Detection Of Organic Molecules Research Articles

Susceptible Detection of Organic Molecules Based on C3B/Graphene and C3N/Graphene van der Waals Heterojunction Gas Sensors.

Constructing van der Waals (vdW) heterostructures is a prospective approach that is essential for developing a new generation of functional two-dimensional (2D) materials and designing new conceptual nanodevices. Using density-functional theory combined with a nonequilibrium Green's function approach allows for the theoretical and systematic exploration of the electronic structure, transport properties, and sensitivity of organic small molecules adsorbed on 2D C3B/graphene (Gra) and C3N/Gra vdW heterojunctions. Calculations show the metallic properties of C3B/Gra and C3N/Gra after the formation of heterojunctions. Interestingly, the heterojunctions C3B/Gra (C3N/Gra) for the adsorption of small organic molecules (C2H2, C2H4, CH3OH, CH4, and HCHO) at the C3B (C3N) side are sensitive to the chemisorption of C2H2 and C2H4. Similarly, the Gra/C3B is chemisorbed for both C2H2 and C2H4 when adsorbed on Gra side, while it is only chemisorbed for C2H2 in Gra/C3N. Interestingly, all heterojunctions on different sides are physisorbed for CH3OH, CH4, and HCHO. Furthermore, the calculated I-V curves demonstrate that the devices based on the adsorption of C2H2 and C2H4 at each side of the heterojunction have remarkable anisotropy, in with the current being considerably greater in the zigzag direction than in the armchair direction. More specifically, with C2H2 adsorbed on the Gra side, the sensitivity along the armchair direction is up to 85.0% for Gra/C3B and close to 100% for Gra/C3N. This study reveals that C3B/Gra (C3N/Gra) heterojunctions with high selectivity, high anisotropy, and excellent sensitivity are highly prospective 2D materials for applications, which further contributes new insights into the development of future electronic nanodevices.

Epitaxial Growth of Monolayer WS2 Single Crystals on Au(111) Toward Direct Surface-Enhanced Raman Spectroscopy Detection.

The epitaxial growth of wafer-scale two-dimensional (2D) semiconducting transition metal dichalcogenides (STMDCs) single crystals is the key premise for their applications in next-generation electronics. Despite significant advancements, some fundamental factors affecting the epitaxy growth have not been fully uncovered, e.g., interface coupling strength, adlayer-substrate lattice matching, substrate step-edge-guiding effects, etc. Herein, we develop a model system to tackle these issues concurrently, and realize the epitaxial growth of wafer-scale monolayer tungsten disulfide (WS2) single crystals on the Au(111) substrate. This epitaxial system is featured with good adlayer-substrate lattice matching, obvious step-edge-guiding effect for the unidirectionally aligned nucleation/growth, and relatively weaker interfacial interaction than that of monolayer MoS2/Au(111), as evidenced by the evolution of a uniform Moiré pattern and an intrinsic band gap, according to on-site scanning tunneling microscopy/spectroscopy (STM/STS) characterizations and density functional theory calculations. Intriguingly, the unidirectionally aligned monolayer WS2 domains along the Au(111) steps can behave as ultrasensitive templates for surface-enhanced Raman scattering detection of organic molecules, due to the obvious charge transfer occurred at substrate step edges. This work should hereby deepen our understanding of the epitaxy mechanism of 2D STMDCs on single-crystal substrates, and propel their wafer-scale production and applications in various cutting-edge fields.

Photo-Thermal Conversion and Raman Sensing Properties of Three-Dimensional Gold Nanostructure

Three-dimensional plasma nanostructures with high light–thermal conversion efficiency show the prospect of industrialization in various fields and have become a research hotspot in areas of light–heat utilization, solar energy capture, and so on. In this paper, a simple chemical synthesis method is proposed to prepare gold nanoparticles, and the electrophoretic deposition method is used to assemble large-area three-dimensional gold nanostructures (3D-GNSs). The light–thermal water evaporation monitoring and surface-enhanced Raman scattering (SERS) measurements of 3D-GNSs were performed via theoretical simulation and experiments. We reveal the physical processes of local electric field optical enhancement and the light–thermal conversion of 3D-GNSs. The results show that with the help of the efficient optical trapping and super-hydrophilic surface properties of 3D-GNSs, they have a significant effect in accelerating water evaporation, which was increased by nearly eight times. At the same time, the three-dimensional SERS substrates based on gold nanosphere particles (GNSPs) and gold nanostar particles (GNSTs) had limited sensitivities of 10−10 M and 10−12 M to R6G molecules, respectively. Therefore, 3D-GNSs show strong competitiveness in the fields of solar-energy-induced water purification and the Raman trace detection of organic molecules.

Why Is Surface-Enhanced Raman Scattering Insensitive to Liquid Water?

Surface-enhanced Raman scattering (SERS) is widely recognized as a remarkably powerful analytical technique that enables trace-level detection of organic molecules on a metal surface in aqueous systems with negligible spectral interference of water. This insensitivity of SERS to liquid water is violated in a restrictive manner under specific electrochemical conditions. However, the origin of such different SERS sensitivities to liquid water remains unclear. Here, we show that hydrogen-bond networks of water play a pivotal role in losing SERS enhancement for liquid water, and SERS detection of water requires local defects in the hydrogen-bond networks, which are formed around hydration shells of solute ions or on a polarized electrode surface. This work gives a new perspective on in situ SERS investigations in aqueous systems, including electrochemical and biological reactions.

Hybrid SERS substrate based on cotton swab for sensitive detection of organic molecules

For the last two decades, the development of substrates for Surface Enhanced Raman Spectroscopy (SERS) has been continuously pushed for better performances. In this research, we designed SERS substrates with better detection capability and more efficient sample collection. In particular, morphology-controlled Ag nanoparticles were deposited onto cotton swab (cotton Q-tip), followed by a thin cover layer of graphene oxide by the dip-coating method. The graphene oxide overlay was expected to not only protect Ag nanoparticles from degradation by the environment but also contribute to sample adsorption and signal enhancement. To demonstrate the performance of the SERS substrates, different concentrations of Rhodamine B as low as 10–10 M were successfully detected and the enhancement factors were estimated to be 3 × 1010–5 × 1010. It is our expectation that these cotton swab-based substrates will contribute to our ongoing efforts toward low-cost, high-efficiency and durable SERS substrate.

Murchison Meteorite Analysis Using Tetramethylammonium Hydroxide (TMAH) Thermochemolysis Under Simulated Sample Analysis at Mars (SAM) Pyrolysis‐Gas Chromatography‐Mass Spectrometry Conditions

AbstractThe Sample Analysis at Mars (SAM) instrument aboard the Curiosity Rover at Gale crater can characterize organic molecules from scooped and drilled samples via pyrolysis of solid materials. In addition, SAM can conduct wet chemistry experiments which enhance the detection of organic molecules bound in macromolecules and convert polar organic compounds into volatile derivatives amenable to gas chromatography‐mass spectrometry analyses. Specifically, N‐tert‐butyldimethylsilyl‐N‐methyltrifluoroacetamide (MTBSTFA) is a silylation reagent whereas tetramethylammonium hydroxide (TMAH) is a thermochemolysis methylation reagent. Shortly after arriving at Mars, the SAM team discovered that at least one of the MTBSFTA cups was leaking, contributing to a continuous background inside SAM with the potential to interfere with future TMAH reactions. Therefore, here we characterized possible interactions between the two reagents to determine byproducts and implications for the detection of indigenous organics. SAM‐like pyrolysis experiments supplemented with flash pyrolysis were accordingly conducted with fragments of the Murchison meteorite as a reference for exogenous organic matter delivered to Mars. Flash TMAH experiments yielded various aromatic acids, dicarboxylic acids, and amino acids while SAM‐like pyrolysis presented mixtures of methylated and non‐methylated compounds due to decreased reaction efficiency at slower ramp rates. All experiments in the presence of simulated MTBSTFA vapor produced pervasive silylated byproducts which co‐elute and obscure the identification of Murchison‐derived compounds. Despite challenges, a significant diversity of pyrolyzates and TMAH derivatives could still be identified in flash pyrolysis in presence of MTBSTFA. However SAM‐like experiments with TMAH and MTBSTFA are hindered by both decreased methylation yields and additional co‐eluting compounds.

Seed-assisted electrodeposition of multilayer Au nanoparticles-assembled films for sensitive surface-enhanced Raman scattering detection

Surface-enhanced Raman scattering (SERS) spectroscopy can be used to realize sensitive rapid detection of molecules. Three-dimensional (3D) SERS substrates can provide more hotspots within the excitation laser beam when compared with the corresponding two-dimensional (2D) SERS substrates. Most of the methods for fabrication of 3D SERS substrates involve complex processes. Therefore, it is significant to develop a simple and effective method for fabrication of 3D SERS substrates. Here, a seed-assisted electrodeposition approach is developed for fabrication of a 3D SERS substrate composed of multilayer Au nanoparticles. Interestingly, it is demonstrated that a uniform film composed of multilayer Au nanoparticles that can serve as a 3D SERS substrate can be achieved directly by one-step electrodeposition on a conductive surface coated with monolayer Au seeds. It is found that a diffusion-controlled growth during electrodeposition narrows the nanoparticle size distribution and results monosized Au nanoparticles. The as-prepared multilayer Au nanoparticles-assembled film shows high SERS sensitivity and good spectral uniformity. For SERS detection of rhodamine 6G, a limit of detection as low as 3.4×10−12 M has been achieved. Moreover, good spectral uniformity (relative standard deviation ∼7.8%) and high substrate-to-substrate reproducibility (relative standard deviation ∼8.6%) have also been demonstrated. The as-prepared multilayer Au nanoparticles-assembled film is used to detect organic pollutants such as dye molecule crystal violet (CV) and methylene blue (MB). Calibration curves with a linear correlation between the logarithmic SERS intensity and logarithmic concentration of CV and MB have been obtained. Limit of detections for CV and MB are 1.2×10−8 M and 9.8×10−10 M, respectively. Therefore, the fabricated 3D SERS substrate has good application prospects in sensitive detection of organic molecules.

Influence of pH and salts on DMF-DMA derivatization for future Space Applications

For gas chromatography - mass spectrometry (GC-MS) analyses performed in situ, pH and salts (e.g., chlorides, sulfates) may enhance or inhibit the detection of targeted molecules of interest for astrobiology (e.g. amino acids, fatty acids, nucleobases). Obviously, salts influence the ionic strength of the solutions, the pH value, and the salting effect. But the presence of salts may also produce complexes or mask ions in the sample (masking effect on hydroxide ion, ammonia, etc.). For future space missions, wet chemistry will be conducted before GC-MS analyses to detect the full organic content of a sample. The defined organic targets for space GC-MS instrument requirements are generally strongly polar or refractory organic compounds, such as amino acids playing a role in the protein production and metabolism regulations for life on Earth, nucleobases essential for DNA and RNA formation and mutation, and fatty acids that composed most of the eukaryote and prokaryote membranes on Earth and resist to environmental stress long enough to still be observed on Mars or ocean worlds in geological well-preserved records. The wet-chemistry chemical treatment consists of reacting an organic reagent with the sample to extract and volatilize polar or refractory organic molecules (i.e. dimethylformamide dimethyl acetal (DMF-DMA) in this study). DMF-DMA derivatizes functional groups with labile H in organics, without modifying their chiral conformation. The influence of pH and salt concentration of extraterrestrial materials on the DMF-DMA derivatization remains understudied. In this research, we studied the influence of different salts and pHs on the derivatization of organic molecules of astrobiological interest with DMF-DMA, such as amino acids, carboxylic acids, and nucleobases. Results show that salts and pH influence the derivatization yield, and that their effect depend on the nature of the organics and the salts studied. Second, monovalent salts lead to a higher or similar organic recovery compared to divalent salts regardless of pH below 8. However, a pH above 8 inhibits the DMF-DMA derivatization influencing the carboxylic acid function to become an anionic group without labile H. Overall, considering the negative effect of the salts on the detection of organic molecules, future space missions may have to consider a desalting step prior to derivatization and GC-MS analyses.

First principal study of interaction of copper doped gold nanoclusters with glycine

Gold nanoclusters and bimetallic gold nanoclusters are interesting areas of research. These nanoclusters are used for the detection of organic molecules, cancer treatment, bio-imaging, drug delivery etc. In this paper, we studied the interaction of copper doped Au nanoclusters of five, eight, thirteen, fifteen, and eighteen atoms with glycine amino acid. Their HOMO-LUMO gap, adsorption energy, non-covalent interaction, hardness, electrophilicity index, electrochemical potential, and UV-Visible spectra were analyzed. The maximum adsorption energy is found in the nanoclusters Au4Cug(A,B) and Au12Cug(C). Additionally, strong non-covalent interaction is observed in the Au4Cug(A,B) and Au12Cug(B) nanoclusters, which makes them suitable for applications like drug delivery, biosensing etc. These nanoclusters are also more stable compared to other nanoclusters in this work (only exception Au7Cu(A,B,C)) owing to their large HOMO-LUMO gap and symmetric structure.

JWST/MIRI Spectroscopy of the Disk of the Young Eruptive Star EX Lup in Quiescence

EX Lup is a low-mass pre-main-sequence star that occasionally shows accretion-related outbursts. Here, we present JWST/MIRI medium-resolution spectroscopy obtained for EX Lup 14 yr after its powerful outburst. EX Lup is now in quiescence and displays a Class II spectrum. We detect a forest of emission lines from molecules previously identified in infrared spectra of classical T Tauri disks: H2O, OH, H2, HCN, C2H2, and CO2. The detection of organic molecules demonstrates that they are back after disappearing during the large outburst. Spectral lines from water and OH are for the first time deblended and will provide a much-improved characterization of their distribution and density in the inner disk. The spectrum also shows broad emission bands from warm, submicron-size amorphous silicate grains at 10 and 18 μm. During the outburst, in 2008, crystalline forsterite grains were annealed in the inner disk within 1 au, but their spectral signatures in the 10 μm silicate band later disappeared. With JWST we rediscovered these crystals via their 19.0, 20.0, and 23.5 μm emission, the strength of which implies that the particles are at ∼3 au from the star. This suggests that crystalline grains formed in 2008 were transported outwards and now approach the water snowline, where they may be incorporated into planetesimals. Containing several key tracers of planetesimal and planet formation, EX Lup is an ideal laboratory to study the effects of variable luminosity on the planet-forming material and may provide an explanation for the observed high crystalline fraction in solar system comets.

Comparison of tetramethylammonium hydroxide (TMAH), trimethylsulfonium hydroxide (TMSH), and trimethylphenylammonium hydroxide (TMPAH) thermochemolysis for in situ space analysis of organic molecules in planetary environments

One of the main objectives of present and future space exploration missions dedicated to astrobiology is the detection of organic molecules of interest for life (e.g. amino and fatty acids). With this aim, a sample preparation and a gas chromatograph (connected to a mass spectrometer) are generally used. To date, tetramethylammonium hydroxide (TMAH) has been the first and only thermochemolysis reagent to be used for in situ sample preparation and chemical analysis of planetary environments. Although TMAH is widely used in terrestrial laboratories, numerous applications also leverage other thermochemolysis reagents that may be more relevant than TMAH to meet both scientific and technical objectives of space instrumentation. The present study compares the performance of tetramethylammonium hydroxide (TMAH), trimethylsulfonium hydroxide (TMSH), and trimethylphenylammonium hydroxide (TMPAH) reagents on molecules of interest to astrobiology. The study focuses on the analyses of 13 carboxylic acids (C7–C30), 17 proteinic amino acids, and the 5 nucleobases. Here we report the derivatization yield without stirring or adding solvents, the detection sensitivity with mass spectrometry, and the nature of the degradation products from the reagents produced during pyrolysis. We conclude that TMSH and TMAH are the best reagents for analyzing carboxylic acids and nucleobases. Amino acids are not relevant targets for a thermochemolysis over 300 °C as they are degraded and showed high limits of detection. As TMAH, and probably TMSH, meet the space instrumentation requirements, this study informs sample treatment approaches prior to GC-MS analysis in in situ space studies. The thermochemolysis reaction using TMAH or TMSH is also recommended for space return missions to extract organics from a macromolecular matrix, derivatize polar or refractory organic targets, and volatilize with the fewest organic degradations.

The photochemical evolution of polycyclic aromatic hydrocarbons and nontronite clay on early Earth and Mars

The photochemical evolution of polycyclic aromatic hydrocarbons (PAHs), an abundant form of meteoritic organic carbon, is of great interest to early Earth and Mars origin-of-life studies and current organic molecule detection efforts on Mars. Fe-rich clay environments were abundant on early Earth and Mars, and may have played a role in prebiotic chemistry, catalyzing the breakdown of PAHs and freeing up carbon for subsequent chemical complexification. Current Mars is abundant in clay-rich environments, which are most promising for harboring organic molecules and have comprised the main studied features by the Curiosity rover in search of them. In this work we studied the photocatalytic effects of the Fe-rich clay nontronite on adsorbed PAHs. We tested the effect of ultraviolet radiation on pyrene, fluoranthene, perylene, triphenylene, and coronene adsorbed to nontronite using the spike technique, and in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in a Mars simulation chamber. We studied the infrared vibrational PAH bands with first order reaction kinetics and observed an extensive decrease of bands of pyrene, fluoranthene, and perylene, accompanied by the formation of PAH cations, while triphenylene and coronene remained preserved. We further analyzed our irradiated samples with nuclear magnetic resonance (NMR). Our study showed certain PAHs to be degraded via the (photo)Fenton mechanism, even under a dry, hypoxic atmosphere. Using solar spectra representative of early Earth, early Mars, and current Mars surface illumination up to 400 nm, the processes occurring in our set up are indicative of the UV-induced photochemistry taking place in Fe-rich clay environments on early Earth and Mars.

Analytical capabilities of a thermodesorption spectrometer with a surface-ionization detection of organic molecules in air

This paper presents the results of research on the development of a mathematical model of thermal desorption spectrometry with a surface ionization method for detecting molecules of organic substances, as well as an analysis of the capabilities of a thermal desorption spectrometer operating on the basis of this method. The mathematical model of the method was developed on the basis of the regularities of thermal desorption spectrometry, as well as the regularities of surface ionization of molecules of organic substances under non-stationary conditions. The spectrometer consists of a surface ionization detector and an evaporator of substances heated in a thermally programmed mode. The adjustment and selection of the operating mode of the spectrometer were carried out on the basis of the mathematical model of the method. The analytical capabilities of the spectrometer were studied by comparing the thermodesorption spectra of a mixture of chromatographically pure cannabinoids and an extract of the biological fluids of a marijuana user (blood, urine), as well as the spectra of chromatographically pure morphine and urine extracts of a heroin user. The results of the analysis showed the perspectives of the proposed method and instrument for the detection and analysis of drugs and psychotropic drugs in extracts of biomaterials of consumers of these substances without chromatographic separation. Keywords: biosamples of drug users, mathematical model of the method, thermal desorption spectrum, identification and quantitative analysis.

Multifold Enhanced Raman Detection of Organic Molecules as Environmental Water Pollutants

Organic molecules, including the benzene series, have been identified as pollutants in environmental water. Due to their very low solubility, they have very small concentrations in water, and they are difficult to be detected by conventional techniques. In particular, there is a lack of real-time, accurate, and rapid detection methods for such molecules in water. However, they are detrimental to human health in many aspects. Toluene has been an important indicator of such environmental pollution detections. In this work, we propose a 3D SERS scheme consisting of a hollow fiber that is coated on the inner wall with densely arranged silver nanoparticles, which supplies multifold Raman enhancement by the plasmonic microcavity. Strong confinement of excitation laser energy and strongly enhanced Raman signals with the bidirectional collection are utilized to achieve high-sensitivity detection of toluene molecules in water. Raman signal with a reasonable signal-to-noise ratio has been measured for a concentration of 0.53 mg/L, indicating a detection limit even lower than this value for such a Raman spectroscopic technique. The corresponding enhancement factor is higher than 6 × 103 with respect to the available systems. Thus, this device not only enables direct trace detection and real-time monitoring of the water-polluting status by organic molecules but also supplies a practical approach for biological sensing.

Nanoporous Ag-Decorated Ag7O8NO3 Micro-Pyramids for Sensitive Surface-Enhanced Raman Scattering Detection

Porous noble metal nanomaterials can be employed to construct sensitive surface-enhanced Raman scattering (SERS) substrates, because the plasmonic nanopores and nanogaps of the porous materials can provide a larger number of hotspots, and can also serve as containers of analyte molecules. However, the fabrication processes of nanoporous noble metal are generally complicated. Here, a facile method is presented to prepare nanoporous Ag nanoparticles-decorated Ag7O8NO3 micro-pyramids, which are fabricated through the chemical reduction of the electrodeposited Ag7O8NO3 micro-pyramids using NaBH4. The Ag7O8NO3 micro-pyramids are fabricated by electrodeposition by using a simple aqueous solution of AgNO3 as electrolyte. Then, porous Ag-decorated Ag7O8NO3 micro-pyramids are achieved by the chemical reduction of the surface of the electrodeposited Ag7O8NO3 micro-pyramids with NaBH4. The high-density nanopores and nanogaps of the fabricated nanoporous Ag can provide plenty of hot spots for Raman enhancement. Additionally, the nanopores have an effective capacity to trap and enrich analytes. Using rhodamine 6G (R6G) as a probe molecule, the SERS performance of the fabricated SERS substrate has been investigated. It is found that a limit of detection (LOD) ~1.0 × 10−15 M can be achieved for R6G. Then, the SERS substrates are employed to detect dye molecule (crystal violet) and pesticide (thiram), and their LODs are calculated down to 9.6 × 10−13 M and 1.3 × 10−15 M, respectively. The enhancement factor of the fabricated SERS substrate is estimated to be as high as 5.6 × 108. Therefore, the nanoporous Ag-decorated Ag7O8NO3 micro-pyramids have shown promising application in the sensitive SERS detection of organic molecules.

Plasmon Coupling and Efficient Charge Transfer in Rough-Surfaced Au Nanotriangles/MXene Hybrids as an Ultrasensitive Surface-Enhanced Raman Scattering Platform.

The rational design of Raman substrate materials with prominent electromagnetic enhancement and charge transfer is quite important for surface-enhanced Raman scattering (SERS). Herein, an efficient SERS substrate based on two-dimensional ultrathin Ti3C2T x MXene and rough-surfaced Au nanotriangles (NTs) was successfully prepared for efficient detection of organic molecules due to the synthetic effect of an optimized electromagnetic field and charge transfer. Uniform Au NTs with tunable surface roughness were controllably prepared by selectively depositing of Au on the smooth Au NTs. Due to the large surface area, tunable plasmon resonance, and abundant hotspots on the planar surface, the modified Au NTs showed much better SERS performance than initial Au NTs. By combination of the rough-surfaced Au NTs with MXene, the Ti3C2T x /Au NT hybrids exhibited much better SERS performance than initial Au NTs and Au NTs with a rough surface. The detection limit is down to 10-12 M, and the analytical enhancement factors reach 3.6 × 109 (at 1174 cm-1) on detecting crystal violet excited at 785 nm. This is because the strong plasmon coupling between the in-plane resonance of Au NTs and transversal plasmon resonance of Ti3C2T x MXene around 785 nm can generate an intense interfacial electromagnetic field for amplifying SERS signals. Additionally, the efficient charge transfer between Au NTs, MXene, and molecules also plays an important role in enhancing the SERS performance. This work presents a new insight to develop high-performance SERS substrates based on plasmon.

Surface Functionalization with Polymer Membrane or SEIRA Interface to Improve the Sensitivity of Chalcogenide-Based Infrared Sensors Dedicated to the Detection of Organic Molecules.

Priority substances likely to pollute water can be characterized by mid-infrared spectroscopy based on their specific absorption spectral signature. In this work, the detection of volatile aromatic molecules in the aqueous phase by evanescent-wave spectroscopy has been optimized to improve the detection efficiency of future in situ optical sensors based on chalcogenide waveguides. To this end, a hydrophobic polymer was deposited on the surface of a zinc selenide prism using drop and spin-coating methods. To ensure that the water absorption bands will be properly attenuated for the selenide waveguides, two polymers were selected and compared: polyisobutylene and ethylene/propylene copolymer coating. The system was tested with benzene, toluene, and ortho-, meta-, and para-xylenes at concentrations ranging from 10 ppb to 40 ppm, and the measured detection limit was determined to be equal to 250 ppb under these analytical conditions using ATR-FTIR. The polyisobutylene membrane is promising for pollutant detection in real waters due to the reproducibility of its deposition on selenide materials, the ease of regeneration, the short response time, and the low ppb detection limit, which could be achieved with the infrared photonic microsensor based on chalcogenide materials. To improve the sensitivity of future infrared microsensors, the use of metallic nanostructures on the surface of chalcogenide waveguides appears to be a relevant way, thanks to the plasmon resonance phenomena. Thus, in addition to preliminary surface-enhanced infrared absorption tests using these materials and a functionalization via a self-assembled monolayer of 4-nitrothiophenol, heterostructures combining gold nanoparticles/chalcogenide waveguides have been successfully fabricated with the aim of proposing a SEIRA microsensor device.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Silver cluster interactions with Pterin: Complex structure, binding energies and spectroscopy

Metal nanoclusters (NCs) are widely present today in biosensing, bioimaging, and diagnostics due to their small size, great biocompatibility, and sensitivity to the biomolecular environment. Silver (Ag) NCs often possess intense fluorescence, photostability, and low photobleaching, which is in high demand during the detection of organic molecules. Pterins are small compounds, which are used in medicine as biomarkers of oxidative stress, cardiovascular diseases, neurotransmitter synthesis, inflammation and immune system activation. It is experimentally possible to detect pterin (Ptr) through the adsorption on Ag colloid. We optimized geometries and evaluated the binding energy in Ptr-Agnq complexes (n = 1–6; q = 0, +1, +2) using quantum chemistry methods. Different Ptr atoms were preferential for silver attachment depending on NC charge and size. The highest Eb was obtained for the complexes between the Ptr0 and Ag32+ (-50.8 kcal mol−1), between Ptr-1 and Ag32+ (-64.8 kcal mol−1), which means that these complexes should be formed preferably in aqueous solutions in acidic and alkaline media, respectively. The colorimetric detection of pterin with silver clusters does not seem to be promising. However, intense S0→S1 transitions of Ag5+ complexes look promising for luminescent Ptr detection. SERS detection of pterin is better to be done at pH > 8 since deprotonated pterin Raman undergo more dramatic changes upon addition of Ag than the neutral pterin. The characteristics of absorption and vibrational spectra of silver-pterin should be exploited during biosensor development.

Nanosers devices based on Au-studded ZnO nanorod for R6G detection

Introduction: The prospect of wielding semiconductor–noble metal hybrid nanomaterials as surface-enhanced Raman scattering (SERS) substrates for the ultrasensitive detection of organic molecules in sensing applications has attracted ever-increasing attention. In this study, nanoSERS devices based on Au-studded ZnO nanorods (Au/ZnO) were fabricated using a facile photochemical deposition method for the detection of low-concentration rhodamine 6G (R6G) molecules. Methods: Analytical techniques such as SEM, EDX, XRD, and UV‒Vis spectroscopy were utilized to investigate the morphology, elemental composition, crystalline structure, and optical absorption of the Au/ZnO nanostructure, respectively. Raman scattering spectroscopy was used to evaluate rhodamine 6G. Results: The results show that vertically well-aligned ZnO nanorods (NRs) were effectively grown on the seeded glass substrate at 90°C for 4 h, and Au nanoparticles (NPs) with a diameter of approximately 20 nm were successfully deposited onto their surface. Comparing the obtained Au/ZnO substrate to the ZnO NRs and glass substrates, it exhibited superior SERS performance with R6G at a low concentration of 10-3 M. Significantly, it was found that the Au/ZnO for the R6G sensitive limit was approximately 10-9 M. This could be explained due to the surface plasmon resonance (SPR)-induced electromagnetic field enhancement of Au NPs as well as the charge-transfer mechanism between the Au/ZnO substrate and adsorbed R6G molecules under 532 nm laser excitation. Conclusion: This work demonstrates the potential SERS activity of Au/ZnO substrates, which can identify organic substances at trace levels using the Raman analysis method.