Electronic properties of two-dimensional(2D) materials can be strongly modulated by localized strain. The typical spatial resolution of conventional Kelvin probe force microscopy(KPFM) is usually limited in a few hund...Electronic properties of two-dimensional(2D) materials can be strongly modulated by localized strain. The typical spatial resolution of conventional Kelvin probe force microscopy(KPFM) is usually limited in a few hundreds of nanometers, and it is difficult to characterize localized electronic properties of 2D materials at nanoscales. Herein, tip-enhanced Raman spectroscopy(TERS) is proposed to combine with KPFM to break this restriction. TERS scan is conducted on ReS2bubbles deposited on a rough Au thin film to obtain strain distribution by using the Raman peak shift. The localized contact potential difference(CPD) is inversely calculated with a higher spatial resolution by using strain measured by TERS and CPD-strain working curve obtained using conventional KPFM and atomic force microscopy. This method enhances the spatial resolution of CPD measurements and can be potentially used to characterize localized electronic properties of 2D materials.展开更多
Tip-enhanced Raman spectroscopy(TERS)imaging is a super-resolution imaging technique that features the merits of both surface-enhanced Raman spectroscopy(SERS)and scanning probe microscopy(SPM),such as the high chemic...Tip-enhanced Raman spectroscopy(TERS)imaging is a super-resolution imaging technique that features the merits of both surface-enhanced Raman spectroscopy(SERS)and scanning probe microscopy(SPM),such as the high chemical sensitivity from the former and the nanoscale spatial resolution from the latter.These advantages make TERS an essential nanospectroscopic characterization technique for chemical analysis,materials science,bio-sensing,etc.TERS probes,the most critical factor determining the TERS imaging quality,are expected to provide a highly confined electromagnetic hotspot with a minimized scattering background for the generation of Raman signals with high spatial resolution.After two decades of development,numerous probe design concepts have been proposed and demonstrated.This review provides a comprehensive overview of the state-of-the-art TERS probe designs,from the working mechanism to the practical performance.We start with reviewing the recent development of TERS configurations and the corresponding working mechanisms,including the SPM platforms,optical excitation/collection techniques,and probe preparation methods.We then review the emerging novel TERS probe designs,including the remote-excitation probes,the waveguide-based nanofocusing probes,the metal-coated nanofocusing probes,the nanowire-assisted selective-coupling probes,and the tapered metal-insulator-metal probes.Our discussion focuses on a few critical aspects,including the surface-plasmon-polariton(SPP)hotspot excitation technique,conversion efficiency,working frequency,and controllability.In the end,we review the latest TERS applications and give a perspective on the future of TERS.展开更多
Chemistry on solid surfaces is central to many research areas of practical interest,such as synthesis,catalysis,electrochemistry,photochemistry,and materials science.A comprehensive understanding of the nanoscale on-s...Chemistry on solid surfaces is central to many research areas of practical interest,such as synthesis,catalysis,electrochemistry,photochemistry,and materials science.A comprehensive understanding of the nanoscale on-surface chemistry involved in these areas is important for establishing composition-structure-performance relationships.With the rapid development of tip-enhanced Raman spectroscopy(TERS),it has become possible to investigate physical and chemical processes on suitable surfaces at the nanoscale level and in real space.In this review,after a brief introduction of the background of onsurface chemistry and TERS,we systematically discuss the progress in the application of TERS in this field.Our focus is the applications of TERS to nanoscale coordination processes,decomposition reactions,polymerization processes,electrochemical reactions,catalytic chemistry,and functionalization chemistry on solid surfaces.We conclude by discussing the future challenges and development of TERS techniques and related applications in on-surface chemistry.展开更多
Tip-enhanced Raman spectroscopy (TERS) has been used to obtain the Raman signal of surface species on silicon single crystal surfaces without the necessity for surface enhancement by addition of Ag nanoparticles. By i...Tip-enhanced Raman spectroscopy (TERS) has been used to obtain the Raman signal of surface species on silicon single crystal surfaces without the necessity for surface enhancement by addition of Ag nanoparticles. By illuminating the hydrogen terminated silicon surface covered with a droplet of 4-vinylpyridine with UV light, a 4-ethylpyridine modified silicon surface can be easily obtained. By bringing a scanning tunneling microscope (STM) Au tip with a nanoscale tip apex to a distance of ca. 1 nm from the modified silicon surface, enhanced Raman signals of the silicon phonon vibrations and the surface-bonded 4-ethylpyridine were obtained. The Raman enhancement factor was estimated to be close to 107. By comparing the surface enhanced Raman scattering (SERS) signal obtained after surface enhancement with Ag nanoparticles and the TERS signal of the surface, the advantage of TERS over SERS for characterizing the surface species on substrates becomes apparent: TERS readily affords vibrational information about the system without disturbing it by surface enhancement. In this sense, TERS can be considered a truly non-invasive tool which is ideal for characterizing the actual surface species on substrates.展开更多
Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely use...Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.展开更多
Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly ...Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly important to effectively control the aging process of CSB,reduce quality deterioration,and promote the industrial production of CSB.Raman spectroscopy has been widely used in the study of food structure and properties due to its non-destructive and high-sensitivity characteristics,particularly demonstrating unique advantages in the analysis of starch structure.This study explored the possibility of analyzing the staling of CSB using Raman spectroscopy based on hardness and moisture content.Analysis of the correlation between the hardness of CSB and the full width at half maximum(FWHM)at 480 cm^(−1)during storage was conducted,and a significant positive correlation between them was found,with R^(2)above 0.8.Besides,nine characteristic peaks of CSB samples related to starch were selected for analysis.As the moisture content of CSB decreased,the peak intensities and areas of showed an upward trend during storage,with the best correlation coefficient above 0.8 revealed by linear regression analysis.Therefore,Raman spectra could be used as a potential method for the fast prediction of CSB staling.展开更多
Raman spectroscopy is a powerful technique in chemical information characterization. However, this spectral method is subject to two obstacles in nano-material detection. One is diffraction limited spatial resolution,...Raman spectroscopy is a powerful technique in chemical information characterization. However, this spectral method is subject to two obstacles in nano-material detection. One is diffraction limited spatial resolution, and the other is its inherent small Raman cross section and weak signaling. To resolve these problems, a new approach has been developed, denoted as tip-enhanced Raman spectroscopy (TERS). TERS is capable of high-resolution and high-sensitivity detection and demonstrated to be a promising spectroscopic and micro-topographic method to characterize nano-materials and nanostructures. In this paper, the principle and experimental system of TERS are discussed. The latest application of TERS in molecule detection, biological specimen identification, nanao-material characterization, and semi-conductor material determination with some specific experimental examples are presented.展开更多
Due to its ubiquitous occurrence in igneous,metamorphic,and sedimentary rocks and its wide application in geochronology and geochemistry,zircon has become the most widely used accessory mineral in the geological commu...Due to its ubiquitous occurrence in igneous,metamorphic,and sedimentary rocks and its wide application in geochronology and geochemistry,zircon has become the most widely used accessory mineral in the geological community.Nevertheless,the decay of U and Th causes radiation damage to the zircon structure,resulting in various degrees of metamictization,which can affect the accuracy of U–Pb dates and Hf and O isotope results.If the degree of zircon radiation damage can be quantified,the influence on geochemical analyses can be evaluated,and the results can be corrected more precisely.In this paper,synthetic and natural zircon crystals with different crystallization ages were selected for Raman spectroscopy analysis,cathodoluminescence imaging,and determination of the U and Th concentrations.The results show that Raman FWHM(full width at half bandmaximum)and Raman shift correlate with alpha dose(Da)ofzirconsfollowingtheseequations,FWHM=44.36(±2.32)×[1-exp(-2.74×Da)]-+1.7(±0.19),Raman Shift=-6.53×Da+1007.69.Analysis of synthetic zircon crystals shows that doped REEs(rare earth elements and P)can also lead to an increase in the FWHM.However,this effect can be ignored for natural zircon samples with REE contents at a normal level of hundreds to a few thousand ppm.The FWHM and Raman shift can be used as proxies to measure the degree of zircon radiation damage.Using the updated equations to calculate the latest age when zircon began to accumulate radiation damage,a more accurate and more meaningful“radiation damage age”can be obtained.展开更多
The skin is the largest organ in humans.It comprises about 16%of our body.Many diseases originate from the skin,including acne vulgaris,skin cancer,fungal skin disease,etc.As a common skin cancer in China,melanoma alo...The skin is the largest organ in humans.It comprises about 16%of our body.Many diseases originate from the skin,including acne vulgaris,skin cancer,fungal skin disease,etc.As a common skin cancer in China,melanoma alone grows at year rate of nearly 4%.Therefore,it is crucial to develop an objective,reliable,accurate,non-invasive,and easy-to-use diagnostic method for skin diseases to support clinical decision-making.Raman spectroscopy is a highly specic imaging technique,which is sensitive,even to the single-cell level in skin diagnosis.Raman spectroscopy provides a pattern of signals with narrow bandwidths,making it a common and essential tool for researching individual characteristics of skin cells.Raman spectroscopy already has a number of clinical applications,including in thyroid,cervical and colorectal cancer.This review will introduce the advantages and recent developments in Raman spectroscopy,before focusing on the advances in skin diagnosis,including the advantages,methods,results,analysis,and notications.Finally,we discuss the current limitations and future progress of Raman spectroscopy in the context of skin diagnosis.展开更多
BACKGROUND Cancer detection is a global research focus,and novel,rapid,and label-free techniques are being developed for routine clinical practice.This has led to the development of new tools and techniques from the b...BACKGROUND Cancer detection is a global research focus,and novel,rapid,and label-free techniques are being developed for routine clinical practice.This has led to the development of new tools and techniques from the bench side to routine clinical practice.In this study,we present a method that uses Raman spectroscopy(RS)to detect cancer in unstained formalin-fixed,resected specimens of the esophagus and stomach.Our method can record a clear Raman-scattered light spectrum in these specimens,confirming that the Raman-scattered light spectrum changes because of the histological differences in the mucosal tissue.AIM To evaluate the use of Raman-scattered light spectrum for detecting endoscopically resected specimens of esophageal squamous cell carcinoma(SCC)and gastric adenocarcinoma(AC).METHODS We created a Raman device that is suitable for observing living tissues,and attempted to acquire Raman-scattered light spectra in endoscopically resected specimens of six esophageal tissues and 12 gastric tissues.We evaluated formalin-fixed tissues using this technique and captured shifts at multiple locations based on feasibility,ranging from six to 19 locations 200 microns apart in the vertical and horizontal directions.Furthermore,a correlation between the obtained Raman scattered light spectra and histopathological diagnosis was performed.RESULTS We successfully obtained Raman scattered light spectra from all six esophageal and 12 gastric specimens.After data capture,the tissue specimens were sent for histopathological analysis for further processing because RS is a label-free methodology that does not cause tissue destruction or alterations.Based on data analysis of molecular-level substrates,we established cut-off values for the diagnosis of esophageal SCC and gastric AC.By analyzing specific Raman shifts,we developed an algorithm to identify the range of esophageal SCC and gastric AC with an accuracy close to that of histopathological diagnoses.CONCLUSION Our technique provides qualitative information for real-time morphological diagnosis.However,further in vivo evaluations require an excitation light source with low human toxicity and large amounts of data for validation.展开更多
As one type of spatially offset Raman spectroscopy(SORS), inverse SORS is particularly suited to in vivo biomedical measurements due to its ring-shaped illumination scheme. To explain inhomogeneous Raman scattering du...As one type of spatially offset Raman spectroscopy(SORS), inverse SORS is particularly suited to in vivo biomedical measurements due to its ring-shaped illumination scheme. To explain inhomogeneous Raman scattering during in vivo inverse SORS measurements, the light–tissue interactions when excitation and regenerated Raman photons propagate in skin tissue were studied using Monte Carlo simulation. An eight-layered skin model was first built based on the latest transmission parameters. Then, an open-source platform, Monte Carlo e Xtreme(MCX), was adapted to study the distribution of 785 nm excitation photons inside the model with an inverse spatially shifted annular beam. The excitation photons were converted to emission photons by an inverse distribution method based on excitation flux with spatial offsets Δs of 1 mm, 2 mm, 3 mm and 5 mm. The intrinsic Raman spectra from separated skin layers were measured by continuous linear scanning to improve the simulation accuracy. The obtained results explain why the spectral detection depth gradually increases with increasing spatial offset, and address how the intrinsic Raman spectrum from deep skin layers is distorted by the reabsorption and scattering of the superficial tissue constituents. Meanwhile, it is demonstrated that the spectral contribution from subcutaneous fat will be improved when the offset increases to 5 mm, and the highest detection efficiency for dermal layer spectral detection could be achieved when Δs = 2 mm. Reasonably good matching between the calculated spectrum and the measured in vivo inverse SORS was achieved, thus demonstrating great utility of our modeling method and an approach to help understand the clinical measurements.展开更多
Bronze phase titanium dioxide(TiO_(2)(B))could be a promising high-power anode for lithium ion battery.However,TiO_(2)(B)is a metastable material,so the as-synthesized samples are inevitably accompanied by the existen...Bronze phase titanium dioxide(TiO_(2)(B))could be a promising high-power anode for lithium ion battery.However,TiO_(2)(B)is a metastable material,so the as-synthesized samples are inevitably accompanied by the existence of anatase phases.It has been found that the TiO_(2)(B)'s purity is positively correlated with its electrochemical performance.Herein,we have established an accurate quantification of the TiO_(2)(B)/anatase ratio,by figuring out the function between the purity of TiO_(2)(B)phase in the high purity range and its Raman spectra features in combination of the calibration by the synchrotron radiation X-ray diffraction(XRD).Compared with the time-consuming electrochemical method,the rapid,sensitive and non-destructive features of Raman spectroscopy have made it a promising candidate for determining the purity of TiO_(2)(B).Further,the correlations developed in this work should be instructive in synthesizing pure TiO_(2)(B)and furthermore optimizing its electrochemical charge storage properties.展开更多
Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible ...Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.展开更多
The application of vibrational spectroscopy in the pharmaceutical industry is widely investigated, from the quality assurance of the product during the production process control to the final products’ quality contro...The application of vibrational spectroscopy in the pharmaceutical industry is widely investigated, from the quality assurance of the product during the production process control to the final products’ quality control and the authentication of products on the markets. This study focuses on non-contact and noninvasive detection and identification of pain-relievers at 1-5 meters standoff distances. The specimens analyzed include standard laboratory-grade active ingredients and commercially available pain relievers in powder, solid and liquid forms. All the remote measurements captured revealed the Raman signatures of the specimens, with varying peak intensities. To correlate the band intensities captured with the standoff distances between the laser source and the specimens, the intensity ratios of the two prominent peaks of the laboratory grade reference active ingredient (1607 and 1319 cm<sup>-1</sup>) normalized with 1319 cm<sup>-1</sup> are used. The results of the study suggest the viability of standoff Raman spectroscopy for routine monitoring and identification of pharma-ceuticals, including counterfeit pain relievers.展开更多
Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-s...Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.展开更多
We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
Angle-resolved polarized Raman(ARPR) spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropi...Angle-resolved polarized Raman(ARPR) spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations: 1) to change the polarization of the incident laser, 2) to rotate the sample, and 3) to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite(HOPG) exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.展开更多
Oxidative stress is implicated in male infertility and significantly higher reactive oxygen species are detected in 25% of infertile males. Although different agents of various alternative medicines, including traditi...Oxidative stress is implicated in male infertility and significantly higher reactive oxygen species are detected in 25% of infertile males. Although different agents of various alternative medicines, including traditional Chinese medicine, have been tried with varying success, evidence remains limited on whether and how much herbs or supplements might help increase the anti-oxidant ability of the sperm. This study examined the anti-oxidative effects of icariin, a flavonoid isolated from Herba Epimedii, on the human sperm. We prepared the FeSO4/H202-damaged human sperms, which were co-cultured with icariin in vitro, and then observed the changes of the sperm by employing Raman mi- cro-spectroscopy. The results showed that Raman mapping with a 514 nm excitation laser allowed clear differentiation of the nucleus, neck, and, in particular, the mitochondria-rich middle piece of a human sperm cell. The effect oficariin on different organelles of the sperm was quantified by localized spectral Raman signatures obtained within milli-seconds, and icariin could keep the "Raman fingerprint" of the human sperm the same as the control groups, suggesting that icariin could protect the human sperm from being damaged by FeSO4/H202. Icariin may serve as a tonifying and replenishing agent of herbal origin for enhancing reproductive fimctions.展开更多
The molten mixtures of alkali metal fluorides and aluminum fluoride are applied as aluminum electrolytes or brazing fluxes.However,the presence of Al2F-7^-in such molten systems is disputed.In the present study,MF-AlF...The molten mixtures of alkali metal fluorides and aluminum fluoride are applied as aluminum electrolytes or brazing fluxes.However,the presence of Al2F-7^-in such molten systems is disputed.In the present study,MF-AlF3(M=K,Cs)systems with molar ratios<1 were studied by in-situ Raman spectroscopy and molecular simulation.The results show that,in addition to AlF6^(3-),AlF5^(2-),and AlF4^-,the systems also contained Al2F-7^-.The characteristic bands in the Raman spectra belonging to Al2F-7^-were located at about 225 cm^-1,315 cm^-1,479 cm^-1,and 720 cm^-1.There are two possible structures of Al2F-7^-,which belong to the D3d and D3hpoint groups.Both of these structures are linear,and their single-point energies were found to differ by only 0.31 kcal/mol.展开更多
基金Project supported by the Zhejiang Provincial Natural Science Foundation of China (Grant No. LZ22A040003)the National Natural Science Foundation of China (Grant No. 52027809)。
文摘Electronic properties of two-dimensional(2D) materials can be strongly modulated by localized strain. The typical spatial resolution of conventional Kelvin probe force microscopy(KPFM) is usually limited in a few hundreds of nanometers, and it is difficult to characterize localized electronic properties of 2D materials at nanoscales. Herein, tip-enhanced Raman spectroscopy(TERS) is proposed to combine with KPFM to break this restriction. TERS scan is conducted on ReS2bubbles deposited on a rough Au thin film to obtain strain distribution by using the Raman peak shift. The localized contact potential difference(CPD) is inversely calculated with a higher spatial resolution by using strain measured by TERS and CPD-strain working curve obtained using conventional KPFM and atomic force microscopy. This method enhances the spatial resolution of CPD measurements and can be potentially used to characterize localized electronic properties of 2D materials.
基金supported by the National Science Foundation(Nos.1654746 and 1810453).
文摘Tip-enhanced Raman spectroscopy(TERS)imaging is a super-resolution imaging technique that features the merits of both surface-enhanced Raman spectroscopy(SERS)and scanning probe microscopy(SPM),such as the high chemical sensitivity from the former and the nanoscale spatial resolution from the latter.These advantages make TERS an essential nanospectroscopic characterization technique for chemical analysis,materials science,bio-sensing,etc.TERS probes,the most critical factor determining the TERS imaging quality,are expected to provide a highly confined electromagnetic hotspot with a minimized scattering background for the generation of Raman signals with high spatial resolution.After two decades of development,numerous probe design concepts have been proposed and demonstrated.This review provides a comprehensive overview of the state-of-the-art TERS probe designs,from the working mechanism to the practical performance.We start with reviewing the recent development of TERS configurations and the corresponding working mechanisms,including the SPM platforms,optical excitation/collection techniques,and probe preparation methods.We then review the emerging novel TERS probe designs,including the remote-excitation probes,the waveguide-based nanofocusing probes,the metal-coated nanofocusing probes,the nanowire-assisted selective-coupling probes,and the tapered metal-insulator-metal probes.Our discussion focuses on a few critical aspects,including the surface-plasmon-polariton(SPP)hotspot excitation technique,conversion efficiency,working frequency,and controllability.In the end,we review the latest TERS applications and give a perspective on the future of TERS.
基金We acknowledge financial support from the ERC program(Grant No.741431-2DNanoSpec).
文摘Chemistry on solid surfaces is central to many research areas of practical interest,such as synthesis,catalysis,electrochemistry,photochemistry,and materials science.A comprehensive understanding of the nanoscale on-surface chemistry involved in these areas is important for establishing composition-structure-performance relationships.With the rapid development of tip-enhanced Raman spectroscopy(TERS),it has become possible to investigate physical and chemical processes on suitable surfaces at the nanoscale level and in real space.In this review,after a brief introduction of the background of onsurface chemistry and TERS,we systematically discuss the progress in the application of TERS in this field.Our focus is the applications of TERS to nanoscale coordination processes,decomposition reactions,polymerization processes,electrochemical reactions,catalytic chemistry,and functionalization chemistry on solid surfaces.We conclude by discussing the future challenges and development of TERS techniques and related applications in on-surface chemistry.
基金supported by the National Natural Science Foundation of China (Grant Nos. 20673086, 20827003 and 20825313)the 973 Program(2009CB930703 and 2007CB935603)the Fok Ying Tung Foundation (101015)
文摘Tip-enhanced Raman spectroscopy (TERS) has been used to obtain the Raman signal of surface species on silicon single crystal surfaces without the necessity for surface enhancement by addition of Ag nanoparticles. By illuminating the hydrogen terminated silicon surface covered with a droplet of 4-vinylpyridine with UV light, a 4-ethylpyridine modified silicon surface can be easily obtained. By bringing a scanning tunneling microscope (STM) Au tip with a nanoscale tip apex to a distance of ca. 1 nm from the modified silicon surface, enhanced Raman signals of the silicon phonon vibrations and the surface-bonded 4-ethylpyridine were obtained. The Raman enhancement factor was estimated to be close to 107. By comparing the surface enhanced Raman scattering (SERS) signal obtained after surface enhancement with Ag nanoparticles and the TERS signal of the surface, the advantage of TERS over SERS for characterizing the surface species on substrates becomes apparent: TERS readily affords vibrational information about the system without disturbing it by surface enhancement. In this sense, TERS can be considered a truly non-invasive tool which is ideal for characterizing the actual surface species on substrates.
基金the immense support provided by the National Research Foundation of Korea(NRF)Grant funded by the Korean Government(MSIT)(RS-2023–00210114)the National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(2021M3D1A2051636)。
文摘Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.
基金the support from Scientific Research Project of Wuhan Polytechnic University(532100308).
文摘Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly important to effectively control the aging process of CSB,reduce quality deterioration,and promote the industrial production of CSB.Raman spectroscopy has been widely used in the study of food structure and properties due to its non-destructive and high-sensitivity characteristics,particularly demonstrating unique advantages in the analysis of starch structure.This study explored the possibility of analyzing the staling of CSB using Raman spectroscopy based on hardness and moisture content.Analysis of the correlation between the hardness of CSB and the full width at half maximum(FWHM)at 480 cm^(−1)during storage was conducted,and a significant positive correlation between them was found,with R^(2)above 0.8.Besides,nine characteristic peaks of CSB samples related to starch were selected for analysis.As the moisture content of CSB decreased,the peak intensities and areas of showed an upward trend during storage,with the best correlation coefficient above 0.8 revealed by linear regression analysis.Therefore,Raman spectra could be used as a potential method for the fast prediction of CSB staling.
基金supported by the National Natural Science Foundation of China (Grant No. 60427003)the National Basic Research Program of China, Project Research on Optical Detection in Nanometric Scale (Grant No. 2007CB936801)
文摘Raman spectroscopy is a powerful technique in chemical information characterization. However, this spectral method is subject to two obstacles in nano-material detection. One is diffraction limited spatial resolution, and the other is its inherent small Raman cross section and weak signaling. To resolve these problems, a new approach has been developed, denoted as tip-enhanced Raman spectroscopy (TERS). TERS is capable of high-resolution and high-sensitivity detection and demonstrated to be a promising spectroscopic and micro-topographic method to characterize nano-materials and nanostructures. In this paper, the principle and experimental system of TERS are discussed. The latest application of TERS in molecule detection, biological specimen identification, nanao-material characterization, and semi-conductor material determination with some specific experimental examples are presented.
基金supported by funds from the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(XDB 41000000)the National Natural Science Foundation of China(41973002,41772187)+1 种基金the Fundamental Research Funds for the Central UniversitiesNatural Sciences and Engineering Research Council of Canada(NSERC)Discovery Grant to J.M Hanchar(RGPIN/004649-2015)。
文摘Due to its ubiquitous occurrence in igneous,metamorphic,and sedimentary rocks and its wide application in geochronology and geochemistry,zircon has become the most widely used accessory mineral in the geological community.Nevertheless,the decay of U and Th causes radiation damage to the zircon structure,resulting in various degrees of metamictization,which can affect the accuracy of U–Pb dates and Hf and O isotope results.If the degree of zircon radiation damage can be quantified,the influence on geochemical analyses can be evaluated,and the results can be corrected more precisely.In this paper,synthetic and natural zircon crystals with different crystallization ages were selected for Raman spectroscopy analysis,cathodoluminescence imaging,and determination of the U and Th concentrations.The results show that Raman FWHM(full width at half bandmaximum)and Raman shift correlate with alpha dose(Da)ofzirconsfollowingtheseequations,FWHM=44.36(±2.32)×[1-exp(-2.74×Da)]-+1.7(±0.19),Raman Shift=-6.53×Da+1007.69.Analysis of synthetic zircon crystals shows that doped REEs(rare earth elements and P)can also lead to an increase in the FWHM.However,this effect can be ignored for natural zircon samples with REE contents at a normal level of hundreds to a few thousand ppm.The FWHM and Raman shift can be used as proxies to measure the degree of zircon radiation damage.Using the updated equations to calculate the latest age when zircon began to accumulate radiation damage,a more accurate and more meaningful“radiation damage age”can be obtained.
基金support received from the Medicine and Engineering Cross Research Foundation of Shanghai Jiao Tong University(Project No.YG2022QN047)as well as the National Nature Science Foundation of China(Grant No.62027824)the National Key Research and Development Program of China(2019YFC1604604).
文摘The skin is the largest organ in humans.It comprises about 16%of our body.Many diseases originate from the skin,including acne vulgaris,skin cancer,fungal skin disease,etc.As a common skin cancer in China,melanoma alone grows at year rate of nearly 4%.Therefore,it is crucial to develop an objective,reliable,accurate,non-invasive,and easy-to-use diagnostic method for skin diseases to support clinical decision-making.Raman spectroscopy is a highly specic imaging technique,which is sensitive,even to the single-cell level in skin diagnosis.Raman spectroscopy provides a pattern of signals with narrow bandwidths,making it a common and essential tool for researching individual characteristics of skin cells.Raman spectroscopy already has a number of clinical applications,including in thyroid,cervical and colorectal cancer.This review will introduce the advantages and recent developments in Raman spectroscopy,before focusing on the advances in skin diagnosis,including the advantages,methods,results,analysis,and notications.Finally,we discuss the current limitations and future progress of Raman spectroscopy in the context of skin diagnosis.
基金Supported by MEXT KAKENHI,JP17K09022 and JP20K07643.
文摘BACKGROUND Cancer detection is a global research focus,and novel,rapid,and label-free techniques are being developed for routine clinical practice.This has led to the development of new tools and techniques from the bench side to routine clinical practice.In this study,we present a method that uses Raman spectroscopy(RS)to detect cancer in unstained formalin-fixed,resected specimens of the esophagus and stomach.Our method can record a clear Raman-scattered light spectrum in these specimens,confirming that the Raman-scattered light spectrum changes because of the histological differences in the mucosal tissue.AIM To evaluate the use of Raman-scattered light spectrum for detecting endoscopically resected specimens of esophageal squamous cell carcinoma(SCC)and gastric adenocarcinoma(AC).METHODS We created a Raman device that is suitable for observing living tissues,and attempted to acquire Raman-scattered light spectra in endoscopically resected specimens of six esophageal tissues and 12 gastric tissues.We evaluated formalin-fixed tissues using this technique and captured shifts at multiple locations based on feasibility,ranging from six to 19 locations 200 microns apart in the vertical and horizontal directions.Furthermore,a correlation between the obtained Raman scattered light spectra and histopathological diagnosis was performed.RESULTS We successfully obtained Raman scattered light spectra from all six esophageal and 12 gastric specimens.After data capture,the tissue specimens were sent for histopathological analysis for further processing because RS is a label-free methodology that does not cause tissue destruction or alterations.Based on data analysis of molecular-level substrates,we established cut-off values for the diagnosis of esophageal SCC and gastric AC.By analyzing specific Raman shifts,we developed an algorithm to identify the range of esophageal SCC and gastric AC with an accuracy close to that of histopathological diagnoses.CONCLUSION Our technique provides qualitative information for real-time morphological diagnosis.However,further in vivo evaluations require an excitation light source with low human toxicity and large amounts of data for validation.
基金Project supported by the National Natural Science Foundation of China (Grant No. 61911530695)the Key Research and Development Project of Shaanxi Province, China (Grant No. 2023-YBSF-671)。
文摘As one type of spatially offset Raman spectroscopy(SORS), inverse SORS is particularly suited to in vivo biomedical measurements due to its ring-shaped illumination scheme. To explain inhomogeneous Raman scattering during in vivo inverse SORS measurements, the light–tissue interactions when excitation and regenerated Raman photons propagate in skin tissue were studied using Monte Carlo simulation. An eight-layered skin model was first built based on the latest transmission parameters. Then, an open-source platform, Monte Carlo e Xtreme(MCX), was adapted to study the distribution of 785 nm excitation photons inside the model with an inverse spatially shifted annular beam. The excitation photons were converted to emission photons by an inverse distribution method based on excitation flux with spatial offsets Δs of 1 mm, 2 mm, 3 mm and 5 mm. The intrinsic Raman spectra from separated skin layers were measured by continuous linear scanning to improve the simulation accuracy. The obtained results explain why the spectral detection depth gradually increases with increasing spatial offset, and address how the intrinsic Raman spectrum from deep skin layers is distorted by the reabsorption and scattering of the superficial tissue constituents. Meanwhile, it is demonstrated that the spectral contribution from subcutaneous fat will be improved when the offset increases to 5 mm, and the highest detection efficiency for dermal layer spectral detection could be achieved when Δs = 2 mm. Reasonably good matching between the calculated spectrum and the measured in vivo inverse SORS was achieved, thus demonstrating great utility of our modeling method and an approach to help understand the clinical measurements.
基金This work was financially supported by the National Natural Science Foundation of China(22075074)Outstanding Young Scientists Research Funds from Hunan Province(2020JJ2004)+3 种基金Major Science and Technology Program of Hunan Province(2020WK2013)Natural Science Foundation of Hunan Province(2020JJ5035)National Natural Science Foundation of China(Grant No.11704185)the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure(SKL201802SIC).
文摘Bronze phase titanium dioxide(TiO_(2)(B))could be a promising high-power anode for lithium ion battery.However,TiO_(2)(B)is a metastable material,so the as-synthesized samples are inevitably accompanied by the existence of anatase phases.It has been found that the TiO_(2)(B)'s purity is positively correlated with its electrochemical performance.Herein,we have established an accurate quantification of the TiO_(2)(B)/anatase ratio,by figuring out the function between the purity of TiO_(2)(B)phase in the high purity range and its Raman spectra features in combination of the calibration by the synchrotron radiation X-ray diffraction(XRD).Compared with the time-consuming electrochemical method,the rapid,sensitive and non-destructive features of Raman spectroscopy have made it a promising candidate for determining the purity of TiO_(2)(B).Further,the correlations developed in this work should be instructive in synthesizing pure TiO_(2)(B)and furthermore optimizing its electrochemical charge storage properties.
基金We gratefully acknowledge the support from the National Natural Science Foundation of China(Nos.21735006 and 21127901),and the CAS Key Technology Talent Program.
文摘Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.
文摘The application of vibrational spectroscopy in the pharmaceutical industry is widely investigated, from the quality assurance of the product during the production process control to the final products’ quality control and the authentication of products on the markets. This study focuses on non-contact and noninvasive detection and identification of pain-relievers at 1-5 meters standoff distances. The specimens analyzed include standard laboratory-grade active ingredients and commercially available pain relievers in powder, solid and liquid forms. All the remote measurements captured revealed the Raman signatures of the specimens, with varying peak intensities. To correlate the band intensities captured with the standoff distances between the laser source and the specimens, the intensity ratios of the two prominent peaks of the laboratory grade reference active ingredient (1607 and 1319 cm<sup>-1</sup>) normalized with 1319 cm<sup>-1</sup> are used. The results of the study suggest the viability of standoff Raman spectroscopy for routine monitoring and identification of pharma-ceuticals, including counterfeit pain relievers.
基金financially supported by the National Natural Science Foundation of China(31972149)funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnologythe Dodd-Walls Centre for Photonic and Quantum Technologies。
文摘Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
基金supported by the National Key Research and Development Program of China(Grant No.2016YFA0301204)the National Natural Science Foundation of China(Grant Nos.11604326,11434010,11474277,and 11225421)
文摘Angle-resolved polarized Raman(ARPR) spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations: 1) to change the polarization of the incident laser, 2) to rotate the sample, and 3) to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite(HOPG) exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.
基金supported partially by grants from the National Natural Sciences Foundation of China(Nos.81370705 and 81070487)China Postdoctoral Science Foundation(No.2013M542191)the Natural Science Foundation of Guangdong Province,China(Nos.S2012010009140 and S2013040016159)
文摘Oxidative stress is implicated in male infertility and significantly higher reactive oxygen species are detected in 25% of infertile males. Although different agents of various alternative medicines, including traditional Chinese medicine, have been tried with varying success, evidence remains limited on whether and how much herbs or supplements might help increase the anti-oxidant ability of the sperm. This study examined the anti-oxidative effects of icariin, a flavonoid isolated from Herba Epimedii, on the human sperm. We prepared the FeSO4/H202-damaged human sperms, which were co-cultured with icariin in vitro, and then observed the changes of the sperm by employing Raman mi- cro-spectroscopy. The results showed that Raman mapping with a 514 nm excitation laser allowed clear differentiation of the nucleus, neck, and, in particular, the mitochondria-rich middle piece of a human sperm cell. The effect oficariin on different organelles of the sperm was quantified by localized spectral Raman signatures obtained within milli-seconds, and icariin could keep the "Raman fingerprint" of the human sperm the same as the control groups, suggesting that icariin could protect the human sperm from being damaged by FeSO4/H202. Icariin may serve as a tonifying and replenishing agent of herbal origin for enhancing reproductive fimctions.
基金the National Natural Science Foundation of China(grant no.51474060)the National Key R&D Program of China(grant no.2017 YFC0805100)+1 种基金the National Natural Science Foundation of Liaoning Province(China)(grant no.2019-MS-129)the Fundamental Research Funds for the Central Universities of China(grant no.N162502002).
文摘The molten mixtures of alkali metal fluorides and aluminum fluoride are applied as aluminum electrolytes or brazing fluxes.However,the presence of Al2F-7^-in such molten systems is disputed.In the present study,MF-AlF3(M=K,Cs)systems with molar ratios<1 were studied by in-situ Raman spectroscopy and molecular simulation.The results show that,in addition to AlF6^(3-),AlF5^(2-),and AlF4^-,the systems also contained Al2F-7^-.The characteristic bands in the Raman spectra belonging to Al2F-7^-were located at about 225 cm^-1,315 cm^-1,479 cm^-1,and 720 cm^-1.There are two possible structures of Al2F-7^-,which belong to the D3d and D3hpoint groups.Both of these structures are linear,and their single-point energies were found to differ by only 0.31 kcal/mol.