utilized in the design of an efficient, stable SERS-activity tag for intracellular applications.

Microwave assisted in situ synthesis of Ag–NaCMC films and their reproducible surface-enhanced Raman scattering signals

International Nuclear Information System (INIS)

Jiang, Tao; Li, Junpeng; Zhang, Li; Wang, Binbing; Zhou, Jun

2014-01-01

Graphical abstract: Two kinds of Ag–NaCMC films for surface-enhanced Raman scattering (SERS) were prepared by conventional heating and microwave assisted in situ reduction methods without any additional capping or reducing agents. A relatively narrow and symmetric surface plasmon resonance band was observed in the absorption spectra of the films fabricated by the microwave assisted in situ reduction method. More uniform silver nanoparticles (NPs) implied by the symmetric absorption spectrum were further confirmed by the scanning electron microscopy images. After the simulation of the E-field intensity distribution around the silver NPs in NaCMC film, the Raman scattering enhancement factors (EFs) of these films were then investigated with 4-mercaptobenzoic acid molecule as a SERS reporter. Improved reproducibility of SERS signal was obtained in the microwave assisted synthesized Ag–NaCMC film, although it maintained an EF as only 1.11 × 10 8 . The reproducible SERS signal of the Ag–NaCMC film is particularly attractive and this microwave assisted in situ reduction method is suitable for the production of excellent substrate for biosensor application. - Highlights: • The synthesis of Ag–NaCMC films was successfully fulfilled by a low-cost microwave method. • More uniform silver nanoparticles were observed in Ag–NaCMC film synthesized by microwave. • Improved reproducibility of SERS signal was obtained in microwave synthesized Ag–NaCMC film. - Abstract: Two kinds of Ag–NaCMC films for surface-enhanced Raman scattering (SERS) were prepared by conventional heating and microwave assisted in situ reduction methods without any additional capping or reducing agents. A relatively narrow and symmetric surface plasmon resonance band was observed in the absorption spectra of the films fabricated by the microwave assisted in situ reduction method. More uniform silver nanoparticles (NPs) implied by the symmetric absorption spectrum were further confirmed by

Multiple atomic scale solid surface interconnects for atom circuits and molecule logic gates

International Nuclear Information System (INIS)

Joachim, C; Martrou, D; Gauthier, S; Rezeq, M; Troadec, C; Jie Deng; Chandrasekhar, N

2010-01-01

The scientific and technical challenges involved in building the planar electrical connection of an atomic scale circuit to N electrodes (N > 2) are discussed. The practical, laboratory scale approach explored today to assemble a multi-access atomic scale precision interconnection machine is presented. Depending on the surface electronic properties of the targeted substrates, two types of machines are considered: on moderate surface band gap materials, scanning tunneling microscopy can be combined with scanning electron microscopy to provide an efficient navigation system, while on wide surface band gap materials, atomic force microscopy can be used in conjunction with optical microscopy. The size of the planar part of the circuit should be minimized on moderate band gap surfaces to avoid current leakage, while this requirement does not apply to wide band gap surfaces. These constraints impose different methods of connection, which are thoroughly discussed, in particular regarding the recent progress in single atom and molecule manipulations on a surface.

In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy

Science.gov (United States)

Wang, Fei; Wang, Hua-Lin; Qiu, Yang; Chang, Yu-Long; Long, Yi-Tao

2015-12-01

In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation.

Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

Energy Technology Data Exchange (ETDEWEB)

Meng, Qingyong, E-mail: mengqingyong@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, 116023 Dalian (China); Meyer, Hans-Dieter, E-mail: hans-dieter.meyer@pci.uni-heidelberg.de [Theoretische Chemie, Physikalisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)

2015-10-28

Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

Enhancement of molecular NMR signal induced by polarization transfer from laser-polarized 129Xe

International Nuclear Information System (INIS)

Sun Xianping

2001-01-01

There is a large non-equilibrium nuclear polarization and a longer relaxation time in the laser-polarized 129 Xe produced by means of optical pumping and spin exchange. The characteristics of the laser-polarized 129 Xe permit the transfer of the polarization to enhance the atomic nuclear spin in liquid, solid and surface of solid molecules. Therefore, the sensitivity in nuclear magnetic resonance measurements for the molecules is enhanced and applications in the investigations of materials and surface sciences are expanded. The progress in the investigations of materials and surface sciences are expanded. The progress in the investigations of the polarization transfer between laser-polarized 129 Xe and the atomic nuclei in the molecules, the relative physics and the measurement of some parameters are introduced

Surface-imprinted core–shell Au nanoparticles for selective detection of bisphenol A based on surface-enhanced Raman scattering

International Nuclear Information System (INIS)

Xue, Jin-Qun; Li, Da-Wei; Qu, Lu-Lu; Long, Yi-Tao

2013-01-01

Graphical abstract: -- Highlights: •The molecularly imprinted polymer capped core–shell AuNPs (MIP-ir-AuNPs) were fabricated as a specific functional SERS substrate. •MIP-ir-AuNPs could be utilized in rapid and selective detection of BPA. •MIP-ir-AuNPs displayed good capability for determination of BPA in real samples. -- Abstract: Surface-imprinted core–shell Au nanoparticles (AuNPs) were explored for the highly selective detection of bisphenol A (BPA) by surface-enhanced Raman scattering (SERS). A triethoxysilane-template complex (BPA-Si) was synthesized and then utilized to fabricate a molecularly imprinted polymer (MIP) layer on the AuNPs via a sol–gel process. The imprinted BPA molecules were removed by a simple thermal treatment to generated the imprint-removed material, MIP-ir-AuNPs, with the desired recognition sites that could selectively rebind the BPA molecules. The morphological and polymeric characteristics of MIP-ir-AuNPs were investigated by transmission electron microscopy and Fourier-transform infrared spectroscopy. The results demonstrated that the MIP-ir-AuNPs were fabricated with a 2 nm MIP shell layer within which abundant amine groups were generated. The rebinding kinetics study showed that the MIP-ir-AuNPs could reach the equilibrium adsorption for BPA within 10 min owning to the advantage of ultrathin core–shell nanostructure. Moreover, a linear relationship between SERS intensity and the concentration of BPA on the MIP-ir-AuNPs was observed in the range of 0.5–22.8 mg L −1 , with a detection limit of 0.12 mg L −1 (blank ± 3 × s.d.). When applied to SERS detection, the developed surface-imprinted core–shell MIP-ir-AuNPs could recognize BPA and prevent interference from the structural analogues such as hexafluorobisphenol A (BPAF) and diethylstilbestrol (DES). These results revealed that the proposed method displayed significant potential utility in rapid and selective detection of BPA in real samples

Surface plasmon enhanced quantum transport in a hybrid metal nanoparticle array

International Nuclear Information System (INIS)

Sun, Lin; Nan, Yali; Xu, Shang; Zhang, Sishi; Han, Min

2014-01-01

Hybrid Pd–Ag nanoparticle arrays composed of randomly distributed Pd nanoparticles in dense packing and a small number of dispersed Ag nanoparticles were fabricated with controlled coverage. Photo-enhanced conductance was observed in the nanoparticle arrays. Largest enhancement, which can be higher than 20 folds, was obtained with 450 nm light illumination. This wavelength was found to correlate with the surface plasmon resonance of the Ag nanoparticles. Electron transport measurements showed there were significant Coulomb blockade in the nanoparticle arrays and the blockade could be overcome with the surface plasmon enhanced local field of Ag nanoparticles induced by light illumination. - Highlights: • We study photo-enhanced electron conductance of a hybrid Pd–Ag nanoparticle array. • The light-induced conductance enhancement is as high as 20 folds at 10 K. • The enhancement is correlate with the surface plasmon resonance of Ag nanoparticles. • Coulomb blockades is overcome with the surface plasmon enhanced local field

Plasmonics and single-molecule detection in evaporated silver-island films

Energy Technology Data Exchange (ETDEWEB)

Moula, G.; Aroca, R.F. [Materials and Surface Science Group, University of Windsor, Ontario (Canada); Rodriguez-Oliveros, R.; Sanchez-Gil, J.A. [Instituto de Estructura de la Materia, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain); Albella, P. [Centro de Fisica de Materiales (CSIC-UPV/EHU) and Donostia International Physics Center (DIPC), 20018 Donostia, San Sebastian (Spain)

2012-11-15

The plasmonic origin of surface-enhanced Raman scattering (SERS) leads to the concept of hotspots and plasmon coupling that can be realized in the interstitial regions, or on specially engineered, silver and gold nanostructures. It is also possible to achieve spatial locations of high local field or hotspots on silver-island films (SIF) allowing single-molecule detection (SMD). When a single monomolecular layer coating the SIFs contains dye molecules dispersed in it, single-molecule impurities, (with an average of one hundred dye molecules in 1 {mu}m{sup 2}, which is the field of view of the micro-Raman system), SMD is observed as a rare statistical event. Here, the SMD results for silver-island films are presented, with the same nominal mass thickness, but differing in the localized surface plasmon resonance that is a function of the temperature of substrate during deposition. A blue-shifted plasmon can be seen as a decrease in plasmon coupling for deposition at higher temperature. A simple two-particle model for localized plasmon resonance coupling calculations, including the shape and substrate effects seems to explain the trend of observations. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Assessing Telomere Length Using Surface Enhanced Raman Scattering

Science.gov (United States)

Zong, Shenfei; Wang, Zhuyuan; Chen, Hui; Cui, Yiping

2014-11-01

Telomere length can provide valuable insight into telomeres and telomerase related diseases, including cancer. Here, we present a brand-new optical telomere length measurement protocol using surface enhanced Raman scattering (SERS). In this protocol, two single strand DNA are used as SERS probes. They are labeled with two different Raman molecules and can specifically hybridize with telomeres and centromere, respectively. First, genome DNA is extracted from cells. Then the telomere and centromere SERS probes are added into the genome DNA. After hybridization with genome DNA, excess SERS probes are removed by magnetic capturing nanoparticles. Finally, the genome DNA with SERS probes attached is dropped onto a SERS substrate and subjected to SERS measurement. Longer telomeres result in more attached telomere probes, thus a stronger SERS signal. Consequently, SERS signal can be used as an indicator of telomere length. Centromere is used as the inner control. By calibrating the SERS intensity of telomere probe with that of the centromere probe, SERS based telomere measurement is realized. This protocol does not require polymerase chain reaction (PCR) or electrophoresis procedures, which greatly simplifies the detection process. We anticipate that this easy-operation and cost-effective protocol is a fine alternative for the assessment of telomere length.

Isotope separation using vibrationally excited molecules

International Nuclear Information System (INIS)

Woodroffe, J.A.; Keck, J.C.

1979-01-01

Vibrational excitation of molecules having components of a selected isotope type is used to produce a conversion from vibrational to translational excitation of the molecules by collision with the molecules of a heavy carrier gas. The resulting difference in translaton between the molecules of the selected isotope type and all other molecules of the same compound permits their separate collection. When applied to uranium enrichment, a subsonic cryogenic flow of molecules of uranium hexafluoride in combination with an argon carrier gas is directed through a cooled chamber that is illuminated by laser radiaton tuned to vibrationally excite the uranium hexafluoride molecules of a specific uranium isotope. The excited molecules collide with carrier gas molecules, causing a conversion of the excitation energy into a translation of the excited molecule, which results in a higher thermal energy or diffusivity than that of the other uranium hexafluoride molecules. The flowing molecules including the excited molecules directly enter a set of cryogenically cooled channels. The higher thermal velocity of the excited molecules increases the probability of their striking a collector surface. The molecules which strike this surface immediately condense. After a predetermined thickness of molecules is collected on the surface, the flow of uranium hexafluoride is interrupted and the chamber heated to the point of vaporization of the collected hexafluoride, permitting its removal. (LL)

Dependence of partial molecules surface area on the third component in lyotropic liquid crystals

International Nuclear Information System (INIS)

Badalyan, H.G.; Ghazaryan, Kh.M.; Yayloyan, S.M.

2015-01-01

Free surface of one amphiphilic molecule head of a lyotropic liquid crystal has been investigated by X-Ray diffraction method, at small and large angles, in the presence of the third component. The pentadecilsulphonat-water system in the presence of cholesterol as well as the lecithin-water system in the presence of decanol were investigated. It is shown that the above mentioned free surface decreases if the cholesterol concentration increases, while this surface increases in the case of water concentration increase. However, it increases slower than in the case of the two-component system. The same is observed for the lecithin-water-decanol system

Molecule-surface interaction processes of relevance to gas blanket type fusion device divertor design

Energy Technology Data Exchange (ETDEWEB)

Snowdon, K.J. [Newcastle Univ. (United Kingdom). Dept. of Physics; Tawara, H.

1997-01-01

The mechanisms which may lead to the departure of molecular species from surfaces exposed to low energy (0.1-100 eV) particle or photon and electron irradiation are reviewed. Where possible, the charge and electronic state, angular, translational and internal energy distributions of the departing molecules are described and the physical origin of the nature of those distributions identified. The consequences, for the departing molecules, of certain material choices become apparent from such an analysis. Such information may help guide the choice of appropriate materials for plasma facing components of gas-blanket type divertors such as that recently proposed for the International Thermonuclear Experimental Reactor (ITER). (author). 71 refs.

Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

Science.gov (United States)

Zhao, Hongxia; Yang, Yong; Shu, Xin; Wang, Yanwei; Ran, Qianping

2018-04-09

First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products. Copyright © 2017. Published by Elsevier B.V.

A ternary functional Ag@GO@Au sandwiched hybrid as an ultrasensitive and stable surface enhanced Raman scattering platform

Science.gov (United States)

Zhang, Cong-yun; Hao, Rui; Zhao, Bin; Hao, Yao-wu; Liu, Ya-qing

2017-07-01

The graphene-mediated surface enhanced Raman scattering (SERS) substrates by virtues of plasmonic metal nanostructures and graphene or its derivatives have attracted tremendous interests which are expected to make up the deficiency of traditional plasmonic metal substrates. Herein, we designed and fabricated a novel ternary Ag@GO@Au sandwich hybrid wherein the ultrathin graphene oxide (GO) films were seamlessly wrapped around the hierarchical flower-like Ag particle core and meanwhile provided two-dimensional anchoring scaffold for the coating of Au nanoparticles (NPs). The surface coverage density of loading Au NPs could be readily controlled by tuning the dosage amount of Au particle solutions. These features endowed the sandwiched structures high enrichment capability for analytes such as aromatic molecules and astonishing SERS performance. The Raman signals were enormously enhanced with an ultrasensitive detection limit of rhodamine-6G (R6G) as low as 10-13 M based on the chemical enhancement from GO and multi-dimensional plasmonic coupling between the metal nanoparticles. In addition, the GO interlayer as an isolating shell could effectively prevent the metal-molecule direct interaction and suppress the oxidation of Ag after exposure at ambient condition which enabled the substrates excellent reproducibility with less than 6% signal variations and prolonged life-time. To evaluate the feasibility and the practical application for SERS detection in real-world samples based on GO sandwiched hybrid as SERS-active substrate, three different prohibited colorants with a series of concentrations were measured with a minimum detected concentration down to 10-9 M. Furthermore, the prepared GO sandwiched nanostructures can be used to identify different types of colorants existing in red wine, implying the great potential applications for single-particle SERS sensing of biotechnology and on-site monitoring in food security.

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

Science.gov (United States)

Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

2016-07-08

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

High Surface Area of Porous Silicon Drives Desorption of Intact Molecules

Science.gov (United States)

Northen, Trent R.; Woo, Hin-Koon; Northen, Michael T.; Nordström, Anders; Uritboonthail, Winnie; Turner, Kimberly L.; Siuzdak, Gary

2007-01-01

The surface structure of porous silicon used in desorption/ionization on porous silicon (DIOS) mass analysis is known to play a primary role in the desorption/ionization (D/I) process. In this study, mass spectrometry and scanning electron microscopy (SEM) are used to examine the correlation between intact ion generation with surface ablation, and surface morphology. The DIOS process is found to be highly laser energy dependent and correlates directly with the appearance of surface ions (Sin+ and OSiH+). A threshold laser energy for DIOS is observed (10 mJ/cm2), which supports that DIOS is driven by surface restructuring and is not a strictly thermal process. In addition, three DIOS regimes are observed which correspond to surface restructuring and melting. These results suggest that higher surface area silicon substrates may enhance DIOS performance. A recent example which fits into this mechanism is silicon nanowires surface which have a high surface energy and concomitantly requires lower laser energy for analyte desorpton. PMID:17881245

Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

KAUST Repository

Pump, Eva; Viger-Gravel, Jasmine; Abou-Hamad, Edy; Samantaray, Manoja; Hamzaoui, Bilel; Gurinov, Andrei; Anjum, Dalaver H.; Gajan, David; Lesage, Anne; Bendjeriou-Sedjerari, Anissa; Emsley, Lyndon; Basset, Jean-Marie

2016-01-01

Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

KAUST Repository

Pump, Eva

2016-08-15

Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

Geometry of GLP on silver surface by surface-enhanced Raman spectroscopy

Science.gov (United States)

Bao, PeiDi; Bao, Lang; Huang, TianQuan; Liu, XinMing; Wu, GuoFeng

2000-05-01

Leptospirosis is one of the most harmful zoonosis, it is a serious public health issue in some area of Sichuan province. Surface-Enhance Raman Scattering (SERS) Spectroscopy is an effective approach for the study of biomolecular adsorption on metal surface and provides information about the adsorbed species. Two samples of Leptospiral Glycolipoprotein (GLP-1) and GLP-2 which have different toxic effects have been obtained and investigated.

Microassay for measurement of binding of radiolabelled ligands to cell surface molecules

International Nuclear Information System (INIS)

Woof, J.M.; Burton, D.R.

1988-01-01

An improved technique for measuring the binding of radiolabelled ligands to cell surface molecules has been developed by modification of a procedure using centrifugation through a water-immiscible oil to separate free and cell-bound ligand. It maximises the percentage of ligand bound since cell-bound and free ligand can be separated easily and reproducibly even when very small reaction volumes are used. This permits low levels of ligand radiolabelling and relatively low numbers of cells to be used

Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

International Nuclear Information System (INIS)

Ye, ChuanXiang; Zhao, Yi; Liang, WanZhen

2015-01-01

The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT

Periodic array-based substrates for surface-enhanced infrared spectroscopy

Science.gov (United States)

Mayerhöfer, Thomas G.; Popp, Jürgen

2018-01-01

At the beginning of the 1980s, the first reports of surface-enhanced infrared spectroscopy (SEIRS) surfaced. Probably due to signal-enhancement factors of only 101 to 103, which are modest compared to those of surface-enhanced Raman spectroscopy (SERS), SEIRS did not reach the same significance up to date. However, taking the compared to Raman scattering much larger cross-sections of infrared absorptions and the enhancement factors together, SEIRS reaches about the same sensitivity for molecular species on a surface in terms of the cross-sections as SERS and, due to the complementary nature of both techniques, can valuably augment information gained by SERS. For the first 20 years since its discovery, SEIRS relied completely on metal island films, fabricated by either vapor or electrochemical deposition. The resulting films showed a strong variance concerning their structure, which was essentially random. Therefore, the increase in the corresponding signal-enhancement factors of these structures stagnated in the last years. In the very same years, however, the development of periodic array-based substrates helped SEIRS to gather momentum. This development was supported by technological progress concerning electromagnetic field solvers, which help to understand plasmonic properties and allow targeted design. In addition, the strong progress concerning modern fabrication methods allowed to implement these designs into practice. The aim of this contribution is to critically review the development of these engineered surfaces for SEIRS, to compare the different approaches with regard to their performance where possible, and report further gain of knowledge around and in relation to these structures.

An efficient solution to the decoherence enhanced trivial crossing problem in surface hopping

Science.gov (United States)

Bai, Xin; Qiu, Jing; Wang, Linjun

2018-03-01

We provide an in-depth investigation of the time interval convergence when both trivial crossing and decoherence corrections are applied to Tully's fewest switches surface hopping (FSSH) algorithm. Using one force-based and one energy-based decoherence strategies as examples, we show decoherence corrections intrinsically enhance the trivial crossing problem. We propose a restricted decoherence (RD) strategy and incorporate it into the self-consistent (SC) fewest switches surface hopping algorithm [L. Wang and O. V. Prezhdo, J. Phys. Chem. Lett. 5, 713 (2014)]. The resulting SC-FSSH-RD approach is applied to general Hamiltonians with different electronic couplings and electron-phonon couplings to mimic charge transport in tens to hundreds of molecules. In all cases, SC-FSSH-RD allows us to use a large time interval of 0.1 fs for convergence and the simulation time is reduced by over one order of magnitude. Both the band and hopping mechanisms of charge transport have been captured perfectly. SC-FSSH-RD makes surface hops in the adiabatic representation and can be implemented in both diabatic and locally diabatic representations for wave function propagation. SC-FSSH-RD can potentially describe general nonadiabatic dynamics of electrons and excitons in organics and other materials.

Preparation of surface enhanced Raman substrate and its characterization

Science.gov (United States)

Liu, Y.; Wang, J. Y.; Wang, J. Q.

2017-10-01

Surface enhanced Raman spectroscopy (SERS) is a fast, convenient and highly sensitive detection technique, and preparing the good effect and repeatable substrate is the key to realize the trace amount and quantitative detection in the field of food safety detection. In this paper, a surface enhanced Raman substrate based on submicrometer silver particles structure was prepared by chemical deposition method, and characterized its structure and optical properties.

Single-Molecule Interfacial Electron Transfer

Energy Technology Data Exchange (ETDEWEB)

Lu, H. Peter [Bowling Green State Univ., Bowling Green, OH (United States). Dept. of Chemistry and Center for Photochemical Sciences

2017-11-28

This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static and dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO₂ and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO₂ nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO₂ nanoparticle surfaces by using ultrafast single-molecule

Elucidating the role of surface passivating ligand structural parameters in hole wave function delocalization in semiconductor cluster molecules.

Science.gov (United States)

Teunis, Meghan B; Nagaraju, Mulpuri; Dutta, Poulami; Pu, Jingzhi; Muhoberac, Barry B; Sardar, Rajesh; Agarwal, Mangilal

2017-09-28

This article describes the mechanisms underlying electronic interactions between surface passivating ligands and (CdSe) 34 semiconductor cluster molecules (SCMs) that facilitate band-gap engineering through the delocalization of hole wave functions without altering their inorganic core. We show here both experimentally and through density functional theory calculations that the expansion of the hole wave function beyond the SCM boundary into the ligand monolayer depends not only on the pre-binding energetic alignment of interfacial orbitals between the SCM and surface passivating ligands but is also strongly influenced by definable ligand structural parameters such as the extent of their π-conjugation [π-delocalization energy; pyrene (Py), anthracene (Anth), naphthalene (Naph), and phenyl (Ph)], binding mode [dithiocarbamate (DTC, -NH-CS 2 - ), carboxylate (-COO - ), and amine (-NH 2 )], and binding head group [-SH, -SeH, and -TeH]. We observe an unprecedentedly large ∼650 meV red-shift in the lowest energy optical absorption band of (CdSe) 34 SCMs upon passivating their surface with Py-DTC ligands and the trend is found to be Ph- wave function delocalization rather than carrier trapping and/or phonon-mediated relaxation. Taken together, knowledge of how ligands electronically interact with the SCM surface is crucial to semiconductor nanomaterial research in general because it allows the tuning of electronic properties of nanomaterials for better charge separation and enhanced charge transfer, which in turn will increase optoelectronic device and photocatalytic efficiencies.

Optimal Hotspots of Dynamic Surfaced-Enhanced Raman Spectroscopy for Drugs Quantitative Detection.

Science.gov (United States)

Yan, Xiunan; Li, Pan; Zhou, Binbin; Tang, Xianghu; Li, Xiaoyun; Weng, Shizhuang; Yang, Liangbao; Liu, Jinhuai

2017-05-02

Surface-enhanced Raman spectroscopy (SERS) as a powerful qualitative analysis method has been widely applied in many fields. However, SERS for quantitative analysis still suffers from several challenges partially because of the absence of stable and credible analytical strategy. Here, we demonstrate that the optimal hotspots created from dynamic surfaced-enhanced Raman spectroscopy (D-SERS) can be used for quantitative SERS measurements. In situ small-angle X-ray scattering was carried out to in situ real-time monitor the formation of the optimal hotspots, where the optimal hotspots with the most efficient hotspots were generated during the monodisperse Au-sol evaporating process. Importantly, the natural evaporation of Au-sol avoids the nanoparticles instability of salt-induced, and formation of ordered three-dimensional hotspots allows SERS detection with excellent reproducibility. Considering SERS signal variability in the D-SERS process, 4-mercaptopyridine (4-mpy) acted as internal standard to validly correct and improve stability as well as reduce fluctuation of signals. The strongest SERS spectra at the optimal hotspots of D-SERS have been extracted to statistics analysis. By using the SERS signal of 4-mpy as a stable internal calibration standard, the relative SERS intensity of target molecules demonstrated a linear response versus the negative logarithm of concentrations at the point of strongest SERS signals, which illustrates the great potential for quantitative analysis. The public drugs 3,4-methylenedioxymethamphetamine and α-methyltryptamine hydrochloride obtained precise analysis with internal standard D-SERS strategy. As a consequence, one has reason to believe our approach is promising to challenge quantitative problems in conventional SERS analysis.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

Science.gov (United States)

Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

2016-07-01

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental properties of molecules on surfaces. Molecular switching and interaction of magnetic molecules with superconductors

Energy Technology Data Exchange (ETDEWEB)

Hatter, Nino

2016-12-14

In this thesis, we investigate individual molecular switches and metal-organic complexes on surfaces with scanning tunneling microscopy (STM) and spectroscopy (STS) at low temperatures. One focus addresses the switching ability and mechanism of diarylethene on Ag(111). The other focus lies on resolving and tuning magnetic interactions of individual molecules with superconductors. 4,4'-(4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis (5-methylthiophene-4,2-diyl)dip yridine (PDTE) is a prototypical photochromic switch. We can induce a structural change of individual PDTE molecules on Ag(111) with the STM tip. This change is accompanied by a reduction of the energy gap between the occupied and unoccupied molecular orbitals. Density functional theory (DFT) calculations reveal that the induced switching corresponds to a ring-closing reaction from an open isomer in a flat adsorption configuration to a ring-closed isomer with its methyl groups in a cis configuration. The final product is thermodynamically stabilized by strong dispersion interactions with the surface. A linear dependence of the switching threshold with the tip-sample distance with a minimal threshold of 1.4 V is found, which we assign to a combination of an electric-field induced process and a tunneling-electron contribution. DFT calculations suggest a large activation barrier for a ring-closing reaction from the open flat configuration into the closed cis configuration. The interaction of magnetic molecules with superconductors is studied on manganese phthalocyanine (MnPc) adsorbed on Pb(111). We find triplets of Shiba states inside the superconducting gap. Different adsorption sites of MnPc provide a large variety of exchange coupling strengths, which lead to a collective energy shift of the Shiba triplets. We can assign the splitting of the Shiba states to be an effect of magnetic anisotropy in the system. A quantum phase transition from a ''Kondo screened'' to a &apos

The effect of oxygen molecule adsorption on lead iodide perovskite surface by first-principles calculation

Science.gov (United States)

Ma, Xia-Xia; Li, Ze-Sheng

2018-01-01

Oxygen molecule has a negative effect on perovskite solar cells, which has been investigated experimentally. However, detailed theoretical research is still rare. This study presents a microscopic view to reveal the interaction mechanism between O2 and perovskite based on the first-principles calculation. The results show that O2 is adsorbed on the (100) surface of MAPbI3 perovskite mainly by Van der Waals force. O2 adsorption makes the MAPbI3 surface generate a small number of positive charges, which leads to the increase of the work function of the MAPbI3 surface. This is in agreement with the experimental measurement. And increased work function of MAPbI3 surface is not beneficial to electron transfer from perovskite to electronic extraction layer (such as TiO2). Comparison of the density of states (DOS) of the clean (100) surface and the adsorbed system shows that an in-gap state belonging to O2 appears, which can explain the phenomenon observed from experiments that electron transfers from the surface of perovskite to O2 to form superoxide. The theoretical power conversion efficiency of the system with and without O2 adsorption is evaluated, and it turns out that the power conversion efficiency of the system with O2 adsorption is slightly lower than that of the system without O2 adsorption. This result indicates that avoiding the introduction of O2 molecules between perovskite and electronic extraction layer is beneficial to the perovskite solar cell.

Pool boiling CHF enhancement by micro/nanoscale modification of zircaloy-4 surface

International Nuclear Information System (INIS)

Ahn, Ho Seon; Lee, Chan; Kim, Hyungdae; Jo, HangJin; Kang, SoonHo; Kim, Joonwon; Shin, Jeongseob; Kim, Moo Hwan

2010-01-01

Consideration of the critical heat flux (CHF) requires difficult compromises between economy and safety in many types of thermal systems, including nuclear power plants. Much research has been directed towards enhancing the CHF, and many recent studies have revealed that the significant CHF enhancement in nanofluids is due to surface deposition of nanoparticles. The surface deposition of nanoparticles influenced various surface characteristics. This fact indicated that the surface wettability is a key parameter for CHF enhancement and so is the surface morphology. In this study, surface wettability of zircaloy-4 used as cladding material of fuel rods in nuclear power plants was modified using surface treatment technique (i.e. anodization). Pool boiling experiments of distilled water on the prepared surfaces was conducted at atmospheric and saturated conditions to examine effects of the surface modification on CHF. The experimental results showed that CHF of zircaloy-4 can be significantly enhanced by the improvement in surface wettability using the surface modification, but only the wettability effect cannot explain the CHF increase on the treated zircaloy-4 surfaces completely. It was found that below a critical value of contact angle (10 o ), micro/nanostructures created by the surface treatment increased spreadability of liquid on the surface, which could lead to further increase in CHF even beyond the prediction caused only by the wettability improvement. These micro/nanostructures with multiscale on heated surface induced more significant CHF enhancement than it based on the wettability effect, due to liquid spreadability.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions.

Science.gov (United States)

Li, Da; Liu, Jingquan; Barrow, Colin J; Yang, Wenrong

2014-08-04

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

Functionalised zinc oxide nanowire gas sensors: Enhanced NO(2) gas sensor response by chemical modification of nanowire surfaces.

Science.gov (United States)

Waclawik, Eric R; Chang, Jin; Ponzoni, Andrea; Concina, Isabella; Zappa, Dario; Comini, Elisabetta; Motta, Nunzio; Faglia, Guido; Sberveglieri, Giorgio

2012-01-01

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO(2) produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO(2) down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO(2) compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO(2) target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Bonding and vibrational dynamics of a large π-conjugated molecule on a metal surface

International Nuclear Information System (INIS)

Temirov, R; Soubatch, S; Lassise, A; Tautz, F S

2008-01-01

The interplay between the substrate bonding of a large π-conjugated semiconductor molecule and the dynamical properties of the metal-organic interface is studied, employing the prototypical PTCDA/Ag(111) monolayer as an example. Both the coupling of molecular vibrations to the electron-hole-pair continuum of the metal surface and the inelastic scattering of tunnelling electrons by the molecular vibrations on their passage through the molecule are considered. The results of both types of experiment are consistent with the findings of measurements which probe the geometric and electronic structure of the adsorbate-substrate complex directly; generally speaking, they can be understood in the framework of standard theories for the electron-vibron coupling. While the experiments reported here in fact provide additional qualitative insights into the substrate bonding of our π-conjugated model molecule, their detailed quantitative understanding would require a full calculation of the dynamical interface properties, which is currently not available

Quantitative Determination of Nicotine in a PDMS Microfluidic Channel Using Surface Enhanced Raman Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Jung, Jae Hyun; Choo, Jae Bum [Hanyang University, Ansan (Korea, Republic of); Kim, Duck Joong [Dankook University, Cheonan (Korea, Republic of); Lee, Sang Hoon [Korea University, Seoul (Korea, Republic of)

2006-02-15

Rapid and highly sensitive determination of nicotine in a PDMS microfluidic channel was investigated using surface enhanced Raman spectroscopy (SERS). A three-dimensional PDMS microfluidic channel was fabricated for this purpose. This channel shows a high mixing efficiency because the transverse and vertical dispersions of the fluid occur simultaneously through the upper and lower zig zag-type blocks. A higher efficiency of mixing could also be obtained by splitting each of the confluent streams into two sub-streams that then joined and recombined. The SERS signal was measured after nicotine molecules were effectively adsorbed onto silver nanoparticles by passing through the three-dimensional channel. A quantitative analysis of nicotine was performed based on the measured peak area at 1030 cm{sup -1}. The detection limit was estimated to be below 0.1 ppm. In this work, the SERS detection, in combination with a PDMS microfluidic channel, has been applied to the quantitative analysis of nicotine in aqueous solution. Compared to the other conventional analytical methods, the detection sensitivity was enhanced up to several orders of magnitude.

Shape-dependent surface-enhanced Raman scattering in gold–Raman-probe–silica sandwiched nanoparticles for biocompatible applications

International Nuclear Information System (INIS)

Li Ming; Cushing, Scott K; Lankford, Jessica; Wu, Nianqiang; Zhang Jianming; Ma Dongling; Aguilar, Zoraida P

2012-01-01

To meet the requirement of Raman probes (labels) for biocompatible applications, a synthetic approach has been developed to sandwich the Raman-probe (malachite green isothiocyanate, MGITC) molecules between the gold core and the silica shell in gold–SiO 2 composite nanoparticles. The gold–MGITC–SiO 2 sandwiched structure not only prevents the Raman probe from leaking out but also improves the solubility of the nanoparticles in organic solvents and in aqueous solutions even with high ionic strength. To amplify the Raman signal, three types of core, gold nanospheres, nanorods and nanostars, have been chosen as the substrates of the Raman probe. The effect of the core shape on the surface-enhanced Raman scattering (SERS) has been investigated. The colloidal nanostars showed the highest SERS enhancement factor while the nanospheres possessed the lowest SERS activity under excitation with 532 and 785 nm lasers. Three-dimensional finite-difference time domain (FDTD) simulation showed significant differences in the local electromagnetic field distributions surrounding the nanospheres, nanorods, and nanostars, which were induced by the localized surface plasmon resonance (LSPR). The electromagnetic field was enhanced remarkably around the two ends of the nanorods and around the sharp tips of the nanostars. This local electromagnetic enhancement made the dominant contribution to the SERS enhancement. Both the experiments and the simulation revealed the order nanostars > nanorods > nanospheres in terms of the enhancement factor. Finally, the biological application of the nanostar–MGITC–SiO 2 nanoparticles has been demonstrated in the monitoring of DNA hybridization. In short, the gold–MGITC–SiO 2 sandwiched nanoparticles can be used as a Raman probe that features high sensitivity, good water solubility and stability, low-background fluorescence, and the absence of photobleaching for future biological applications. (paper)

Coupling of carbon monoxide molecules over oxygen-defected UO2(111) single crystal and thin film surfaces.

Science.gov (United States)

Senanayake, S D; Waterhouse, G I N; Idriss, H; Madey, Theodore E

2005-11-22

While coupling reactions of carbon-containing compounds are numerous in organometallic chemistry, they are very rare on well-defined solid surfaces. In this work we show that the reductive coupling of two molecules of carbon monoxide to C2 compounds (acetylene and ethylene) could be achieved on oxygen-defected UO2(111) single crystal and thin film surfaces. This result allows in situ electron spectroscopic investigation of a typical organometallic reaction such as carbon coupling and extends it to heterogeneous catalysis and solids. By using high-resolution photoelectron spectroscopy (HRXPS) it was possible to track the changes in surface states of the U and O atoms as well as identify the intermediate of the reaction. Upon CO adsorption U cations in low oxidation states are oxidized to U4+ ions; this was accompanied by an increase of the O-to-U surface ratios. The HRXPS C 1s lines show the presence of adsorbed species assigned to diolate species (-OCH=CHO-) that are most likely the reaction intermediate in the coupling of two CO molecules to acetylene and ethylene.

Coupling of Carbon Monoxide Molecules over Oxygen Defected UO2 (111) Single Crystal and Thin Film Surfaces

International Nuclear Information System (INIS)

Senanayake, S.; Waterhouse, G.; Idriss, H.; Madey, T.

2005-01-01

While coupling reactions of carbon-containing compounds are numerous in organometallic chemistry, they are very rare on well-defined solid surfaces. In this work we show that the reductive coupling of two molecules of carbon monoxide to C 2 compounds (acetylene and ethylene) could be achieved on oxygen-defected UO 2 (111) single crystal and thin film surfaces. This result allows in situ electron spectroscopic investigation of a typical organometallic reaction such as carbon coupling and extends it to heterogeneous catalysis and solids. By using high-resolution photoelectron spectroscopy (HRXPS) it was possible to track the changes in surface states of the U and O atoms as well as identify the intermediate of the reaction. Upon CO adsorption U cations in low oxidation states are oxidized to U 4+ ions; this was accompanied by an increase of the O-to-U surface ratios. The HRXPS C 1s lines show the presence of adsorbed species assigned to diolate species (-OCH=CHO-) that are most likely the reaction intermediate in the coupling of two CO molecules to acetylene and ethylene

Epitaxially Grown Films of Standing and Lying Pentacene Molecules on Cu(110) Surfaces

Science.gov (United States)

2011-01-01

Here, it is shown that pentacene thin films (30 nm) with distinctively different crystallographic structures and molecular orientations can be grown under essentially identical growth conditions in UHV on clean Cu(110) surfaces. By X-ray diffraction, we show that the epitaxially oriented pentacene films crystallize either in the “thin film” phase with standing molecules or in the “single crystal” structure with molecules lying with their long axes parallel to the substrate. The morphology of the samples observed by atomic force microscopy shows an epitaxial alignment of pentacene crystallites, which corroborates the molecular orientation observed by X-ray diffraction pole figures. Low energy electron diffraction measurements reveal that these dissimilar growth behaviors are induced by subtle differences in the monolayer structures formed by slightly different preparation procedures. PMID:21479111

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

Science.gov (United States)

Li, Xiang; Brinckerhoff, William B.; Pinnick, Veronica T; van Amerom, Friso H. W.; Danell, Ryan M.; Arevalo, Ricardo D., Jr.; Getty, Stephanie; Mahaffy, Paul R.

2015-01-01

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

In situ Silver Spot Preparation and on-Plate Surface-Enhanced Raman Scattering Detection in Thin Layer Chromatography Separation

Science.gov (United States)

Herman, K.; Mircescu, N. E.; Szabo, L.; Leopold, L. F.; Chiş, V.; Leopold, N.

2013-05-01

An improved approach for surface-enhanced Raman scattering (SERS) detection of mixture constituents after thin layer chromatography (TLC) separation is presented. A SERS active silver substrate was prepared under open air conditions, directly on the thin silica film by photo-reduction of silver nitrate, allowing the detection of binary mixtures of cresyl violet, bixine, crystal violet, and Cu(II) complex of 4-(2-pyridylazo)resorcinol. The recorded SERS spectrum provides a unique spectral fingerprint for each molecule; therefore the use of analyte standards is avoided, thus rendering the presented procedure advantageous compared to the conventional detection methodology in TLC.

Direct visual evidence of end-on adsorption geometry of pyridine on silver surface investigated by surface enhanced Raman scattering and density functional theory calculations.

Science.gov (United States)

Bhunia, Snehasis; Forster, Stefan; Vyas, Nidhi; Schmitt, Hans-Christian; Ojha, Animesh K

2015-12-05

Fourier transform Raman (FT-Raman) spectra of neat pyridine (Py) and surface enhanced Raman scattering (SERS) spectra of Py with silver nanoparticles (AgNPs) solution at different molar concentrations (X=1.5M, 1.0M, 0.50 M, 0.25 M, and 0.125 M) were recorded using 1064 nm excitation wavelength. The intensity of Raman bands at ∼1003 (ν11) and ∼1035 (ν21) cm(-1) of Py is enhanced in the SERS spectra. Two new Raman bands were observed at ∼1009 (ν12) and ∼1038 (ν22) cm(-1) in the SERS spectra. These bands correspond to the ring breathing vibrations of Py molecules adsorbed at the AgNPs surface. The value of intensity ratios (I12/I11) and (I21/I22) is increased with dilution and attains a maximum value at X=0.5M and upon further dilution (0.25 and 0.125 M) it drops gradually. The theoretically calculated Raman spectra were found to be in good agreement with experimentally observed Raman spectra. Both, experimental and theoretical investigations have confirmed that the Py interacts with AgNPs via the end-on geometry. Copyright © 2015 Elsevier B.V. All rights reserved.

Coupling between diffusion and orientation of pentacene molecules on an organic surface.

Science.gov (United States)

Rotter, Paul; Lechner, Barbara A J; Morherr, Antonia; Chisnall, David M; Ward, David J; Jardine, Andrew P; Ellis, John; Allison, William; Eckhardt, Bruno; Witte, Gregor

2016-04-01

The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

Organizing and addressing magnetic molecules.

Science.gov (United States)

Gatteschi, Dante; Cornia, Andrea; Mannini, Matteo; Sessoli, Roberta

2009-04-20

Magnetic molecules ranging from simple organic radicals to single-molecule magnets (SMMs) are intensively investigated for their potential applications in molecule-based information storage and processing. The goal of this Article is to review recent achievements in the organization of magnetic molecules on surfaces and in their individual probing and manipulation. We stress that the inherent fragility and redox sensitivity of most SMM complexes, combined with the noninnocent role played by the substrate, ask for a careful evaluation of the structural and electronic properties of deposited molecules going beyond routine methods for surface analysis. Detailed magnetic information can be directly obtained using X-ray magnetic circular dichroism or newly emerging scanning probe techniques with magnetic detection capabilities.

Surface-enhanced light olefin yields during steam cracking

NARCIS (Netherlands)

Golombok, M.; Kornegoor, M.; Brink, van den P.; Dierickx, J.; Grotenbreg, R.

2000-01-01

Various papers have shown enhanced olefin yields during steam cracking when a catalytic surface is introduced. Our studies reveal that increased light olefin yields during catalytic steam cracking are mainly due to a surface volume effect and not to a traditional catalytic effect. Augmentation of

Multiple layered metallic nanostructures for strong surface-enhanced Raman spectroscopy enhancement

International Nuclear Information System (INIS)

Xia, Ming; Xie, Ya-Hong; Qiao Kuan; Cheng Zhiyuan

2016-01-01

We report a systematic study on a practical way of patterning metallic nanostructures to achieve high surface-enhanced Raman spectroscopy (SERS) enhancement factors (EFs) and high hot-spot density. By simply superimposing a 1-layer Au nanotriangle array on another to form a multilayer nanotriangle array, the SERS signal can be enhanced by 2 orders of magnitude compared with a 1-layer nanotriangle array. The drastic increases in the SERS EF and the hot spot density of the multilayer Au nanotriangle array are due to the increase in the number of gaps formed between Au nanotriangles and the decrease of the gap width. (author)

Surface-enhanced Raman spectroscopy based on conical holed enhancing substrates

International Nuclear Information System (INIS)

Chen, Yao; Chen, Zeng-Ping; Zuo, Qi; Shi, Cai-Xia; Yu, Ru-Qin

2015-01-01

In this contribution, surface-enhanced Raman spectroscopy (SERS) based on conical holed glass substrates deposited with silver colloids was reported for the first time. It combines the advantages of both dry SERS assays based on plane films deposited with silver colloids and wet SERS assays utilizing cuvettes or capillary tubes. Compared with plane glass substrates deposited with silver colloids, the conical holed glass substrates deposited with silver colloids exhibited five-to ten-folds of increase in the rate of signal enhancement, due to the internal multiple reflections of both the excitation laser beam and the Raman scattering photons within conical holes. The application of conical holed glass substrates could also yield significantly stronger and more reproducible SERS signals than SERS assays utilizing capillary tubes to sample the mixture of silver colloids and the solution of the analyte of interest. The conical holed glass substrates in combination with the multiplicative effects model for surface-enhanced Raman spectroscopy (MEM SERS ) achieved quite sensitive and precise quantification of 6-mercaptopurine in complex plasma samples with an average relative prediction error of about 4% and a limit of detection of about 0.02 μM using a portable i-Raman 785H spectrometer. It is reasonable to expect that SERS technique based on conical holed enhancing substrates in combination with MEM SERS model can be developed and extended to other application areas such as drug detection, environmental monitoring, and clinic analysis, etc. - Highlights: • A novel conical holed SERS enhancing substrate was designed and manufactured. • The optimal conical holed glass substrates can produce stronger SERS signal. • The novel substrates can overcome the shortcomings of both dry and wet methods. • The novel substrates coupled with MEM SERS can realize quantitative SERS assays

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

Science.gov (United States)

Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

2016-01-26

surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.

Surface-enhanced Raman Spectroscopy of Ethephone Adsorbed on Silver Surface

International Nuclear Information System (INIS)

Lee, Chul Jae; Kim, Hee Jin; Karim, Mohammad Rezaul; Lee, Mu Sang

2006-01-01

We investigated the Surface-enhanced Raman Spectroscopy (SERS) spectrum of ethephone (2- chloroethylphosphonic acid). We observed significant signals in the ordinary Raman spectrum for solid-state ethephone as well as when it was adsorbed on a colloidal silver surface, strong vibrational signals were obtained at a very low concentration. The SERS spectra were obtained by silver colloids that were prepared by the γ - irradiation method. The influence of pH and the influence of anion (Cl - , Br - , I - ) on the adsorption orientation were investigated. Two different adsorption mechanisms were deduced, depending on the experimental conditions. The chlorine atom or the chlorine and two oxygen atoms were adsorbed on the colloidal silver surface. Among halide ions, Br - and I - were more strongly adsorbed on the colloidal silver surfaces. As a result, the adsorption of ethephone was less effective due to their steric hinderance

Plasmon-enhanced absorption in a metal nanoparticles and photosynthetic molecules hybrid system

Science.gov (United States)

Fan, Zhiyuan; Govorov, Alexander

2010-03-01

Photosystem I from cyanobacteria is one of nature's most efficient light harvesting complexes, converting light energy into electronic energy with a quantum yield of 100% and an energy yield about 58%. It is very attractive to the nanotechnology community because of its nanoscale dimensions and excellent optoelectronic properties. This protein has the potential to be utilized in devices such as solar cells, electric switches, photo-detectors, etc. However, there is one limiting factor for potential applications of a single monolayer of these photosynthetic proteins. One monolayer absorbs less than 1% of sunlight's energy, despite their excellent optoelectronic properties. Recently, experiments [1] have been conducted to enhance light absorption with the assistance of metal nanoparticles as artificial antenna for the photosystem I. Here, we present a theoretical description of the strong plasmon-assisted interactions between the metal nanoparticles and the optical dipoles of the reaction centers observed in the experiments. The resonance and off-resonance plasmon effects enhance the electromagnetic fields around the photosystem-I molecules and, in this way, lead to enhanced absorption. [4pt] [1] I. Carmeli, I. Lieberman, L. Kraversky, Zhiyuan Fan, A. O. Govorov, G. Markovich, and S. Richter, submitted.

Energy-switching potential energy surface for the water molecule revisited: A highly accurate singled-sheeted form.

Science.gov (United States)

Galvão, B R L; Rodrigues, S P J; Varandas, A J C

2008-07-28

A global ab initio potential energy surface is proposed for the water molecule by energy-switching/merging a highly accurate isotope-dependent local potential function reported by Polyansky et al. [Science 299, 539 (2003)] with a global form of the many-body expansion type suitably adapted to account explicitly for the dynamical correlation and parametrized from extensive accurate multireference configuration interaction energies extrapolated to the complete basis set limit. The new function mimics also the complicated Sigma/Pi crossing that arises at linear geometries of the water molecule.

Amplification of Surface-Enhanced Raman Scattering Due to Substrate-Mediated Localized Surface Plasmons in Gold Nanodimers

KAUST Repository

Yue, Weisheng

2017-03-28

Surface-enhanced Raman scattering (SERS) is ubiquitous in chemical and biochemical sensing, imaging and identification. Maximizing SERS enhancement is a continuous effort focused on the design of appropriate SERS substrates. Here we show that significant improvement in a SERS signal can be achieved with substrates combining localized surface plasmon resonances and a nonresonant plasmonic substrate. By introducing a continuous gold (Au) film underneath Au nanodimers antenna arrays, an over 10-fold increase in SERS enhancement is demonstrated. Triangular, rectangle and disc dimers were studied, with bowtie antenna providing highest SERS enhancement. Simulations of electromagnetic field distributions of the Au nanodimers on the Au film support the observed enhancement dependences. The hybridization of localized plasmonic modes with the image modes in a metal film provides a straightforward way to improve SERS enhancement in designer SERS substrate.

Local Intensity Enhancements in Spherical Microcavities: Implications for Photonic Chemical and Biological Sensors

Science.gov (United States)

Fuller, Kirk A.

2005-01-01

In this report, we summarize recent findings regarding the use spherical microcavities in the amplification of light that is inelastically scattered by either fluorescent or Raman-active molecules. This discussion will focus on Raman scattering, with the understanding that analogous processes apply to fluorescence. Raman spectra can be generated through the use of a very strong light source that stimulates inelastic light scattering by molecules, with the scattering occurring at wavelengths shifted from that of the source and being most prominent at shifts associated with the molecules natural vibrational frequencies. The Raman signal can be greatly enhanced by exposing a molecule to the intense electric fields that arise near surfaces (typically of gold or silver) exhibiting nanoscale roughness. This is known as surface-enhanced Raman scattering (SERS). SERS typically produces gain factors of 103 - 106, but under special conditions, factors of 1010 - 1014 have been achieved.

Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

Science.gov (United States)

Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

2015-04-01

The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor

First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe(110) surface

International Nuclear Information System (INIS)

Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

2010-01-01

Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C 2 H 2 molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C 2 H 2 molecules. The most stable site for C 2 H 2 on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C 2 H 2 molecule, the barrier height energies for the C atom, C 2 -dimer and CH as well as the C 2 H 2 molecule are estimated using the nudged elastic band method. The barrier height energy for C 2 H 2 is 0.71 eV and this indicates that the C 2 H 2 diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C 2 H 2 on Fe. The first step is the dissociation of C 2 H 2 into C 2 H and H, and the second step is that of C 2 H into C 2 and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C 2 H 2 into C 2 H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C 2 H 2 . The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C 2 H 2 which characterizes the beginning of the formation of the graphene.

First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe110 surface.

Science.gov (United States)

Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

2010-09-29

Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C(2)H(2) molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C(2)H(2) molecules. The most stable site for C(2)H(2) on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C(2)H(2) molecule, the barrier height energies for the C atom, C(2)-dimer and CH as well as the C(2)H(2) molecule are estimated using the nudged elastic band method. The barrier height energy for C(2)H(2) is 0.71 eV and this indicates that the C(2)H(2) diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C(2)H(2) on Fe. The first step is the dissociation of C(2)H(2) into C(2)H and H, and the second step is that of C(2)H into C(2) and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C(2)H(2) into C(2)H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C(2)H(2). The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C(2)H(2) which characterizes the beginning of the formation of the graphene.

Carbon-based nanostructured surfaces for enhanced phase-change cooling

Science.gov (United States)

Selvaraj Kousalya, Arun

To maintain acceptable device temperatures in the new generation of electronic devices under development for high-power applications, conventional liquid cooling schemes will likely be superseded by multi-phase cooling solutions to provide substantial enhancement to the cooling capability. The central theme of the current work is to investigate the two-phase thermal performance of carbon-based nanostructured coatings in passive and pumped liquid-vapor phase-change cooling schemes. Quantification of the critical parameters that influence thermal performance of the carbon nanostructured boiling surfaces presented herein will lead to improved understanding of the underlying evaporative and boiling mechanisms in such surfaces. A flow boiling experimental facility is developed to generate consistent and accurate heat transfer performance curves with degassed and deionized water as the working fluid. New means of boiling heat transfer enhancement by altering surface characteristics such as surface energy and wettability through light-surface interactions is explored in this work. In this regard, carbon nanotube (CNT) coatings are exposed to low-intensity irradiation emitted from a light emitting diode and the subcooled flow boiling performance is compared against a non-irradiated CNT-coated copper surface. A considerable reduction in surface superheat and enhancement in average heat transfer coefficient is observed. In another work involving CNTs, the thermal performance of CNT-integrated sintered wick structures is evaluated in a passively cooled vapor chamber. A physical vapor deposition process is used to coat the CNTs with varying thicknesses of copper to promote surface wetting with the working fluid, water. Thermal performance of the bare sintered copper powder sample and the copper-functionalized CNT-coated sintered copper powder wick samples is compared using an experimental facility that simulates the capillary fluid feeding conditions of a vapor chamber

Osmium Atoms and Os2 Molecules Move Faster on Selenium-Doped Compared to Sulfur-Doped Boronic Graphenic Surfaces.

Science.gov (United States)

Barry, Nicolas P E; Pitto-Barry, Anaïs; Tran, Johanna; Spencer, Simon E F; Johansen, Adam M; Sanchez, Ana M; Dove, Andrew P; O'Reilly, Rachel K; Deeth, Robert J; Beanland, Richard; Sadler, Peter J

2015-07-28

We deposited Os atoms on S- and Se-doped boronic graphenic surfaces by electron bombardment of micelles containing 16e complexes [Os(p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-diselenate/dithiolate)] encapsulated in a triblock copolymer. The surfaces were characterized by energy-dispersive X-ray (EDX) analysis and electron energy loss spectroscopy of energy filtered TEM (EFTEM). Os atoms moved ca. 26× faster on the B/Se surface compared to the B/S surface (233 ± 34 pm·s(-1) versus 8.9 ± 1.9 pm·s(-1)). Os atoms formed dimers with an average Os-Os distance of 0.284 ± 0.077 nm on the B/Se surface and 0.243 ± 0.059 nm on B/S, close to that in metallic Os. The Os2 molecules moved 0.83× and 0.65× more slowly than single Os atoms on B/S and B/Se surfaces, respectively, and again markedly faster (ca. 20×) on the B/Se surface (151 ± 45 pm·s(-1) versus 7.4 ± 2.8 pm·s(-1)). Os atom motion did not follow Brownian motion and appears to involve anchoring sites, probably S and Se atoms. The ability to control the atomic motion of metal atoms and molecules on surfaces has potential for exploitation in nanodevices of the future.

Fabrication of Annealed Gold Nanostructures on Pre-Treated Glow-Discharge Cleaned Glasses and Their Used for Localized Surface Plasmon Resonance (LSPR and Surface Enhanced Raman Spectroscopy (SERS Detection of Adsorbed (Biomolecules

Directory of Open Access Journals (Sweden)

Rodica Elena Ionescu

2017-01-01

Full Text Available Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography or inexpensive (e.g., thermal synthesis approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C. The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR and surface enhanced Raman spectroscopy (SERS optical responses and where used for the detection of low concentrations of two model (biochemical molecules, namely the human cytochrome b5 (Cyt-b5 and trans-1,2-bis(4-pyridylethylene (BPE.

MSINDO quantum chemical modeling study of water molecule adsorption at nano-sized anatase TiO2 surfaces

International Nuclear Information System (INIS)

Wahab, Hilal S.; Bredow, Thomas; Aliwi, Salah M.

2008-01-01

In this work, we studied the adsorption of water molecule onto the (1 0 0), (0 1 0) and (0 0 1) surfaces of nano-sized anatase TiO 2 with semiempirical SCF MO method, MSINDO. The anatase TiO 2 particles are modeled with free clusters (TiO 2 ) n, where n = 20-80. Whereas, the surfaces have been modeled with two saturated clusters, Ti 21 O 58 H 32 and Ti 36 O 90 H 36 . The surface lattice fivefold coordinated titanium atoms (Ti 5C ), which represent the Lewis acid sites, are selected as adsorption centers. We also investigated the effect of TiO 2 cluster size on the computed band gap energy. Results reveal that the electronic properties of a cluster in the lowest excited state differ from that of the ground state. Furthermore, the MSINDO band gap energies of 3.68-3.77 eV for the anatase TiO 2 are in a fair accordance with other literature data. In agreement with other computational and experimental studies, the dissociated form of water molecule adsorption on anatase TiO 2 surfaces is always more stabilized than the molecular form

Numerical study of surface plasmon enhanced nonlinear absorption and refraction.

Science.gov (United States)

Kohlgraf-Owens, Dana C; Kik, Pieter G

2008-07-07

Maxwell Garnett effective medium theory is used to study the influence of silver nanoparticle induced field enhancement on the nonlinear response of a Kerr-type nonlinear host. We show that the composite nonlinear absorption coefficient, beta(c), can be enhanced relative to the host nonlinear absorption coefficient near the surface plasmon resonance of silver nanoparticles. This enhancement is not due to a resonant enhancement of the host nonlinear absorption, but rather due to a phase shifted enhancement of the host nonlinear refractive response. The enhancement occurs at the expense of introducing linear absorption, alpha(c), which leads to an overall reduced figure of merit beta(c)/alpha(c) for nonlinear absorption. For thin (< 1 microm) composites, the use of surface plasmons is found to result in an increased nonlinear absorption response compared to that of the host material.

Vibrations of a molecule in an external force field.

Science.gov (United States)

Okabayashi, Norio; Peronio, Angelo; Paulsson, Magnus; Arai, Toyoko; Giessibl, Franz J

2018-05-01

The oscillation frequencies of a molecule on a surface are determined by the mass distribution in the molecule and the restoring forces that occur when the molecule bends. The restoring force originates from the atomic-scale interaction within the molecule and with the surface, which plays an essential role in the dynamics and reactivity of the molecule. In 1998, a combination of scanning tunneling microscopy with inelastic tunneling spectroscopy revealed the vibrational frequencies of single molecules adsorbed on a surface. However, the probe tip itself exerts forces on the molecule, changing its oscillation frequencies. Here, we combine atomic force microscopy with inelastic tunneling spectroscopy and measure the influence of the forces exerted by the tip on the lateral vibrational modes of a carbon monoxide molecule on a copper surface. Comparing the experimental data to a mechanical model of the vibrating molecule shows that the bonds within the molecule and with the surface are weakened by the proximity of the tip. This combination of techniques can be applied to analyze complex molecular vibrations and the mechanics of forming and loosening chemical bonds, as well as to study the mechanics of bond breaking in chemical reactions and atomic manipulation.

Surface-enhanced Raman scattering detection of silver nanoparticles in environmental and biological samples

Energy Technology Data Exchange (ETDEWEB)

Guo, Huiyuan [Stockbridge School of Agriculture, University of Massachusetts, Amherst, MA 01003 (United States); Xing, Baoshan, E-mail: bx@umass.edu [Stockbridge School of Agriculture, University of Massachusetts, Amherst, MA 01003 (United States); Hamlet, Leigh C.; Chica, Andrea [Stockbridge School of Agriculture, University of Massachusetts, Amherst, MA 01003 (United States); He, Lili, E-mail: lilihe@foodsci.umass.edu [Department of Food Science, University of Massachusetts, Amherst, MA 01003 (United States)

2016-06-01

Growing concerns over the potential release and threat of silver nanoparticles (AgNPs) to environmental and biological systems urge researchers to investigate their fate and behavior. However, current analytical techniques cannot meet the requirements for rapidly, sensitively and reliably probing AgNPs in complex matrices. Surface-enhanced Raman spectroscopy (SERS) has shown great capability for rapid detection of AgNPs based on an indicator molecule that can bind on the AgNP surface. The objective of this study was to exploit SERS to detect AgNPs in environmental and biological samples through optimizing the Raman indicator for SERS. Seven indicator molecules were selected and determined to obtain their SERS signals at optimal concentrations. Among them, 1,2-di(4-pyridyl)ethylene (BPE), crystal violet and ferric dimethyl-dithiocarbamate (ferbam) produced the highest SERS intensities. Further experiments on binding competition between each two of the three candidates showed that ferbam had the highest AgNPs-binding ability. The underlying mechanism lies in the strong binding affinity of ferbam with AgNPs via multiple sulfur atoms. We further validated ferbam to be an effective indicator for SERS detection of as low as 0.1 mg/L AgNPs in genuine surface water and 0.57 mg/L in spinach juice. Moreover, limited interference on SERS detection of AgNPs was found from environmentally relevant inorganic ions, organic matter, inorganic particles, as well as biologically relevant components, demonstrating the ferbam-assisted SERS is an effective and sensitive method to detect AgNPs in complex environmental and biological samples. - Graphical abstract: SERS signal intensity of ferbam indicates the concentration of AgNPs. - Highlights: • Ferbam was found to be the best indicator for SERS detection of AgNPs. • SERS was able to detect AgNPs in both environmental and biological samples. • Major components in the two matrices had limited effect on AgNP detection.

Surface-enhanced Raman scattering detection of silver nanoparticles in environmental and biological samples

International Nuclear Information System (INIS)

Guo, Huiyuan; Xing, Baoshan; Hamlet, Leigh C.; Chica, Andrea; He, Lili

2016-01-01

Growing concerns over the potential release and threat of silver nanoparticles (AgNPs) to environmental and biological systems urge researchers to investigate their fate and behavior. However, current analytical techniques cannot meet the requirements for rapidly, sensitively and reliably probing AgNPs in complex matrices. Surface-enhanced Raman spectroscopy (SERS) has shown great capability for rapid detection of AgNPs based on an indicator molecule that can bind on the AgNP surface. The objective of this study was to exploit SERS to detect AgNPs in environmental and biological samples through optimizing the Raman indicator for SERS. Seven indicator molecules were selected and determined to obtain their SERS signals at optimal concentrations. Among them, 1,2-di(4-pyridyl)ethylene (BPE), crystal violet and ferric dimethyl-dithiocarbamate (ferbam) produced the highest SERS intensities. Further experiments on binding competition between each two of the three candidates showed that ferbam had the highest AgNPs-binding ability. The underlying mechanism lies in the strong binding affinity of ferbam with AgNPs via multiple sulfur atoms. We further validated ferbam to be an effective indicator for SERS detection of as low as 0.1 mg/L AgNPs in genuine surface water and 0.57 mg/L in spinach juice. Moreover, limited interference on SERS detection of AgNPs was found from environmentally relevant inorganic ions, organic matter, inorganic particles, as well as biologically relevant components, demonstrating the ferbam-assisted SERS is an effective and sensitive method to detect AgNPs in complex environmental and biological samples. - Graphical abstract: SERS signal intensity of ferbam indicates the concentration of AgNPs. - Highlights: • Ferbam was found to be the best indicator for SERS detection of AgNPs. • SERS was able to detect AgNPs in both environmental and biological samples. • Major components in the two matrices had limited effect on AgNP detection.

Self-consistent meta-generalized gradient approximation study of adsorption of aromatic molecules on noble metal surfaces

DEFF Research Database (Denmark)

Ferrighi, Lara; Madsen, Georg Kent Hellerup; Hammer, Bjørk

2011-01-01

aromatic molecules considered. The adsorption of pentacene is studied on Au, Ag, and Cu surfaces. In agreement with experiment, the adsorption energies are found to increase with decreasing nobleness, but the dependency is underestimated. We point out how the kinetic energy density can discriminate between...

Condensation Enhancement by Surface Porosity: Three-Stage Mechanism.

Science.gov (United States)

Yarom, Michal; Marmur, Abraham

2015-08-18

Surface defects, such as pores, cracks, and scratches, are naturally occurring and commonly found on solid surfaces. However, the mechanism by which such imperfections promote condensation has not been fully explored. In the current paper we thermodynamically analyze the ability of surface porosity to enhance condensation on a hydrophilic solid. We show that the presence of a surface-embedded pore brings about three distinct stages of condensation. The first is capillary condensation inside the pore until it is full. This provides an ideal hydrophilic surface for continuing the condensation. As a result, spontaneous condensation and wetting can be achieved at lower vapor pressure than on a smooth surface.

The neural cell adhesion molecule L1 is distinct from the N-CAM related group of surface antigens BSP-2 and D2

DEFF Research Database (Denmark)

Faissner, A; Kruse, J; Goridis, C