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A single platform, integrated by a laser-induced breakdown spectroscopy detector and a Raman spectroscopy sensor, has been designed to remotely (5 m) and simultaneously register the elemental and molecular signatures of rocks under Martian surface conditions. From this information, new data fusion architecture at decisions level is proposed for the correct categorization of the rocks. The approach is based on a decision-making process from the sequential checking of the spectral features representing the cationic and anionic counterparts of the specimen. The scrutiny of the LIBS response by using a moving-window algorithm informs on the diversity of the elemental constituents. The output rate of emission lines allows projecting in a loop the elements as the cationic counterpart of the rock. In parallel, the Raman response of the unknown is compared with all the molecular counterparts of the hypothesized cation that are stored in a spectral library. The largest similarity rate unveils the final identity of the unknown. The identification capabilities of the architecture have been underscored through blind tests of 10 natural rocks with different origins. The great majority of forecasts have matched with the real identities of the inspected targets. The strength of this platform to simultaneously acquire the multielemental and the molecular information from a specimen by using the same laser events greatly enhances the "on-surface" missions for the surveillance of mineralogy. [ABSTRACT FROM AUTHOR]

We present a high-throughput screening Raman spectroscopy (HTS-RS) platform for a rapid and label-free macromolecular fingerprinting of tens of thousands eukaryotic cells. The newly proposed label-free HTS-RS platform combines automated imaging microscopy with Raman spectroscopy to enable a rapid label-free screening of cells and can be applied to a large number of biomedical and clinical applications. The potential of the new approach is illustrated by two applications. (1) HTS-RS-based differential white blood cell count. A classification model was trained using Raman spectra of 52 218 lymphocytes, 48 220 neutrophils, and 7 294 monocytes from four volunteers. The model was applied to determine a WBC differential for two volunteers and three patients, producing comparable results between HTS-RS and machine counting. (2) HTS-RS-based identification of circulating tumor cells (CTCs) in 1:1, 1:9, and 1:99 mixtures of Panc1 cells and leukocytes yielded ratios of 55:45, 10:90, and 3:97, respectively. Because the newly developed HTS-RS platform can be transferred to many existing Raman devices in all laboratories, the proposed implementation will lead to a significant expansion of Raman spectroscopy as a standard tool in biomedical cell research and clinical diagnostics. [ABSTRACT FROM AUTHOR]

Electrochemical deposition of aromatic organic molecules by reduction of diazonium reagents enables formation of molecular layers with sufficient integrity for use in molecular electronic junctions of interest to microelectronics. Characterization of organic films with thicknesses in the 1-10 nm range is difficult with Raman spectroscopy, since most molecular structures of electronic interest have Raman cross sections which are too small to observe as either thin films on solid electrodes or within intact molecular junctions. Layer formation on a 10 nm thick Ag island film on a flat carbon surface (eC/Ag) permitted acquisition of structural information using surface enhanced Raman spectroscopy (SERS), in many cases for molecules with weak Raman scattering. Raman spectra obtained on eC/Ag surfaces were indistinguishable from those on carbon without Ag present, and the spectra of oligomeric molecular layers were completely consistent with those of the monomers. Layer growth was predominantly linear for cases where such growth was sterically allowed, and linear growth correlated strongly with the line width and splitting of the C?C phenyl ring stretches. Molecular bilayers made by successive reduction of different diazonium reagents were also observable and will be valuable for applications of 1-20 nm organic films in molecular electronics. [ABSTRACT FROM AUTHOR]

Polarization-resolved Raman spectroscopy provides much more information than its conventional counterpart. However, it usually either requires a complicated setup with two spectrographs and detectors or two measurements must be performed sequentially. This study presents a simple and straightforward approach to recording both polarization components simultaneously with a single spectrograph and detector. The vertically and a horizontally polarized laser beam exiting a Wollaston prism are focused into the sample with a small spatial separation. The scattered light from both beams is imaged onto the slit of an imaging spectrograph as two spatially separated signals, i.e., the polarized and the depolarized Raman signal. Eventually, both spectra are acquired on a single CCD chip simultaneously. Experimental data of ethanol and dimethyl sulfoxide are shown as proof-of-concept. The new method has a number of advantages, for example, laser intensity fluctuations and the polarization dependence of the diffraction grating do not play a role. The proposed approach will be useful for an improved structural analysis and it will be the enabling technology for temporally resolved enantioselective Raman (esR) spectroscopy. [ABSTRACT FROM AUTHOR]

Product identification is a critical and required analysis for biotheraputics. In addition to regulatory requirements for identity testing on final drug products, in-process identity testing is implemented to reduce business risks associated with fill operations and can also be used as a tool against counterfeiting. Biotherapeutics, in particular monoclonal antibodies, represent a challenging cohort for identity determination because of their similarity in chemical structure. Traditional methods used for product identification can be time and labor intensive, creating a need for quick, inexpensive and reliable methods of drug identification. Here, driven by its molecular-specific and nonperturbative nature, we present Raman spectroscopy as an alternate analytical tool for identity testing. By exploiting subtle differences in vibrational modes of the biologics, we have developed partial least-squares-discriminant analysis derived decision algorithms that offer excellent differentiation capability using spontaneous Raman spectra as well as label-free plasmon-enhanced Raman spectra. Coupled with the robustness to spurious correlations due to its high information content, our results highlight the potential of Raman spectroscopy as a powerful method for rapid, on-site biotherapeutic product identification. [ABSTRACT FROM AUTHOR]

Controlling the packing structure and revealing the intermolecular interaction of self-assembled monolayers (SAMs) on solid surfaces are crucial for manipulating its properties. We utilized tip-enhanced Raman spectroscopy (TERS) to address the challenge in probing the subtle change of the intermolecular interaction during the assembly of a pyridine-terminated aromatic thiol on the single crystal Au (lll) surface that cannot produce enhanced Raman signal, together with electrochemical methods to study the charge transfer properties of SAM. We observed that the aromatic C = C bond stretching vibration can be a marker to monitor the strength of the intermolecular interaction of SAMs, because this Raman peak is very sensitive to the intermolecular π-π stacking. Our results indicate that the SAM experiences a surface restructuring after the formation of a densely packed monolayer. We propose that the intermolecular electrostatic repulsion governs the restructuring when the packing density is high. The correlated TERS and electrochemical studies also suggest that the intermolecular interaction may have some impact on the charge transfer properties of SAM. This study provides a molecular-level insight into understanding and exploiting the intermolecular interactions toward better control over the assembling process and tuning the electrical properties of aromatic thiols. [ABSTRACT FROM AUTHOR]

Here we describe enhanced Raman scattering at Au electrode 1 (E1)/Ag nanowire (NW)/4-aminothiophenol (4- ATP)/Au electrode 2 (E2) nanojunctions fabricated by combining self-assembly and metal electrodeposition at microgap electrodes (E1 and E2). In this method we assemble the 4-ATP on electrode E2 and electrodeposit Ag on the opposite electrode El of an Au interdigitated array (IDA) electrode device. The electrodeposited Ag grows in the form of NWs on E1 and makes nanoscale contact to E2 to form the junctions. The presence of the Ag NW leads to strong Raman scattering of the 4-ATP molecules within the nanojunction leading to estimated enhancement factors ranging from 103 to 106. Scanning electron microscopy (SEM) images provide insight into the morphology of the junctions. The magnitude of the Raman enhancement depends on the extent of contact between the Ag NW and the 4-ATP self-assembled monolayer (SAM). With this approach we could detect 4-ATP molecules diluted by a factor of 1000 with hexanethiol molecules within the junctions. Our approach is simple and fast with the potential to correlate electronic measurements of molecules with Raman spectroscopy data of the same molecules in a nanoscale junction for molecular electronics or chemiresistive sensing applications. [ABSTRACT FROM AUTHOR]

The first use of surface enhanced Raman spectroscopy (SERS) to detect trace organic and/or inorganic species in ambient atmospheric aerosol particles is presented. This new analytical method provides direct, spectroscopic detection of species present at attogram to femtogram levels in individual submicrometer atmospheric particles. An array of spectral features resulting from organic functional groups in secondary organic aerosol (SOA) material were observed in individual particles impacted on silver nanoparticle-coated substrates. The results demonstrate the complexity of organic and inorganic species in SOA formed by oxidation of biogenic volatile organic compounds (BVOCs) at the single particle level. While SOA composition is frequently assumed to be homogeneous between and within individual particles, substantial particle-to-particle variability in SOA composition and changes on scales <1 μm were observed. The observations obtained with this new method demonstrate the power of SERS to probe difficult to detect inter- and intraparticle variability in ambient SOA particles. [ABSTRACT FROM AUTHOR]

The dynamic properties of phospholipid (PL) membranes (phase state and phase transition) play crucial roles in biological systems. However, highly sensitive, direct analytical methods that shed light on the nature of lipids and their assemblies have not been developed to date. Here, we describe the analysis of PL-modified Au nanoparticles (Au@PL) using membrane surface-enhanced Raman spectroscopy (MSERS) and report the properties of the self-assembled PL membranes on the Au nanoparticle. The Raman intensity per PL concentration increased by 50-170 times with Au@PL, as compared to large unilamellar vesicles (LUVs) at the same PL concentration. The phase state and phase transition temperature of the PL membrane of Au@PL were investigated by analyzing the Raman peak ratio (R = I2882/I2930). The enhancement at 714 cm-1 (EF(714)) varied with the hydrocarbon chain length of the PLs and the assembled degree of Au@PLs. In calculation, the EF(714),assembled was estimated to be 111-142 when the distance between AuNPs was 7.0-7.5 nm, which was correlated to the speculative enhancement factor, suggesting that the assembly of the Au@PLs contributed to the MSERS. [ABSTRACT FROM AUTHOR]

A new, novel, rapid method to detect and direct readout of drugs in human urine has been developed using dynamic surface-enhanced Raman spectroscopy (D-SERS) with portable Raman spectrometer on gold nanorods (GNRs) and a classification algorithm called support vector machines (SVM). The high-performance GNRs can generate gigantic enhancement and the SERS signals obtained using D-SERS on it have high reproducibility. On the basis of this feature of DSERS, we have obtained SERS spectra of urine and urine containing methamphetamine (MAMP). SVM model was built using these data for fast identified and visual results. This general method was successfully applied to the detection of 3, 4-methylenedioxy methamphetamine (MDMA) in human urine. To verify the accuracy of the model, drug addicts' urine containing MAMP were detected and identified correctly and rapidly with accuracy more than 90%. The detection results were displayed direcdy without analysis of their SERS spectra manually. Compared with the conventional method in lab, the method only needs a 2 pL sample volume and takes no more than 2 min on the portable Raman spectrometer. It is anticipated that this method will enable rapid, convenient detection of drugs on site for the police. [ABSTRACT FROM AUTHOR]

Hair is one of the most common types of physical evidence found at a crime scene. Forensic examination may suggest a connection between a suspect and a crime scene or victim, or it may demonstrate an absence of such associations. Therefore, forensic analysis of hair evidence is invaluable to criminal investigations. Current hair forensic examinations are primarily based on a subjective microscopic comparison of hair found at the crime scene with a sample of suspect's hair. Since this is often inconclusive, the development of alternative and more-accurate hair analysis techniques is critical. In this study, we utilized surface-enhanced Raman spectroscopy (SERS) to demonstrate that artificial dyes can be directly detected on hair. This spectroscopic technique is capable of a confirmatory identification of analytes with single molecule resolution, requires minimal sample, and has the advantage of fluorescence quenching. Our study reveals that SERS can (1) identify whether hair was artificially dyed or not, (2) determine if a permanent or semipermanent colorants were used, and (3) distinguish the commercial brands that are utilized to dye hair. Such analysis is rapid, minimally destructive, and can be performed directly at the crime scene. This study provides a novel perspective of forensic investigations of hair evidence. [ABSTRACT FROM AUTHOR]

Although surface-enhanced Raman spectroscopy (SERS) has been featured by high sensitivity, additional signal enhancement is still necessary for trace amount of biomolecules detection. In this paper, a SERS amplified approach, featuring "ions-mediated cascade amplification (IMCA)", was proposed by utilizing the dissolved silver ions (Ag+) from silver nanoparticles (AgNPs). We found that using Ag+ as linkage agent can effectively control the gaps between neighboring 4-aminobenzenethiol (4-ABT) encoded gold nanoparticles (AuNPs@4-ABT) toform "hot spots" and thus produce SERS signal output, in which the SERS intensity was proportional to the concentration of Ag+. Inspired by this finding, the IMCA was utilized for ultrasensitive detection of single nucleotide polymorphism in human mitochondrial DNA (16189T → C). Combining with the DNA ligase reaction, each target DNA binding event could successfully cause one AgNP introduction. By detecting the dissolved Ag+ from AgNPs using IMCA, low to 3.0 × 10(-5) fm/μL targeted DNA can be detected, which corresponds to extractions from 200 nL cell suspension containing carcinoma pancreatic β-cell lines from diabetes patients. This IMCA approach is expected to be a universal strategy for ultrasensitive detection of analytes and supply valuable information for biomedical research and clinical early diagnosis. [ABSTRACT FROM AUTHOR]

Interesting properties of water with distinguishable hydrogen-bonding structure on interfacial phase or in confined environment have drawn wide attentions. However, these unique properties of water are only found within the interfacial phase and confined environment, thus, their applications are limited. In addition, quantitative evaluation on these unique properties associating with the enhancement of water's physical and chemical activities represents a notable challenge. Here we report a practicable production of free-standing liquid water at room temperature with weak hydrogen-bonded structure naming Au nanoparticles (NPs)-treated (AuNT) water via treating by plasmon-induced hot electron transfer occurred on resonantly illuminated gold NPs (AuNPs). Compared to well-known untreated bulk water (deionized water), the prepared AuNT water exhibits many distinct activities in generally physical and chemical reactions, such as high solubilities to NaCl and O2. Also, reducing interaction energy within water molecules provides lower overpotential and higher efficiency in electrolytic hydrogen production. In addition, these enhanced catalytic activities of AuNT water are tunable by mixing with deionized water. Also, most of these tunable activities are linearly proportional to its degree of nonhydrogen-bonded structure (DNHBS), which is derived from the O-H stretching in deconvoluted Raman spectrum. [ABSTRACT FROM AUTHOR]

Surface-enhanced Raman spectroscopy (SERS) is generally performed on planar surfaces, which can be difficult to prepare and may limit the interaction of the sensing surface with targets in large volume samples. We propose that nanocomposite materials can be configured that both include SERS probes and provide a high surface area-to-volume format, i.e., fibers. Thiol-yne nanocomposite films and fibers were fabricated using exposure to long-wave ultraviolet light after the inclusion of gold nanoparticles (AuNPs) functionalized with thiophenol. A SERS response was observed that was proportional to the aggregation of the AuNPs within the polymers and the amount of thiophenol present. Overall, this proof-of-concept fabrication of SERS active polymers indicated that thiol-yne nanocomposites may be useful as durable film or fiber SERS probes. Properties of the nanocomposites were evaluated using various techniques including UV-vis spectroscopy, μ-Raman spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, therm ogravimetric analysis, and transmission electron microscopy. [ABSTRACT FROM AUTHOR]