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
Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber,linewidth and intensity,and has found very broad applications in characterizing the energy and charge transport in nanomateria...Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber,linewidth and intensity,and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade.The temperature coefficients of these Raman properties are highly material-dependent,and are subjected to local optical scattering influence.As a result,Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity.Here,a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial(nm WS_(2) film in this work)from 170 to 470 K.A 532 nm laser(2.33 eV photon energy)is used to conduct the Raman experiment.Its photon energy is very close to the excitonic transition energy of WS_(2) at temperatures close to room temperature.A parameter,termed resonance Raman ratio(R3)Ω=I_(A1g)/IE_(2g) is introduced to combine the temperature effects on resonance Raman scattering for the A_(1g) and E_(2g) modes.Ω has a change of more than two orders of magnitude from 177 to 477 K,and such change is independent of film thickness and local optical scattering.It is shown that when Ω is varied by 1%,the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures,respectively.Based on Ω,the in-plane thermal conductivity(k)of a∼25 nm-thick suspended WS_(2) film is measured using our energy transport state-resolved Raman(ET-Raman).k is found decreasing from 50.0 to 20.0 Wm^(−1) K^(−1) when temperature increases from 170 to 470 K.This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman.The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization,non-destructive evaluation,and manufacturing monitoring.展开更多
This study aimed to explore the application of surface-enhanced Raman scattering(SERS)in the rapid diagnosis of gastric cancer.The SERS spectra of 68 serum samples from gastric cancer patients and healthy volunteers w...This study aimed to explore the application of surface-enhanced Raman scattering(SERS)in the rapid diagnosis of gastric cancer.The SERS spectra of 68 serum samples from gastric cancer patients and healthy volunteers were acquired.The characteristic ratio method(CRM)and principal component analysis(PCA)were used to differentiate gastric cancer serum from normal serum.Compared with healthy volunteers,the serum SERS intensity of gastric cancer patients was relatively high at 722 cm^(-1),while it was relatively low at 588,644,861,1008,1235,1397,1445 and 1586 cm^(-1).These results indicated that the relative content of nucleic acids in the serum of gastric cancer patients rises while the relative content of amino acids and carbohydrates decreases.In PCA,the sensitivity and specificity of discriminating gastric cancer were 94.1%and 94.1%,respectively,with the accuracy of 94.1%.Based on the intensity ratios of four characteristic peaks at 722,861,1008 and 1397 cm^(-1),CRM presented the diagnostic sensitivity and specificity of 100%and 97.4%,respectively,and the accuracy of 98.5%.Therefore,the three peak intensity ratios of I_(722)/I_(861),I_(722)/I_(1008)and I_(722)/I_(1397)can be considered as biologicalfingerprint information for gastric cancer diagnosis and can rapidly and directly reflect the physiological and pathological changes associated with gastric cancer development.This study provides an important basis and standards for the early diagnosis of gastric cancer.展开更多
Indium sulfide （InzS3） thin films were prepared by chemical spray pyrolysis technique from solutions with different [S]/[In] ratios on glass substrates at a constant temperature of 250 ~C. Thin films were characteri...Indium sulfide （InzS3） thin films were prepared by chemical spray pyrolysis technique from solutions with different [S]/[In] ratios on glass substrates at a constant temperature of 250 ~C. Thin films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, atomic force microscopy （AFM）, energy disper- sive X-ray spectroscopy （EDS）, Raman spectroscopy and optical transmittance spectroscopy. All samples exhibit a polycrystalline structure with a preferential orientation along （0, 0, 12）. A good stoichiometry was attained for all samples. The morphology of thin film surfaces, as seen by SEM, was dense and no cracks or pinholes were ob- served. Raman spectroscopy analysis shows active modes belonging to j3-1naS3 phase. The optical transmittance in the visible range is higher than 60% and the band gap energy slightly increases with the sulfur to indium ratio, attaining a value of 2.63 eV for [S]/[In] ： 4.5.展开更多
The amide A band of protein is sensitive to the hydrogen bands of amide groups of proteins. However, it is hard to distinguish the amide A band of aqueous protein in situ directly, since it overlaps with O-H stretchin...The amide A band of protein is sensitive to the hydrogen bands of amide groups of proteins. However, it is hard to distinguish the amide A band of aqueous protein in situ directly, since it overlaps with O-H stretching vibration of water. In this work, we presented a new analytical method of Raman ratio spectrum, which can extract the amide A band of proteins in water. To obtain the Raman ratio spectrum, the Raman spectrum of aqueous protein was divided by that of pure water. A mathematical simulation was employed to examine whether Raman ratio spectrum is effective. Two kinds of protein, lysozyme and （^-chymotrypsin were employed. The amide A bands of them in water were extracted from Raman ratio spectra. Additionally, the process of thermal denaturation of lysozyme was detected from Raman ratio spectrum. These results demonstrated the Raman ratio spectra could be employed to study the amide A modes of proteins in water.展开更多
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Support of this work by National Science Foundation(CBET1930866 and CMMI2032464 for X W)National Natural Science Foundation of China(No.52106220 for S X and No.51906161 for Y X)。
文摘Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber,linewidth and intensity,and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade.The temperature coefficients of these Raman properties are highly material-dependent,and are subjected to local optical scattering influence.As a result,Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity.Here,a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial(nm WS_(2) film in this work)from 170 to 470 K.A 532 nm laser(2.33 eV photon energy)is used to conduct the Raman experiment.Its photon energy is very close to the excitonic transition energy of WS_(2) at temperatures close to room temperature.A parameter,termed resonance Raman ratio(R3)Ω=I_(A1g)/IE_(2g) is introduced to combine the temperature effects on resonance Raman scattering for the A_(1g) and E_(2g) modes.Ω has a change of more than two orders of magnitude from 177 to 477 K,and such change is independent of film thickness and local optical scattering.It is shown that when Ω is varied by 1%,the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures,respectively.Based on Ω,the in-plane thermal conductivity(k)of a∼25 nm-thick suspended WS_(2) film is measured using our energy transport state-resolved Raman(ET-Raman).k is found decreasing from 50.0 to 20.0 Wm^(−1) K^(−1) when temperature increases from 170 to 470 K.This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman.The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization,non-destructive evaluation,and manufacturing monitoring.
基金This work was supported by the Natural Science Foundation of Guangdong Province,China(2018 A0303131000)the project of Academician workstation of Guangdong Province,China(2014B090905001)the Fundamental Research Funds for the Central Universities,China(21617406)and the key project of Scientific and Technological projects of Guang Zhou,China(201604040007,201604020168).
文摘This study aimed to explore the application of surface-enhanced Raman scattering(SERS)in the rapid diagnosis of gastric cancer.The SERS spectra of 68 serum samples from gastric cancer patients and healthy volunteers were acquired.The characteristic ratio method(CRM)and principal component analysis(PCA)were used to differentiate gastric cancer serum from normal serum.Compared with healthy volunteers,the serum SERS intensity of gastric cancer patients was relatively high at 722 cm^(-1),while it was relatively low at 588,644,861,1008,1235,1397,1445 and 1586 cm^(-1).These results indicated that the relative content of nucleic acids in the serum of gastric cancer patients rises while the relative content of amino acids and carbohydrates decreases.In PCA,the sensitivity and specificity of discriminating gastric cancer were 94.1%and 94.1%,respectively,with the accuracy of 94.1%.Based on the intensity ratios of four characteristic peaks at 722,861,1008 and 1397 cm^(-1),CRM presented the diagnostic sensitivity and specificity of 100%and 97.4%,respectively,and the accuracy of 98.5%.Therefore,the three peak intensity ratios of I_(722)/I_(861),I_(722)/I_(1008)and I_(722)/I_(1397)can be considered as biologicalfingerprint information for gastric cancer diagnosis and can rapidly and directly reflect the physiological and pathological changes associated with gastric cancer development.This study provides an important basis and standards for the early diagnosis of gastric cancer.
基金supported by the Generalitat valenciana through grant PROMETEUS 2009/2011the European Commission through NanoCIS project (FP7-PEOPLE-2010IRSES ref. 269279)
文摘Indium sulfide （InzS3） thin films were prepared by chemical spray pyrolysis technique from solutions with different [S]/[In] ratios on glass substrates at a constant temperature of 250 ~C. Thin films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, atomic force microscopy （AFM）, energy disper- sive X-ray spectroscopy （EDS）, Raman spectroscopy and optical transmittance spectroscopy. All samples exhibit a polycrystalline structure with a preferential orientation along （0, 0, 12）. A good stoichiometry was attained for all samples. The morphology of thin film surfaces, as seen by SEM, was dense and no cracks or pinholes were ob- served. Raman spectroscopy analysis shows active modes belonging to j3-1naS3 phase. The optical transmittance in the visible range is higher than 60% and the band gap energy slightly increases with the sulfur to indium ratio, attaining a value of 2.63 eV for [S]/[In] ： 4.5.
基金This work was supported by the National Natural Science Foundation of China （No.91127042, No.21103158, No.21273211, No.21473171）, the National Key Basic Research Special Foundation （No.2013CB834602 and No.2010CB923300）, the Fundamental Research Funds for the Central Universities （No.7215623603）, and the Hua-shan Mountain Scholar Program. We also thank Doctor Kang-zhen Tian and Professor Shu-ji Ye for the measurement of IR spectra of aqueous lysozyme.
文摘The amide A band of protein is sensitive to the hydrogen bands of amide groups of proteins. However, it is hard to distinguish the amide A band of aqueous protein in situ directly, since it overlaps with O-H stretching vibration of water. In this work, we presented a new analytical method of Raman ratio spectrum, which can extract the amide A band of proteins in water. To obtain the Raman ratio spectrum, the Raman spectrum of aqueous protein was divided by that of pure water. A mathematical simulation was employed to examine whether Raman ratio spectrum is effective. Two kinds of protein, lysozyme and （^-chymotrypsin were employed. The amide A bands of them in water were extracted from Raman ratio spectra. Additionally, the process of thermal denaturation of lysozyme was detected from Raman ratio spectrum. These results demonstrated the Raman ratio spectra could be employed to study the amide A modes of proteins in water.
