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At least 19 recordsLinked to original sources
PubMed1990

Surface-enhanced Raman scattering of dopamine at polymer-coated silver electrodes.

Attenuation of dopamine surface-enhanced Raman scattering (SERS) spectra at silver electrodes by protein adsorption is described. Polymer-modified electrodes eliminate protein adsorption effects. Partially hydrolyzed cellulose acetate coatings prevent protein adsorption and allow transport of dopamine to and from the electrode surface. Dopamine SERS spectra from these electrodes are similar to those obtained at uncoated electrodes. Perfluorosulfonate (Nafion) coatings also prevent protein adsorption. However, dopamine transported to the electrode remains trapped inside the coating and cannot be removed.

Animals↗
PubMed1990

Surface-enhanced resonance raman scattering spectroscopy of bacterial photosynthetic membranes: orientation of the carotenoids of Rhodobacter sphaeroides 2.4.1.

Surface-enhanced resonance Raman scattering (SERRS) spectra were obtained from carotenoids, in the all-trans configuration, located on the antenna complexes of Rhodobacter sphaeroides 2.4.1 membranes. Since resonance Raman (RR) spectra are barely detectable at the concentration that SERRS signals saturate, SERRS represents a very sensitive means of detecting pigments in biological systems. Prominent SERRS spectra of sphaeroidenone were detected in chromatophores (cytoplasmic side out) but not in spheroplast-derived vesicles (periplasmic side out), demonstrating that the carotenoid is asymmetrically located on the cytoplasmic side of the cell membrane. Comparison of peak frequencies from SERRS and RR spectral data suggests that the carotenoids are oriented into the membrane with the methoxy end of the isoprenoid chains located closest to the cytoplasmic side of the intracytoplasmic membrane. This work not only shows that SERRS spectroscopy can provide information on the location of a chromophore in a biological membrane but also for the first time demonstrates that SERRS data can be used to ascertain the orientation of a chromophore within the membrane. This observation greatly increases the potential of this technique for structural analysis of intact membranes at the molecular level.

Bacterial Chromatophores↗
PubMed1994

Surface-enhanced Raman gene probes.

We report for the first time a new type of DNA gene probe based on surface-enhanced Raman scattering (SERS) label detection. The surface-enhanced Raman gene (SERG) probes do not require the use of radioactive labels and have great potential to provide both sensitivity and selectivity. The SERG probe can be used to detect DNA biotargets (e.g., gene sequences, bacteria, viral DNA fragments) via hybridization to DNA sequences complementary to that probe. The analytical figures of merit and its applications in environmental and biomedical areas are discussed.

DNA Probes↗
PubMed1992

Direct spectroscopic determination of functional sulphydryl groups on intact cell surfaces by surface-enhanced resonance Raman scattering.

Semi-quantitative and direct determination of labelled sulphydryl groups on the surface of intact erythrocytes has been accomplished for the first time with surface-enhanced resonance Raman scattering (SERRS). The method, which involves the use of citrate-reduced silver colloids, is sensitive and selective. A 10(-8) M effective concentration of picomole quantities of sulphydryl groups was determined in the presence of the normally overwhelming signal from haemoglobin. This seminal study suggests that SERRS may be applied to other in situ, site-directed labelling experiments.

Cell Membrane↗
PubMed1988

Surface-enhanced resonance Raman scattering spectroscopy of bacterial photosynthetic membranes. The carotenoid of Rhodospirillum rubrum.

Resonance Raman scattering by the carotenoid, spirilloxanthin (Spx), in a suspension of chromatophores (cytoplasmic side out) isolated from the photosynthetic bacterium, Rhodospirillum rubrum, is greatly enhanced when the membranes are adsorbed onto the surface of an anodized Ag electrode. The phenomenon is the basis for surface-enhanced resonance Raman scattering (SERRS) spectroscopy. The Spx SERRS peaks observed were at 1505-1510, 1150-1155, and 1000-1005 cm-1 with laser excitation wavelengths ranging between 457.9 and 568.2 nm. Similar peaks were not observed with spheroplasts (periplasmic side out) isolated from the same species. The difference in signal detected in chromatophores and spheroplasts is not due to differences in membrane surface charge, presence of residual cell wall on the spheroplast surface, lack of adhesion of spheroplasts to metals, or large differences in pigment content per unit membrane area. Instead, the results indicate an asymmetric distribution of Spx in vivo across the membrane (i.e., it is located on the cytoplasmic side of the membrane). The results also demonstrate that the SERRS effect is extremely distance sensitive, and the thickness of a single bacterial membrane (separating the Ag electrode from the carotenoid) is sufficient to prevent detection of Spx spectra. Studies of chromatophores from the F24 strain (a reaction centerless mutant) have pin-pointed B880 antenna complex as the source of the Spx SERRS spectra, and a schematic model of the minimal structural unit of B880 is presented. This work demonstrates the potential of the SERRS technique as a probe for surface topology of pigmented membranes.

Carotenoids↗
PubMed1993

Evidence for retention of biological activity of a non-heme iron enzyme adsorbed on a silver colloid: a surface-enhanced resonance Raman scattering study.

The structure and catalytic properties of the enzyme (E) chlorocatechol dioxygenase (CCD) adsorbed on a citrate-reduced silver colloid are analyzed by surface-enhanced resonance Raman spectroscopy (SERRS). This is the first SERRS study of a non-heme metalloenzyme. It is demonstrated that the native conformation of CCD is retained in the adsorbed state by comparison of resonance Raman scattering (RRS) from CCD in solution with SERRS from CCD adsorbed on the silver colloid. Both spectra show clear evidence of vibrational bands typical of iron-tyrosinate proteins. Furthermore, it is demonstrated that adsorbed CCD retains 60-85% of its enzymatic activity in the reaction of catechol substrate (S) with O2 to give the dioxygenated product (P) cis,cis-muconate. This is accomplished by enzyme assays of Ag-adsorbed CCD and comparison of the SERRS of Ag-adsorbed enzyme-substrate (ES) complex under anaerobic conditions with that of Ag-adsorbed ES in the presence of dioxygen. The SERRS difference spectrum, ES(aerobic)--ES(anaerobic), shows clear evidence for the appearance of the vibrational modes of adsorbed product. The analogous SERR difference spectroscopy experiment is also carried out for the enzyme-inhibitor (EI) complex of CCD with tetrachlorocatechol (TCC). Slow turnover of CCD-TCC is observed by SERRS on exposure to dioxygen which is consistent with the slow rate of turnover of TCC by CCD in solution.

Adsorption↗
PubMed2026

A point-of-use SERS assay for rapid detecting difenoconazole and flusilazole residues in fruit juices using Au/COF substrate.

We developed a ready-to-use surface-enhanced Raman scattering (SERS) sensor for rapid, pretreatment-free detection of difenoconazole (DIF) and flusilazole (FLU) in peach and lychee juices. The substrate combines Au nanoparticles (AuNPs) with covalent organic frameworks (COF) and is implemented on a portable 25-well plate, enabling in situ testing. Juices can be directly applied to the SERS-active Au/COF composite, allowing simultaneous adsorption and signal generation. The correlation between SERS intensity and logarithmic concentration yielded R-values between 0.925 and 0.986, meeting the monitoring needs of non-laboratory scenarios. The entire workflow completes within 12 min, offering a faster alternative to conventional methods while maintaining high sensitivity and reproducibility. Detection limits reach 0.96-1.22 ppb for DIF and FLU, both of which are below the regulatory maximum residue limits. Distinct SERS fingerprints enable reliable discrimination of mixed residues across juice matrices, supporting rapid on-site monitoring and cost-effective pesticide surveillance.

Triazoles↗
PubMed1989

Immunoassay employing surface-enhanced Raman spectroscopy.

Surface-enhanced Raman scattering (SERS) was used to measure binding between biomolecules with mutual affinity, including antigen-antibody interactions. The conjugation of nitro groups onto bovine serum albumin enhanced their specific SERS activity 10(4)-fold. A dye, 2-[4'-hydroxyphenylazo]benzoic acid (HABA), with a major absorption at the Raman excitation frequency, demonstrated surface-enhanced resonance Raman scattering (SERRS) when captured from solution by avidin-coated silver films. Individual peak intensities showed a logarithmic relationship to the HABA concentration in solution over the range 10(-8) to 10(-5) M. Another resonance dye, p-dimethylaminoazobenzene (DAB) was covalently attached to an antibody directed against human thyroid stimulating hormone (TSH), without loss of antibody activity. The resultant conjugate was used in a sandwich immunoassay for TSH antigen: silver surfaces coated with anti-TSH antibody captured TSH antigen which in turn captured the DAB-anti-TSH antibody conjugate. A linear relationship was observed between the intensity of the resultant SERRS signals and the TSH antigen concentration over a range of from 4 to 60 microIU/ml. These results demonstrate the potential utility of the SERRS effect as a readout in a one-step, no wash immunoassay system.

Animals↗
PubMed1991

Silver-island films as substrates for enhanced Raman scattering: effect of deposition rate on intensity.

The relationship between surface-enhanced resonance Raman scattering (SERRS) intensity and the rate of deposition during silver-island film preparation was examined, using zinc tetraphenylporphine (ZnTPP) as the adsorbate. The effect of the deposition rate on the optical properties of the films at specific wavelengths was also analyzed. The data show that the film extinction (the term extinction is used rather than absorption because the spectra have not been corrected for reflection or scattering losses) increases exponentially at 514 and 458 nm as the deposition rate is decreased. SERRS intensities also increase exponentially at these two excitation wavelengths with a decrease in the deposition rate. The optical density is linearly related to the SERRS intensity, and maximal enhancement is observed for films with the greatest extinction at these excitation wavelengths. In contrast, neither the extinction at 406 nm nor the SERRS scattering intensities resulting from excitation at this wavelength differ substantially. The surface-enhanced Raman scattering (SERS) intensity and the electronic spectra of 4,4'-bipyridine (BP) adsorbed onto silver films as a function deposition rate were also examined. The behavior of the nonresonantly enhanced BP is comparable to that of the resonantly enhanced ZnTPP samples. The effects of the surface morphology, as determined from transmission electron micrographs of the films at various deposition rates, on the corresponding electronic spectra and SERS/SERRS spectra are described.

Electrons↗
PubMedDate not supplied

Measurement of DNA adducts using surface-enhanced Raman spectroscopy.

Hazardous pollutants emitted from energy-related technologies, chemical industries, or waste materials are of increasing public concern because of their potential adverse health effects. Many pollutants have chemical groups of toxicological importance that can be characterized and detected by Raman spectroscopy. Raman spectroscopy, however, has not been widely used in trace organic detection, even though the information contained in a Raman spectrum is valuable for chemical identification. One limitation of conventional Raman spectroscopy is its low sensitivity, which often necessitates the use of powerful and costly laser sources for sample excitation. Raman spectroscopists have recently been able to analyze dilute biological samples as a result of enhancements in the Raman scattering cross section by factors up to 10(10) when a compound is adsorbed on or near a special electron-conducting surface. These spectacular enhancement factors of the normally weak Raman scattering process help overcome the low sensitivity of Raman spectroscopy through a combination of electromagnetic and chemical interactions between the analyte molecule and the surface. The technique associated with this phenomenon is known as surface-enhanced Raman scattering spectroscopy (SERS). The special conductive surface responsible for the scattering enhancement is referred to as a SERS substrate. For the past few years we have developed the SERS technique, using practical SERS-active substrate materials based on silver-coated microspheres deposited on glass. A wide variety of biomarkers have been investigated, including benzo[a]pyrene, dibenz[a,h]anthracene epoxides, 1,N9-ethenoadenine, 3,N4-ethenocytosine, and other substances. These biomarkers were measured at nanogram and subnanogram levels. The experimental results are of great analytical interest, since these chemicals are difficult to detect by other techniques, such as luminescence spectroscopy, because of the weak luminescence quantum yields of these DNA adducts. In this paper the potential usefulness of the SERS technique for assessing environmental and health effects from human exposure to toxic pollutants is demonstrated.

Animals↗
PubMed1990

Flow injection analysis and real-time detection of RNA bases by surface-enhanced Raman spectroscopy.

Surface-enhanced Raman scattering (SERS) spectroscopy has been successfully interfaced with a flow injection analysis system to detect RNA bases in real time. Four of the major base components of RNA, uracil, cytosine, adenine, and guanine, were introduced into the flow injection system and were mixed with a Ag sol prior to SERS measurements. Several experimental parameters including pH, temperature, flow rate, and tubing materials were examined, and their impact on the SERS spectra is presented here. The feasibility of interfacing flow injection based SERS detection methods with liquid or high-performance liquid chromatography for the detection of individual components in a complex mixture is also assessed.

Chromatography, High Pressure Liquid↗
PubMed1994

Molecular interactions of DNA-topoisomerase I and II inhibitor with DNA and topoisomerases and in ternary complexes: binding modes and biological effects for intoplicine derivatives.

Molecular interactions of intoplicine, dual DNA-topoisomerases (Topo) I and II inhibitor, with topoisomerases, plasmid DNA, in ternary cleavable complexes with enzymes and plasmid DNA, and in the reversed cleavable complexes were examined by means of surface-enhanced Raman scattering (SERS) and CD spectroscopy and by biochemical techniques. Detailed spectral analysis of intoplicine derivatives allowed us to assign SERS vibrational modes of chromophores and to propose the models for these complexes. Intoplicine was found to be able to interact specifically with the Topo II alone, but with Topo I only when in the presence of DNA. It shows at least two modes of binding to the DNA: the first was found to be dominant for its derivative 1c (most potent Topo I inhibitor), and the second was dominant for derivative 2a (most potent Topo II inhibitor). The possibility of forming these two types of complexes simultaneously is suggested to be one of the main factors enabling the drug to be a dual Topo I and Topo II inhibitor. The "deep intercalation mode" of the drug from the DNA minor groove with the long axis of the chromophore oriented roughly parallel to the dyad axis has been suggested to be responsible for induction of distortions of the DNA structure by the intercalating drug. Being involved in the formation of Topo I-mediated cleavable ternary complex, the molecules participating in the deep intercalation mode within the DNA do not change their molecular interactions as compared with their complex with the DNA alone. The stabilization of the Topo I-mediated cleavable complex was shown to be followed by the local denaturation of DNA in the AT-rich regions of the helix. When the ternary cleavable complex was reversed, the drug was shown to be in the complex with the plasmid. The "outside binding mode" from the DNA major groove via the hydroxyl group of the A-ring of the chromophore has been suggested to be responsible for Topo II inhibition. These molecules did not induce significant distortions of the DNA structure. Being involved in the formation of Topo II-mediated cleavable ternary complex, the drug changed its molecular interactions as compared with the complex with DNA alone.(ABSTRACT TRUNCATED AT 400 WORDS)

Binding Sites↗
PubMed1989

Surface-enhanced resonance Raman spectroscopy as an ancillary high-performance liquid chromatography detector for nitrophenol compounds.

In this study, the potential application of surface-enhanced resonance Raman scattering (SERRS) spectroscopy as an off-line secondary detector for HPLC has been evaluated. Four nitrophenol compounds, 2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, and 4,6-dinitrocresol were separated by isocratic reverse-phase high-performance liquid chromatography (RP-HPLC) and monitored with a conventional UV detector. Resonance Raman (RR) and SERRS spectroscopy were next used to provide the required specificity for distinguishing the nitrophenol compounds. The SERRS detection limit for both 2-nitrophenol and 4-nitrophenol was calculated to be 14 ppb and that for 2,4-dinitrophenol and 4,6-dinitrocresol was estimated to lie near the parts-per-billion level as well. This detection limit is 2-3 orders of magnitude lower than that obtained by RR spectroscopy.

Chromatography, High Pressure Liquid↗
PubMed1989

Maserlike nonlinear scatter from human breath, a surface-enhanced far infrared scatter effect.

A cotton tip applicator was utilized to stimulate far IR scatter (emission) from human breath. The reticulated cotton tip was vibrated at 200 Hz, the acoustic frequency that matches the average vibration frequency of common species of mosquitoes. Mosquitoes have open resonator dielectric sensillae (spines) on their antenna that match the 643 cm-1 (15.5) Cabannes line in the 667 cm-1 region of CO2 rotation line, acoustic Stokes Brillouin and Stokes Raman lines are noted. Implications of such maserlike (coherent or partial coherent) scatter lines to insect control and disease diagnostics are discussed.

Animals↗