Structural-modulated substrate of MXene for surface-enhanced Raman scattering sensing.

The distinctive structure of MXene offers exceptional electron transport properties, abundant surface chemistry, and robust mechanical attributes, thereby bestowing it with remarkable advantages and promising prospects in the realm of surface-enhanced Raman scattering (SERS). This review comprehensively outlines the evolution, synthesis methodologies, and characterization techniques employed for MXene-based SERS substrates. It delves into the intricacies of its SERS enhancement mechanism, substrate variants, and performance metrics, alongside showcasing its diverse applications spanning molecular detection, biosensing, and environmental monitoring. Furthermore, it endeavors to pinpoint the research bottlenecks and chart the future research trajectories for MXene-based SERS substrates.

Ti3C2TxMXene as surface-enhanced Raman scattering substrate.

The electromagnetic field enhancement mechanisms leading to surface-enhanced Raman scattering (SERS) of R6G molecules near Ti3C2TxMXene flakes of different shapes and sizes are analyzed theoretically in this paper. In COMSOL simulations for the enhancement factor (EF) of SERS, the dye molecule is modeled as a small sphere with polarizability spectrum based on experimental data. It is demonstrated, for the first time, that in the wavelength range of500 nm-1000 nm, the enhancement of Raman signals is largely conditioned by quadrupole surface plasmon (QSP) oscillations that induce a strong polarization of the MXene substrate. We show that the vis-NIR spectral range quadrupole SP resonances are strengthened due to interband transitions (IBTs), which provide EF values of the order of 105-107in agreement with experimental data. The weak sensitivity of the EF to the shape and size of MXene nanoparticles (NPs) is interpreted as a consequence of the low dependence of the absorption cross-section of QSP oscillations and IBT on the geometry of the flakes. This reveals a new feature: the independence of EF on the geometry of MXene substrates, which allows to avoid the monitoring of the shape and size of flakes during their synthesis. Thus, MXene flakes can be advantageous for the easy manufacturing of universal substrates for SERS applications. The electromagnetic SERS enhancement is determined by the 'lightning rod' and 'hot-spot' effects due to the partial overlapping of the absorption spectrum of the R6G molecule with these MXene resonances.

Synthesis of SiO2@Ag Nanocomposite for Investigating Metal-Enhanced Fluorescence and Surface-Enhanced Raman Spectroscopy.

SiO2@Ag nanocomposite (NC) has been synthesized by the chemical reduction and StÓ§ber method for Metal-enhanced fluorescence (MEF) of Rhodmine 6G (R6G) and Surface-enhanced Raman spectroscopy (SERS) of Malachite green (MG). As-synthesized SiO2@Ag NC indicated SiO2 nanosphere (NS) and Ag nanoparticle (NP) morphologies. The SiO2@Ag NC was high quality with a well-defined crystallite phase with average sizes of 24 nm and 132 nm for Ag NP and SiO2 NC, respectively. By using SiO2@Ag NC, the photoluminescence (PL) intensity of the R6G (at 59.17 ppm) was increased approximately 133 times. The SERS of the MG (at 1.0 ppm) with SiO2@Ag NC as substrate clearly observed vibrational modes in MG dye at 798, 916, 1172, 1394, and 1616 cm-1. As a result, the SERS enhancement factor (EFSERS) at 1172 cm-1 obtained 6.3 × 106. This initial study points to the potential of SiO2@Ag NC as a promising material for MEF and SERS substrates to detect dyes at low concentrations.

Self-Mixing Interferometer for Acoustic Measurements through Vibrometric Calibration.

The Self-Mixing Interformeter (SMI) is a self-aligned optical interferometer which has been used for acoustic wave sensing in air through the acousto-optic effect. This paper presents how to use a SMI for the measurement of Sound Pressure Level (SPL) in acoustic waveguides. To achieve this, the SMI is first calibrated in situ as a vibrometer. The optical feedback parameters C and α in the strong feedback regime (C≥4.6) are estimated from the SMI vibrometric signals and by the solving of non-linear equations governing the SMI behaviour. The calibration method is validated on synthetic SMI signals simulated from SMI governing equations for C ranging from 5 to 20 and α ranging from 4 to 10. Knowing C and α, the SMI is then used as an acoustic pressure sensor. The SPLs obtained using the SMI are compared with a reference microphone, and a maximal deviation of 2.2 dB is obtained for plane waves of amplitudes ranging from 20 to 860 Pa and frequencies from 614 to 17,900 Hz. The SPL measurements are carried out for C values ranging from 7.1 to 21.5.

Length-Controllable Gold-Coated Silver Nanowire Probes for High AFM-TERS Scattering Activity.

Tip-enhanced Raman scattering (TERS) microscopy is an advanced technique for investigation at the nanoscale that provides topographic and chemical information simultaneously. The TERS probe plays a crucial role in the microscopic performance. In the recent past, the development of silver nanowire (AgNW) based TERS probes solved the main tip fabrication issues, such as low mechanical strength and reproducibility. However, this fabrication method still suffers from low control of the protruded length of the AgNW. In this work, a simple water-air interface electrocutting method is proposed to achieve wide controllability of the length. This water cutting method was combined with a succedent Au coating on the AgNW surface, and the probe achieved an up to 100× higher enhancement factor (EF) and a 2× smaller spatial resolution compared to pristine AgNW. Thanks to this excellent EF, the water-cut Au-coated AgNW probes were found to possess high TERS activity even in the nongap mode, enabling broad applications.

Surface-Enhanced Raman Spectroscopy (SERS)-Based Sensors for Deoxyribonucleic Acid (DNA) Detection.

Surface-enhanced Raman spectroscopy (SERS) has emerged as a powerful technique for the detection and analysis of biomolecules due to its high sensitivity and selectivity. In recent years, SERS-based sensors have received significant attention for the detection of deoxyribonucleic acid (DNA) molecules, offering promising applications in fields such as medical diagnostics, forensic analysis, and environmental monitoring. This paper provides a concise overview of the principles, advancements, and potential of SERS-based sensors for DNA detection. First, the fundamental principles of SERS are introduced, highlighting its ability to enhance the Raman scattering signal by several orders of magnitude through the interaction between target molecules with metallic nanostructures. Then, the fabrication technologies of SERS substrates tailored for DNA detection are reviewed. The performances of SERS substrates previously reported for DNA detection are compared and analyzed in terms of the limit of detection (LOD) and enhancement factor (EF) in detail, with respect to the technical parameters of Raman spectroscopy (e.g., laser wavelength and power). Additionally, strategies for functionalizing the sensor surfaces with DNA-specific capture probes or aptamers are outlined. The collected data can be of help in selecting and optimizing the most suitable fabrication technology considering nucleotide sensing applications with Raman spectroscopy.

A Multi-Information Spreading Model for One-Time Retweet Information in Complex Networks.

In the realm of online social networks, the spreading of information is influenced by a complex interplay of factors. To explore the dynamics of one-time retweet information spreading, we propose a Susceptible-Infected-Completed (SIC) multi-information spreading model. This model captures how multiple pieces of information interact in online social networks by introducing inhibiting and enhancement factors. The SIC model considers the completed state, where nodes cease to spread a particular piece of information after transmitting it. It also takes into account the impact of past and present information received from neighboring nodes, dynamically calculating the probability of nodes spreading each piece of information at any given moment. To analyze the dynamics of multiple information pieces in various scenarios, such as mutual enhancement, partial competition, complete competition, and coexistence of competition and enhancement, we conduct experiments on BA scale-free networks and the Twitter network. Our findings reveal that competing information decreases the likelihood of its spread while cooperating information amplifies the spreading of mutually beneficial content. Furthermore, the strength of the enhancement factor between different information pieces determines their spread when competition and cooperation coexist. These insights offer a fresh perspective for understanding the patterns of information propagation in multiple contexts.

Highly Sensitive, Robust, and Recyclable TiO2/AgNP Substrate for SERS Detection.

Label-free biosensors provide an important platform for detecting chemical and biological substances without needing extra labeling agents. Unlike surface-based techniques such as surface plasmon resonance (SPR), interference, and ellipsometry, surface-enhanced Raman spectroscopy (SERS) possesses the advantage of monitoring analytes both on surfaces and in solutions. Increasing the SERS enhancement is crucial to preparing high-quality substrates without quickly losing their stability, sensitivity, and repeatability. However, fabrication methods based on wet chemistry, nanoimprint lithography, spark discharge, and laser ablation have drawbacks of waste of time, complicated processes, or nonreproducibility in surface topography. This study reports the preparation of recyclable TiO2/Ag nanoparticle (AgNP) substrates by using simple arc ion plating and direct-current (dc) magnetron sputtering technologies. The deposited anatase-phased TiO2 ensured the photocatalytic degradation of analytes. By measuring the Raman spectra of rhodamine 6G (R6G) in titrated concentrations, a limit of detection (LOD) of 10-8 M and a SERS enhancement factor (EF) of 1.01 × 109 were attained. Self-cleaning was performed via UV irradiation, and recyclability was achieved after at least five cycles of detection and degradation. The proposed TiO2/AgNP substrates have the potential to serve as eco-friendly SERS enhancers for label-free detection of various chemical and biological substances.

Multi-User Scheduling for 6G V2X Ultra-Massive MIMO System.

6G vehicle-to-everything (V2X) communication will be combined with vehicle automatic driving technology and play an important role in automatic driving. However, in 6G V2X systems, vehicle users have the characteristics of high-speed movement. Therefore, how to provide stable and reliable wireless link quality and improve channel gain has become a problem that must be solved. To solve this problem, a new multi-user scheduling algorithm based on block diagonalization (BD) precoding for 6G ultra-massive multiple-input multiple-output (MIMO) systems is proposed in this paper. The algorithm takes advantage of the sensitive nature of BD precoding to channel correlation, uses the Pearson coefficient after matrix vectorization to measure the channel correlation between users, defines the scheduling factor to measure the channel quality according to the user noise enhancement factor, and jointly considers the influence of the correlation between user channels and channel quality, ensuring the selection of high-quality channels while minimizing channel correlation. Simulation results show that compared with the multi-user scheduling algorithm based on subspace correlation, condition number, and geometric angle, the proposed algorithm can obtain higher user channel gain, effectively reduce the system bit error rate, and can be applied to 6G V2X communication.

Impact of the Spectral Composition of Kilovoltage X-rays on High-Z Nanoparticle-Assisted Dose Enhancement.

Nanoparticles (NPs) with a high atomic number (Z) are promising radiosensitizers for cancer therapy. However, the dependence of their efficacy on irradiation conditions is still unclear. In the present work, 11 different metal and metal oxide NPs (from Cu (ZCu = 29) to Bi2O3 (ZBi = 83)) were studied in terms of their ability to enhance the absorbed dose in combination with 237 X-ray spectra generated at a 30-300 kVp voltage using various filtration systems and anode materials. Among the studied high-Z NP materials, gold was the absolute leader by a dose enhancement factor (DEF; up to 2.51), while HfO2 and Ta2O5 were the most versatile because of the largest high-DEF region in coordinates U (voltage) and Eeff (effective energy). Several impacts of the X-ray spectral composition have been noted, as follows: (1) there are radiation sources that correspond to extremely low DEFs for all of the studied NPs, (2) NPs with a lower Z in some cases can equal or overcome by the DEF value the high-Z NPs, and (3) the change in the X-ray spectrum caused by a beam passing through the matter can significantly affect the DEF. All of these findings indicate the important role of carefully planning radiation exposure in the presence of high-Z NPs.

High Contrast Surface Enhanced Fluorescence of Carbon Dot Labeled Bacteria Cells on Aluminum Foil.

Surface enhanced fluorescence (SEF) is observed with very high contrast (100-200) from single E. coli bacteria cells labeled with Carbon nanodots (CDs), on aluminum foil and aluminum film. Likely, it is the first application of organic CDs in SEF. SEF with 633 nm excitation delivered a much higher contrast than SEF with 532 nm excitation. Contrast is the ratio of the fluorescent intensities of labeled CDs to unlabeled (control) cells. High contrast with CDs is also observed on the gold film, silicon, and glass. Enhancement factor (EF) is the ratio of the signal on the metal substrate to the signal on the glass. Single E. coli cells, labeled with commercial graphene quantum dots (GCDs), demonstrated higher EFs (44 on gold, 35 on Al film), but at least one order of magnitude lower contrast (7-10 on aluminum and gold) than cells labeled with organic CDs. Therefore, organic CDs can be a good choice for cell imaging/labeling, capable of achieving a signal to noise (standard deviation of the control) as high as 700 on Al film. Overall, aluminum foil and film are highlighted as inexpensive but efficient substrates for Metal Enhanced Fluorescence, particularly MEF of bacterial cells stained with CDs.

Towards Reliable and Quantitative Surface-Enhanced Raman Scattering (SERS): From Key Parameters to Good Analytical Practice.

Experimental results obtained in different laboratories world-wide by researchers using surface-enhanced Raman scattering (SERS) can differ significantly. We, an international team of scientists with long-standing expertise in SERS, address this issue from our perspective by presenting considerations on reliable and quantitative SERS. The central idea of this joint effort is to highlight key parameters and pitfalls that are often encountered in the literature. To that end, we provide here a series of recommendations on: a) the characterization of solid and colloidal SERS substrates by correlative electron and optical microscopy and spectroscopy, b) on the determination of the SERS enhancement factor (EF), including suitable Raman reporter/probe molecules, and finally on c) good analytical practice. We hope that both newcomers and specialists will benefit from these recommendations to increase the inter-laboratory comparability of experimental SERS results and further establish SERS as an analytical tool.

Strong Surface Enhanced Florescence of Carbon Dot Labeled Bacteria Cells Observed with High Contrast on Gold Film.

Strong surface (metal) enhanced fluorescence (SEF or MEF) is observed from clusters and single E coli bacteria cells labeled with Carbon nanodots (CDs), which were synthesized from date pits. The enhancement factor (EF) for SEF of the cell clusters were close to 50 for both 533 and 633 nm laser excitation wavelength. Those EFs are ratios of emission peak areas from CD labeled cell clusters on gold film to the peak areas of the same batch cell clusters on glass substrate. SEF with 633 nm excitation performed better than SEF with 532 nm excitation, achieving higher fluorescence intensity and much higher contrast. The contrast as high as 66 for cell clusters on gold film is a ratio of fluorescent emission peak area measured at the CD labeled cell clusters to the fluorescent peak area measured at unlabeled cell clusters (autofluorescence) on the same substrate. The contrast with the background (S/N) or the ratio of fluorescent peak area measured at bacteria cells to area measured at bare substrate was as high as 200. This report may pave a way for the broader application of surface enhanced fluorescence and especially metal enhanced fluorescence imaging of CD labeled cells and other biological objects. Graphical abstract Carbon dots, synthesized from dates, are used for direct staining of E coli cells. Emission fluorescent spectroscopy of those CD labelled cells on gold film and glass, demonstrated enhancement factor about 50 for emission on gold as compared to glass, Excitation at 633 nm appears far superior to excitation at 532 nm in terms of contrast (up to 67) with unlabeled cells /control due to decrease in auto fluorescence of cells. Maximum Signal to noise ratio is 200.

Concentration dependence of nitroxyl spin probes in liposomal solution: electron spin resonance and overhauser-enhanced magnetic resonance studies.

In this work, the detailed studies of electron spin resonance (ESR) and overhauser-enhanced magnetic resonance imaging (OMRI) were carried out for permeable nitroxyl spin probe, MC-PROXYL as a function of agent concentration in liposomal solution. In order to compare the impermeable nature of nitroxyl radical, the study was also carried out only at 2 mM concentration of carboxy-PROXYL. The ESR parameters were estimated using L-band and 300 MHz ESR spectrometers. The line width broadening was measured as a function of agent concentration in liposomal solution. The estimated rotational correlation time is proportional to the agent concentration, which indicates that less mobile nature of nitroxyl spin probe in liposomal solution. The partition parameter and permeability values indicate that the diffusion of nitroxyl spin probe distribution into the lipid phase is maximum at 2 mM concentration of MC-PROXYL. The dynamic nuclear polarization (DNP) parameters such as DNP factor, longitudinal relaxivity, saturation parameter, leakage factor and coupling factor were estimated for 2 mM MC-PROXYL in 400 mM liposomal dispersion. The spin lattice relaxation time was shortened in liposomal solution, which leads to the high relaxivity. Reduction in coupling factor is due to less interaction between the electron and nuclear spins, which causes the reduction in enhancement. The leakage factor increases with increasing agent concentration. The increase in DNP enhancement was significant up to 2 mM in liposomal solution. These results paves the way for choosing optimum agent concentration and OMRI scan parameters used in intra and extra membrane water by loading the liposome vesicles with a lipid permeable nitroxyl spin probes in OMRI experiments.

Measuring Linewidth Enhancement Factor by Relaxation Oscillation Frequency in a Laser with Optical Feedback.

This paper presents a new method for measuring the linewidth enhancement factor (alpha factor) by the relaxation oscillation (RO) frequency of a laser with external optical feedback (EOF). A measurement formula for alpha is derived which shows the alpha can be determined by only using the RO frequencies and no need to know any other parameters related to the internal or external parameters associated to the laser. Unlike the existing EOF based alpha measurement methods which require an external target has a symmetric reciprocate movement. The proposed method only needs to move the target to be in a few different positions along the light beam. Furthermore, this method also suits for the case with alpha less than 1. Both simulation and experiment are performed to verify the proposed method.

ESR line width and line shape dependence of Overhauser-enhanced magnetic resonance imaging.

Electron spin resonance and Overhauser-enhanced magnetic resonance imaging studies were carried out for various concentrations of 14 N-labeled 3-carbamoyl-2,2,5,5-tetramethyl-pyrrolidine-1-oxyl in pure water. Overhauser-enhancement factor attains maxima in the range of 2.5-3 mm concentration. The leakage factor showed an asymptotic increase with increasing agent concentration. The coupling parameter showed the interaction between the electron and nuclear spins to be mainly dipolar in origin. The electron spin resonance parameters, such as the line width, line shape and g-factor, were determined. The line width analysis confirms that the line broadening is proportional to the agent concentration, and also the agent concentration is optimized in the range of 2.5-3 mm. The line shape analysis shows that the observed electron spin resonance line shape is a Voigt line shape, in which the Lorentzian component is dominant. The contribution of Lorentzian component was estimated using the winsim package. The Lorentzian component of the resonance line attains maxima in the range of 2.5-3 mm concentration. Therefore, this study reveals that the agent concentration, line width and Lorentzian component are the important factors in determining the Overhauser-enhancement factor. Hence, the agent concentration was optimized as 2.5-3 mm for in vivo/in vitro electron spin resonance imaging and Overhauser-enhanced magnetic resonance imaging phantom studies. Copyright © 2016 John Wiley & Sons, Ltd.

Harmonic demodulation and minimum enhancement factors in field-enhanced near-field optical microscopy.

Field-enhanced scanning optical microscopy relies on the design and fabrication of plasmonic probes which had to provide optical and chemical contrast at the nanoscale. In order to do so, the scattering containing the near-field information recorded in a field-enhanced scanning optical microscopy experiment, has to surpass the background light, always present due to multiple interferences between the macroscopic probe and sample. In this work, we show that when the probe-sample distance is modulated with very low amplitude, the higher the harmonic demodulation is, the better the ratio between the near-field signal and the interferometric background results. The choice of working at a given n harmonic is dictated by the experiment when the signal at the n + 1 harmonic goes below the experimental noise. We demonstrate that the optical contrast comes from the nth derivative of the near-field scattering, amplified by the interferometric background. By modelling the far and near field we calculate the probe-sample approach curves, which fit very well the experimental ones. After taking a great amount of experimental data for different probes and samples, we conclude with a table of the minimum enhancement factors needed to have optical contrast with field-enhanced scanning optical microscopy.

A surface-enhanced infrared absorption spectroscopy (SEIRA) multivariate approach for atrazine detection.

A green, fast and effective multivariate method for the determination of atrazine (ATZ) was developed using conventional infrared equipment furnished with an attenuated total reflectance module (ATR-IR), providing limit of detection (LOD) and limit of quantification (LOQ) in the ranges from 1.9 to 4.6 µg/mL and from 5.6 to 14 µg/mL, respectively. Furthermore, the surface-enhanced infrared absorption (SEIRA) approach was investigated to improve the sensitivity of the measurements and detect ATZ at low concentrations, addressing the compatibility with reference methods. To this end, a substrate formed by silver selenide quantum dots stabilized with mercaptopropionic acid (Ag2Se/MPA), synthesized in aqueous medium by an one-pot synthesis, was used. The spectral data were investigated by univariate and multivariate calibrations, allowing to calculate the enhancement factor (EF) and the multivariate enhancement factor (MEF), respectively. The SEIRA strategy proved to be able to enhance the atrazine signal up to 86-fold, allowing the detection of ATZ at concentrations as low as 0.001 µg/mL.

Refining shape and size of silver nanoparticles using ion irradiation for enhanced and homogeneous SERS activity.

We present green synthesis of silver nanoparticles in water using unirradiated and Ag 15 + ion irradiated phytoextracts of Bergenia Ciliata leaf, Eupatorium adenophorum leaf, Rhododendron arboreum leaf and flower. The use of different plant extracts and their subsequent ion irradiation allow for successful refinement of nanoparticle size and morphology. Due to changes in reducing and capping agents the nanoparticle surface functionalization also varies which not only controls the morphology but also allows for surface oxidation and aggregation processes. In this work, we have synthesized silver nanoparticles which exhibit sizes in the range from 13 to 24 nm and having shapes like spherical, quasispherical, trigonal, hexagonal, cylindrical, dendritic assemblies, and porous nanoparticles. Owing to changes in the size and shape of the nanoparticles, their direct bandgap (2.05 eV - 2.48 eV) and local surface plasmon resonance (420 nm - 490 nm) could also be tuned. These nanoparticles are examined as SERS substrates, where their enhancement factors, limit of detection for methylene blue, and SERS substrate homogeneity have been tested. It has been observed the nanoparticles synthesized using unirradiated plant extracts present an enhancement factor of 10 6 with a limit of detection 10 - 8 M. Whereas nanoparticles with refined morphology and shapes upon irradiation present high enhancement factors of >10 7 and detection limit down to 10 - 9 M. In addition, uniformity in Raman spectra over the SERS substrates has been obtained for selected Ag NPs substrates synthesized using irradiated extracts with minimum relative standard deviation in enhancement factor < 12%.

Experimental and Numerical Study of a Trapezoidal Rib and Fan Groove Microchannel Heat Sink.

A novel microchannel heat sink (TFMCHS) with trapezoidal ribs and fan grooves was proposed, and the microchannel was manufactured using selective laser melting technology. Firstly, the temperature and pressure drop at different power levels were measured through experiments and then combined with numerical simulation to explore the complex flow characteristics within TFMCHSs and evaluate the comprehensive performance of microchannel heat sinks based on the thermal enhancement coefficient. The results show that, compared with rectangular microchannel heat sinks (RMCHSs), the average and maximum temperatures of TFMCHSs are significantly reduced, and the temperature distribution is more uniform. This is mainly caused by the periodic interruption and redevelopment of the velocity boundary layer and thermal boundary layer caused by ribs and grooves. And as the heating power increases, the TFMCHS has better heat dissipation performance. When P=33 W and the inlet flow rate is 32.5 mL/min, the thermal enhancement factor reaches 1.26.