In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

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.

A seven-crystal spectrometer for high-energy resolution X-ray spectroscopy at Shanghai Synchrotron Radiation Facility

A Johann-type X-ray spectrometer was successfully developed at the hard X-ray branch(in-vacuum undulator with a 24-mm periodic length)of the energy material beamline(E-line)at the Shanghai Synchrotron Radiation Facility(SSRF).This spectrometer was utilized to implement X-ray emission spectroscopy(XES),high-energy resolution fluorescence-detected X-ray absorption spectroscopy(HERFD-XAS),and resonant inelastic X-ray scattering.Seven spherically bent crystals were positioned on the respective vertical 500-mm-diameter Rowland circles,adopting an area detector to increase the solid angle to 1.75%of 4πsr,facilitating the study of low-concentrate systems under complex reaction conditions.Operated under the atmosphere pressure,the spectrometer covers the energy region from 3.5 to 18 keV,with the Bragg angle ranging from 73°to 86°during vertical scanning.It offers a promised energy resolution of sub-eV(XES)and super-eV(HERFD-XAS).Generally,these comprehensive core-level spectroscopy methods based on hard X-rays at the E-line with an extremely high photon flux can meet the crucial requirements of a green energy strategy.Moreover,they provide substantial support for scientific advances in fundamental research.

Theoretical characterization of the adsorption configuration of pyrrole on Si(100)surface by x-ray spectroscopy

The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS spectra of these adsorption configurations have been calculated by using the density functional theory(DFT)method and fullcore hole(FCH)approximation to investigate the relationship between the adsorption configurations and the spectra.The result shows that the XPS and NEXAFS spectra are structurally dependent on the configurations of pyrrole absorbed on the Si(100)surface.Compared with the XPS,the NEXAFS spectra are relatively sensitive to the adsorption configurations and can accurately identify them.The NEXAFS decomposition spectra produced by non-equivalent carbon atoms have also been calculated and show that the spectral features vary with the diverse types of carbon atoms and their structural environments.

Application of proton magnetic resonance spectroscopy in metabolic alterations of prefrontal white and gray matter in depression adolescents

BACKGROUND Cases of depression among adolescents are gradually increasing.The study of the physiological basis of cognitive function from a biochemical perspective has therefore been garnering increasing attention.Depression has been hypothesized to be associated with the brain biochemical metabolism of the anterior cingulate gyrus,frontal lobe white matter,and the thalamus.AIM To explore the application of proton magnetic resonance spectroscopy(1H-MRS)in the metabolic alterations in the prefrontal white matter(PWM)and gray matter(GM)in adolescents with depression.METHODS 1H-MRS was performed for semi-quantitative analysis of the biochemical metabolites N-acetylaspartate(NAA),choline(Cho)complexes,creatine(Cr),and myoinositol(mI)in bilateral PWM,anterior cingulate GM,and thalami of 31 adolescent patients with depression(research group)and 35 healthy adolescents(control group),and the NAA/Cr,Cho/Cr,and mI/Cr ratios were calculated.Meanwhile,Hamilton Depression Scale(HAMD)and Wechsler Memory Scale were used to assess the degree of depression and memory function in all adolescents.The correlation of brain metabolite levels with scale scores was also analyzed.RESULTS The research group had markedly higher HAMD-24 scores and lower memory quotient(MQ)compared with the control group(P<0.05).Adolescents with depression were found to have lower bilateral PWM NAA/Cr and Cho/Cr ratios compared with healthy adolescents(P<0.05).The mI/Cr ratios were found to be similar in both groups(P>0.05).The bilateral anterior cingulate GM NAA/Cr,Cho/Cr,and mI/Cr also did not demonstrate marked differences(P>0.05).No statistical inter-group difference was determined in NAA/Cr of the bilateral thalami(P>0.05),while bilateral thalamic Cho/Cr and mI/Cr were reduced in teenagers with depression compared with healthy adolescents(P<0.05).A significant negative correlation was observed between the HAMD-24 scores in adolescents with depression with bilateral PWM NAA/Cr and Cho/Cr and were inversely linked to bilateral thalamic Cho/Cr and mI/Cr(P<0.05).In adolescents with depressions,MQ positively correlated with right PWH NAA/Cr,left PWH Cho/Cr,and bilateral thalamic Cho/Cr and mI/Cr.CONCLUSION PWM and thalamic metabolic abnormalities might influence teen depression,and the reduction in bilateral PWM NAA/Cr and Cho/Cr could be related to the neuropathology of adolescents with depression suffering from memory impairment.There exists a possibility of dysfunction of nerve cell membrane phospholipids in the thalami of adolescent patients with depression.

Investigation of the sodium storage mechanism of iron fluoride hydrate cathodes using X-ray absorption spectroscopy and mossbauer spectroscopy

Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.

Laser spectroscopy imaging technique coupled withnanomaterials for cancer diagnosis: A review

Laser spectroscopic imaging techniques have received tremendous attention in the-eld of cancer diagnosis due to their high sensitivity,high temporal resolution,and short acquisition time.However,the limited tissue penetration of the laser is still a challenge for the in vivo diagnosis of deep-seated lesions.Nanomaterials have been universally integrated with spectroscopic imaging techniques for deeper cancer diagnosis in vivo.The components,morphology,and sizes of nanomaterials are delicately designed,which could realize cancer diagnosis in vivo or in situ.Considering the enhanced signal emitting from the nanomaterials,we emphasized their combination with spectroscopic imaging techniques for cancer diagnosis,like the surface-enhanced Raman scattering(SERS),photoacoustic,fluorescence,and laser-induced breakdown spectroscopy(LIBS).Applications ofthe above spectroscopic techniques offer new prospectsfor cancer diagnosis.

In situ high-pressure wide-angle hard x-ray photon correlation spectroscopy:A versatile tool probing atomic dynamics of extreme condition matter

With the advent of new synchrotron radiation x-ray sources that provide a significantly enhanced coherent flux,high-energy x-ray photon correlation spectroscopy measurements can be performed on materials in a diamond anvil cell.Essential information on atomic dynamics that was previously inaccessible can be obtained for various novel phenomena emerging under extreme conditions.This article discusses the importance,feasibility,and experimental details of this technique,as well as the opportunities that it offers to address critical scientific challenges.

Exploring battery material failure mechanisms through synchrotron X-ray characterization techniques

Rechargeable battery cycling performance and related safety have been persistent concerns.It is crucial to decipher the capacity fading induced by electrode material failure via a range of techniques.Among these,synchrotron-based X-ray techniques with high flux and brightness play a key role in understanding degradation mechanisms.In this comprehensive review,we summarize recent advancements in degra-dation modes and mechanisms that were revealed by synchrotron X-ray methodologies.Subsequently,an overview of X-ray absorption spectroscopy and X-ray scattering techniques is introduced for charac-terizing failure phenomena at local coordination atomic environment and long-range order crystal struc-ture scale,respectively.At last,we envision the future of exploring material failure mechanism.

Functional near-infrared spectroscopy in non-invasive neuromodulation

Non-invasive cerebral neuromodulation technologies are essential for the reorganization of cerebral neural networks,which have been widely applied in the field of central neurological diseases,such as stroke,Parkinson’s disease,and mental disorders.Although significant advances have been made in neuromodulation technologies,the identification of optimal neurostimulation paramete rs including the co rtical target,duration,and inhibition or excitation pattern is still limited due to the lack of guidance for neural circuits.Moreove r,the neural mechanism unde rlying neuromodulation for improved behavioral performance remains poorly understood.Recently,advancements in neuroimaging have provided insight into neuromodulation techniques.Functional near-infrared spectroscopy,as a novel non-invasive optical brain imaging method,can detect brain activity by measuring cerebral hemodynamics with the advantages of portability,high motion tole rance,and anti-electromagnetic interference.Coupling functional near-infra red spectroscopy with neuromodulation technologies offe rs an opportunity to monitor the cortical response,provide realtime feedbac k,and establish a closed-loop strategy integrating evaluation,feedbac k,and intervention for neurostimulation,which provides a theoretical basis for development of individualized precise neuro rehabilitation.We aimed to summarize the advantages of functional near-infra red spectroscopy and provide an ove rview of the current research on functional near-infrared spectroscopy in transcranial magnetic stimulation,transcranial electrical stimulation,neurofeedback,and braincomputer interfaces.Furthermore,the future perspectives and directions for the application of functional near-infrared spectroscopy in neuromodulation are summarized.In conclusion,functional near-infrared spectroscopy combined with neuromodulation may promote the optimization of central pellral reorganization to achieve better functional recovery form central nervous system diseases.

Differential diagnosis of Crohn’s disease and intestinal tuberculosis based on ATR-FTIR spectroscopy combined with machine learning

BACKGROUND Crohn’s disease(CD)is often misdiagnosed as intestinal tuberculosis(ITB).However,the treatment and prognosis of these two diseases are dramatically different.Therefore,it is important to develop a method to identify CD and ITB with high accuracy,specificity,and speed.AIM To develop a method to identify CD and ITB with high accuracy,specificity,and speed.METHODS A total of 72 paraffin wax-embedded tissue sections were pathologically and clinically diagnosed as CD or ITB.Paraffin wax-embedded tissue sections were attached to a metal coating and measured using attenuated total reflectance fourier transform infrared spectroscopy at mid-infrared wavelengths combined with XGBoost for differential diagnosis.RESULTS The results showed that the paraffin wax-embedded specimens of CD and ITB were significantly different in their spectral signals at 1074 cm^(-1) and 1234 cm^(-1) bands,and the differential diagnosis model based on spectral characteristics combined with machine learning showed accuracy,specificity,and sensitivity of 91.84%,92.59%,and 90.90%,respectively,for the differential diagnosis of CD and ITB.CONCLUSION Information on the mid-infrared region can reveal the different histological components of CD and ITB at the molecular level,and spectral analysis combined with machine learning to establish a diagnostic model is expected to become a new method for the differential diagnosis of CD and ITB.

A rened analytical model for reconstruction problems in diuse reectance spectroscopy

A rened analytical model of spatially resolved diffuse reectance with small source-detector separations(SDSs)for the in vivo skin studies is proposed.Compared to the conventional model developed by Farrell et al.,it accounts for the limited acceptance angle of the detectorber.The rened model is validated in the wide range of optical parameters by Monte Carlo simulations of skin diffuse reectance at SDSs of units of mm.Cases of uniform dermis and two-layered epidermis-dermis structures are studied.Higher accuracy of the rened model compared to the conventional one is demonstrated in the separate,constraint-free reconstruction of absorption and reduced scattering spectra of uniform dermis from the Monte Carlo simulated data.In the case of epidermis-dermis geometry,the recovered values of reduced scattering in dermis are overestimated and the recovered values of absorption are underestimated for both analytical models.Presumably,in the presence of a thin mismatched topical layer,only the effective attenuation coe±cient of the bottom layer can be accurately recovered using a diffusion theorybased analytical model while separate reconstruction of absorption and reduced scattering fails due to the inapplicability of the method of images.These-ndings require implementation of more sophisticated models of light transfer in inhomogeneous media in the recovery algorithms.

Incorporating empirical knowledge into data-driven variable selection for quantitative analysis of coal ash content by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy(LIBS)has become a widely used atomic spectroscopic technique for rapid coal analysis.However,the vast amount of spectral information in LIBS contains signal uncertainty,which can affect its quantification performance.In this work,we propose a hybrid variable selection method to improve the performance of LIBS quantification.Important variables are first identified using Pearson's correlation coefficient,mutual information,least absolute shrinkage and selection operator(LASSO)and random forest,and then filtered and combined with empirical variables related to fingerprint elements of coal ash content.Subsequently,these variables are fed into a partial least squares regression(PLSR).Additionally,in some models,certain variables unrelated to ash content are removed manually to study the impact of variable deselection on model performance.The proposed hybrid strategy was tested on three LIBS datasets for quantitative analysis of coal ash content and compared with the corresponding data-driven baseline method.It is significantly better than the variable selection only method based on empirical knowledge and in most cases outperforms the baseline method.The results showed that on all three datasets the hybrid strategy for variable selection combining empirical knowledge and data-driven algorithms achieved the lowest root mean square error of prediction(RMSEP)values of 1.605,3.478 and 1.647,respectively,which were significantly lower than those obtained from multiple linear regression using only 12 empirical variables,which are 1.959,3.718 and 2.181,respectively.The LASSO-PLSR model with empirical support and 20 selected variables exhibited a significantly improved performance after variable deselection,with RMSEP values dropping from 1.635,3.962 and 1.647 to 1.483,3.086 and 1.567,respectively.Such results demonstrate that using empirical knowledge as a support for datadriven variable selection can be a viable approach to improve the accuracy and reliability of LIBS quantification.

Energy-dispersive X-ray Spectroscopy for the Quantitative Analysis of Pyrite Thin Specimens

To explore ways to improve the accuracy of quantitative analysis of samples in the micrometer to nanometer range of magnitudes,we adopted analytical transmission electron microscopy(AEM/EDS)for qualitative and quantitative analysis of pyrite materials.Additionally,the k factor of pyrite is calculated experimentally.To develop an appropriate non-standard quantitative analysis model for pyrite materials,the experimentally calculated k factor is compared with that estimated from the non-standard quantitative analytical model of the instrument software.The experimental findings demonstrate that the EDS attached to a TEM can be employed for precise quantitative analysis of micro-and nanoscale regions of pyrite materials.Furthermore,it serves as a reference for improving the results of the EDS quantitative analysis of other sulfides.

Fast X-ray imaging beamline at SSRF

The fast X-ray imaging beamline(BL16U2)at Shanghai Synchrotron Radiation Facility(SSRF)is a new beamline that provides X-ray micro-imaging capabilities across a wide range of time scales,spanning from 100 ps toμs and ms.This beamline has been specifically designed to facilitate the investigation of a wide range of rapid phenomena,such as the deformation and failure of materials subjected to intense dynamic loads.In addition,it enables the study of high-pressure and high-speed fuel spray processes in automotive engines.The light source of this beamline is a cryogenic permanent magnet undulator(CPMU)that is cooled by liquid nitrogen.This CPMU can generate X-ray photons within an energy range of 8.7-30 keV.The beamline offers two modes of operation:monochromatic beam mode with a liquid nitrogen-cooled double-crystal monochromator(DCM)and pink beam mode with the first crystal of the DCM out of the beam path.Four X-ray imaging methods were implemented in BL16U2:single-pulse ultrafast X-ray imaging,microsecond-resolved X-ray dynamic imaging,millisecond-resolved X-ray dynamic micro-CT,and high-resolution quantitative micro-CT.Furthermore,BL16U2 is equipped with various in situ impact loading systems,such as a split Hopkinson bar system,light gas gun,and fuel spray chamber.Following the completion of the final commissioning in 2021 and subsequent trial operations in 2022,the beamline has been officially available to users from 2023.

Near Infrared Spectroscopy (NIRS) Model-Based Prediction for Protein Content in Cowpea

Cowpea (Vigna unguiculata L. Walp) is a multi-purpose legume with high quality protein for human consumption and livestock. The objective of this work was to develop near-infrared spectroscopy (NIRS) prediction models to estimate protein content in cowpea. A total of 116 cowpea breeding lines with a wide range of protein contents (19.28 % to 32.04%) were selected to build the model using whole seed and ground seed samples. Partial least-squares discriminant analysis (PLS-DA) regression technique with different pre-treatments (derivatives, standard normal variate, and multiplicative scatter correction) were carried out to develop the protein prediction model. Results showed: 1) spectral plots of both the whole seed and ground seed showed higher spectral scatter at higher wavelengths (>1450 nm), 2) data pre-processing affects prediction accuracy for bot whole seed and ground seed samples, 3) prediction using ground seed samples (0.64 R2 0.85) is better than the whole seed (0.33 R2 0.78), and 4) the data pre-processing second derivative with standard normal variate has the best prediction (R2_whole seed = 0.78, R2_ground seed = 0.85). The results will be of interest in cowpea breeding programs aimed at improving total seed protein content.

Cosmic Ray-driven Bioenergetics for Life in Molecular Clouds

According to models such as panspermia or the Nebula-Relay hypothesis,the ancestors of life on Earth once lived in molecular clouds.Then what are the energy source and bioenergetics for such lifeforms?A new bioenergetic mechanism powered by cosmic ray ionization of hydrogen molecules is proposed and its relation with the origin of chemiosmosis is also discussed in this paper.Based on this mechanism,the Last Universal Common Ancestor may be a type of lifeform that utilizes hydrogen molecules as donors of electron transport chains.

Genetic Enhancement of Indigenous Cowpea with Gamma-Ray Induced Trait Variation

Production of cowpea (Vigna unguiculata (L.) Walp.), a staple legume crop in Sub-Saharan Africa, faces challenges due to biotic and abiotic constraints. Induced mutagenesis was deployed to create genetic variation in two cowpea varieties (KVX396-4-5-2D and Moussa local). The radio-sensitivity tests led to determe the lethal dose 50 (LD50) corresponding to 230 Gy and 220 Gy for KVX396-4-5-2D and Moussa local varieties, respectively. Dried seeds (M0) of each variety were gamma-ray irradiated with LD50 − 50, LD50 and LD50 + 50. M1 seeds were advanced to generate M2, M3 and M4 mutants using the single-seed-descent method. M4 mutant lines were evaluated in rain-fed conditions using a randomized complete block design to assess phenotypic differences. Data on seven qualitative and eleven quantitative traits were collected. The results indicated that the mutation induced variability in three qualitative traits: in KVX 396-4-5-2D mutant lines, with flower and seed color frequencies at 2.61% and 0.56% respectively, and pod dehiscence at a frequency of 0.24%. While in Moussa local mutants, a pod color changed at a frequency of 17%. ANOVA results revealed significant differences between mutants of both varieties for all quantitative traits, including photosynthetic parameters. Positive correlations were observed between leaf diameter and 100-seed weight, and between branch number and 100-seed weight. Hierarchical clustering revealed three clusters among KVX 396-4-5-2D mutants and six clusters among Moussa local mutants. Early maturity and high foliage were induced traits in Cluster 3 of KVX 396-4-5-2D mutants while high hundred-seed weight was induced in Cluster 6 of Moussa local mutants.

Study on the Performance of the GRANDProto300 Particle Detector Array by Simulation

The Giant Radio Array for Neutrino Detection(GRAND)is a proposed large-scale observatory designed to detect cosmic rays,gamma-rays,and neutrinos with energies exceeding 100 Pe V.The GRANDProto300 experiment is proposed as the early stage of the GRAND project,consisting of a hybrid array of radio antennas and scintillator detectors.The latter,as a mature and traditional detector,is used to cross-check the nature of the candidate events selected from radio observations.In this study,we developed a simulation software called G4GRANDProto300,based on the Geant4 software package,to optimize the spacing of the scintillator detector array and to investigate its effective area.The analysis was conducted at various zenith angles under different detector spacings,including 300,500,600,700,and 900 m.Our results indicate that,for large zenith angles used to search for cosmic-ray in the GRAND project,the optimized effective area is with a detector spacing of 500 m.The G4GRANDProto300 software that we developed could be used to further optimize the layout of the particle detector array in future work.

A dual-route optical emission spectroscopy diagnostic with wide spectral range and high wavelength resolution on HL-2A tokamak

A dual-route optical emission spectroscopy(D-OES)diagnostic is newly developed to monitor the optical emission from the X-point plasma region on the HL-2 A tokamak.This diagnostic is composed of an imaging system,a beam-splitting system for dual-route measurements,fiber bundles,a spectrometer system,and a control and acquisition system.One route is used to obtain wide-spectral-range spectra,and the other route is used to acquire high-wavelengthresolution line shapes.The spectral resolution of the wide-range spectrometers is 0.8 nm with a coverage of 800 nm(@200-1000 nm).The spectral resolution of the high-resolution spectrometer is 0.01 nm with a coverage of 6 nm(@200-660 nm).The spatial resolution of each route of D-OES is about 4 cm with 11 channels.The temporal resolution is 16 ms at maximum in the single-channel mode.Wide-range spectra(containing Balmer series and a Fulcher band)and highly resolved Ha line shapes are obtained by D-OES in the hydrogen glow discharge in the lab.D-OES measurements are carried out in the high-density deuterium experiments of HL-2A.The electron density n_(e)and deuterium temperature T_(D) in the X-point multifaceted asymmetric radiation from the edge(MARFE)region are derived simultaneously by fitting the measured D_(a) shape.The density n_(e)is observed to increase from~8.7×10^(18)m^(-3)to~7.8×10^(19)m^(-3),and the temperature T_(D)drops from~14.4 eV to~2.3 eV after the onset of MARFE in the discharge#38260.

Visualizing the electronic structure of kagome magnet LuMn6Sn6 by angle-resolved photoemission spectroscopy

Searching for the dispersionless flat band(FB)in quantum materials,especially in topological systems,becomes an interesting topic.The kagome lattice is an ideal platform for such exploration because the FB can be naturally induced by the underlying destructive interference.Nevertheless,the magnetic kagome system that hosts the FB close to the Fermi level(EF)is exceptionally rare.Here,we study the electronic structure of a kagome magnet LuMn6Sn6 by combining angleresolved photoemission spectroscopy and density functional theory calculations.The observed Fermi-surface topology and overall band dispersions are similar to previous studies of the XMn6Sn6(X=Dy,Tb,Gd,Y)family of compounds.We clearly observe two kagome-derived FBs extending through the entire Brillouin zone,and one of them is located just below EF.The photon-energy-dependent measurements reveal that these FBs are nearly dispersionless along the kz direction as well,supporting the quasi-two-dimensional character of such FBs.Our results complement the XMn6Sn6 family and demonstrate the robustness of the FB features across this family.