Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena...Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.展开更多
A number of useful techniques associated with two-dimensional correlation spectroscopy(2DCOS)to improve its performance and utility have been developed in the last 30years.Evolution of these 2DCOS techniques,including...A number of useful techniques associated with two-dimensional correlation spectroscopy(2DCOS)to improve its performance and utility have been developed in the last 30years.Evolution of these 2DCOS techniques,including some of the very recent developments,is reviewed with examples.Topics include merged or modified asynchronous 2Dcorrelation spectrum,two-dimensional codistribution spectroscopy(2DCDS),Pareto scaling,and null-space projection treatment of spectral dataset.展开更多
In the present study,thermal behavior and crystal transition of pure poly(butylene adipate)(PBA)upon heating process were investigated by FTIR spectroscopy.To gain further insight into the thermal behavior alteration ...In the present study,thermal behavior and crystal transition of pure poly(butylene adipate)(PBA)upon heating process were investigated by FTIR spectroscopy.To gain further insight into the thermal behavior alteration and the phase transition of PBA,we performed two-dimensional(2D)correlation analysis.We found thatβ-form PBA crystal undergoes not only the melting process but also crystal transition upon the heating process.展开更多
We present a comprehensive electron momentum spectroscopy study on the electronic structure of trifluorobromomethane.The binding energy spectrum and electron momentum profiles of the entire outer-valence orbitals and ...We present a comprehensive electron momentum spectroscopy study on the electronic structure of trifluorobromomethane.The binding energy spectrum and electron momentum profiles of the entire outer-valence orbitals and the first inner-valence orbital along with several shake-up states were measured by using a high-sensitivity(e,2e)apparatus at an electron impact energy of 1213 eV.Theoretical calculations employing the density functional theory with B3LYP hybrid functional and the symmetry-adapted cluster configuration-interaction method were performed to interpret the experimental results.Important effects of electron correlations in the initial neutral and final ionic states on the electron momentum profiles have been observed.展开更多
In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagul...In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al（OH）3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH〉 COO-〉NH deformation of amide Ⅱ〉 aliphatic hydroxyl C／OH at p H 5, and COO-〉aliphatic hydroxyl C／OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.展开更多
Recent noteworthy developments in the field of two-dimensional（2D） correlation spectroscopy are reviewed.2D correlation spectroscopy has become a very popular tool due to its versatility and relative ease of use.The...Recent noteworthy developments in the field of two-dimensional（2D） correlation spectroscopy are reviewed.2D correlation spectroscopy has become a very popular tool due to its versatility and relative ease of use.The technique utilizes a spectroscopic or other analytical probe from a number of selections for a broad range of sample systems by employing different types of external perturbations to induce systematic variations in intensities of spectra.Such spectral intensity variations are then converted into2 D spectra by a form of correlation analysis for subsequent interpretation.Many different types of 2D correlation approaches have been proposed.In particular,2D hetero-correlation and multiple perturbation correlation analyses,including orthogonal sample design scheme,are discussed in this review.Additional references to other important developments in the field of 2D correlation spectroscopy,such as projection correlation and codistribution analysis,were also provided.展开更多
Since the theory of generalized two-dimensional (2-D) correlation spectroscopy was proposed, it has been keenly concerned in scientific research and its analytical method has been widely applied in various analytical ...Since the theory of generalized two-dimensional (2-D) correlation spectroscopy was proposed, it has been keenly concerned in scientific research and its analytical method has been widely applied in various analytical fields. The mathematical process to construct generalized 2-D correlation spectroscopy and the physical meaning of 2-D correlation spectral map are described, and three examples in the fields of chemical analysis and molecular biology are provided, such as the component analysis of organic solvent, the analysis of biological molecules in the solvent with different pH values and structural analysis of protein. The theory and analytical method of generalized 2-D correlation spectroscopy are also detailedly commented.展开更多
Chinese liquor Moutai is the “National alcoholic drink” in China and plays a very important role of social activities in Chinese people’s life. In pursuit of high profits, some illegal counterfeit Moutai liquors ha...Chinese liquor Moutai is the “National alcoholic drink” in China and plays a very important role of social activities in Chinese people’s life. In pursuit of high profits, some illegal counterfeit Moutai liquors have begun to appear in the market. Therefore, it is an urgent need for new techniques to discriminate the genuine and counterfeit Moutai liquor. In this work, the conventional Ultraviolet-Visible (UV-Vis) spectroscopy and two-dimensional correlation UV-Vis spectroscopy are applied to obtain the UV-Vis characteristic of Moutai liquor and counterfeit one, respectively. The experimental results reveal that the conventional UV-Vis spectra of the genuine and counterfeit Moutai liquor are similar. However, the two-dimensional correlation UV-Vis spectra of them are different and this method would be applied to differentiate the counterfeit Moutai liquor from the genuine Moutai liquor. Compared with conventional methods, this novel method has the advantages of easy operation, simple instrumentation and direct recognition, which make it a potential tool in the fields of food safety.展开更多
A novel compound, （4,4＇-Hbpy）3[NaMo8O26]（4,4＇-bpy）2（H2O）4 1 （bpy=bipydine）, was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system...A novel compound, （4,4＇-Hbpy）3[NaMo8O26]（4,4＇-bpy）2（H2O）4 1 （bpy=bipydine）, was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system, space group C2/m with a=19.1921（5）, b=18.6931（6）, c=9.3821（3） A° β=104.8020（11）°, V=3254.22（17）A°^3 C50H51Mo8N10NaO30, Mr=2062.52, Z=2, F（000）=2016, μ=1.591 mm^-1 and Dc=2.105 g/cm^3. The final R=0.0283 and wR=0.0912 for 3118 observed reflections （I〉20（I））. Compound 1 contains the β-[Mo8O26]^4-anion, sodium ion, 4,4＇-bpy and lattice crystalline water molecules. The β-[MosO26] units link the sodium ion to form a chain structure. The infinitechains of [Na（Mo8O26）]^3- blocks are surrounded by protonized 4,4＇-bpy cations, 4,4＇-bpy and lattice crystalline water molecules. The 2D-IR correlation spectroscopy study indicates that the stretching vibrations of Mo=O occur more preferentially due to the thermal effect. The TGA analysis shows that compound 1 has high thermal stability.展开更多
Two dimensional asynchronous spectra were used to characterize coordination between carbonyl group of butanone and metal ions by using an approach proposed in our recent paper.Spectral variation of n-π^＊transition b...Two dimensional asynchronous spectra were used to characterize coordination between carbonyl group of butanone and metal ions by using an approach proposed in our recent paper.Spectral variation of n-π^＊transition band of carbonyl group is used to probe the coordination even if metal ions does not possess any characteristic peak in spectra.Experimental results indicate that Ca^2＋ and Al^3＋ show considerable ability to coordinate with the carbonyl group of butanone and bring about spectral variation of the n-π-＊transition band,which is manifested by cross peaks in 2D asynchronous spectra.展开更多
A series of soy protein isolate(SPI)films plasticized by glycerol(Gly)were studied using attenuated total reflectance-Fourier transform infrared spectroscopy(ATR/FTIR).Perturbation-correlation movingwindow two-dimensi...A series of soy protein isolate(SPI)films plasticized by glycerol(Gly)were studied using attenuated total reflectance-Fourier transform infrared spectroscopy(ATR/FTIR).Perturbation-correlation movingwindow two-dimensional(PCMW2D)and two-dimensional correlation(2DCOS)analyses were applied to the amideⅠband and thus the hydrogen bond interaction between SPI and Gly was systematically investigated.When Gly concentrations were in the range 0~35%,the hydrogen bond amongβ-sheets was replaced by the one between SPI chain and Gly molecule,which caused these protein chains being changed toα-helix.However,the transformation ofβ-sheet toα-helix was saturated and both of them tend to change to random coil when Gly concentrations were in the range 35%~60%.展开更多
Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the bind...Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the binding of zinc with organic matters associated with cyanobacterial blooms,including dissolved organic matters（DOM） and attached organic matters（AOM）,were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy（2D-COS）.Metal-induced fluorescent quenching was obviously observed both for DOM and AOM,indicating the formation of metal-ligand complexes.Compared with the one-dimensional spectra,2D-COS revealed the sequences of metal-ligand interaction with the following orders：276 nm 〉 232 ran for DOM and232 nm 〉 276 nm for AOM.Furthermore,the modified Stern-Volmer model showed that the binding constant（logKM） of 276 nm in DOM was higher than that of 232 nm（4.93 vs.4.51）,while AOM was characterized with a high binding affinity for 232 nm（log KM：4.83）.The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples.Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction.展开更多
Moiré superlattices have revolutionized the study of two-dimensional materials, enabling unprecedented control over their electronic, magnetic, optical, and mechanical properties. This review provides a comprehen...Moiré superlattices have revolutionized the study of two-dimensional materials, enabling unprecedented control over their electronic, magnetic, optical, and mechanical properties. This review provides a comprehensive analysis of the latest advancements in moiré physics, focusing on the formation of moiré superlattices due to rotational misalignment or lattice mismatch in two-dimensional materials. These superlattices induce flat band structures and strong correlation effects,leading to the emergence of exotic quantum phases, such as unconventional superconductivity, correlated insulating states,and fractional quantum anomalous Hall effects. The review also explores the underlying mechanisms of these phenomena and discusses the potential technological applications of moiré physics, offering insights into future research directions in this rapidly evolving field.展开更多
The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are consi...The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are considered aspromising candidates due to their exceptional photovoltaic properties,good stability and low cost.The cooling rate of hotcarriers is a key parameter influencing the performance of hot-carrier solar cells.In this work,we successfully detected hotcarrier dynamics in operando LHP devices using the two-pulse photovoltage correlation technique.To enhance the signalto-noise ratio,we applied the delay-time modulation method instead of the traditional power modulation.This advancementallowed us to detect the intraband hot carrier cooling time for the organic LHP CH_(3)NH_(3)PbBr_(3),which is as short as 0.21 ps.In comparison,the inorganic Cs-based LHP CsPbBr_(3)exhibited a longer cooling time of around 0.59 ps due to differentphonon contributions.These results provide us new insights into the optimal design of hot-carrier solar cells and highlightthe potential of LHP materials in advancing solar cell technology.展开更多
The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy...The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy(FT-IR) and high-performance size exclusion chromatography(HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra(2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC.The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution(MWD). According to 2D-COS analysis, microbial humiclike substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence:phenolic and alcoholic C\O groups > aromatic structures containing C_C double bonds >aliphatic C\H. X-ray photoelectron spectroscopy(XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.展开更多
The adsorption behavior of butyl xanthate on the surface of lead oxide was investigated using continuous online in situ attenuated total reflectance Fourier transform infrared（ATR-FTIR） spectroscopy technique and tw...The adsorption behavior of butyl xanthate on the surface of lead oxide was investigated using continuous online in situ attenuated total reflectance Fourier transform infrared（ATR-FTIR） spectroscopy technique and two dimensional（2D） correlation analysis.The adsorbed layer studied was prepared by coating α-PbO particles onto the surfaces of the ZnSe crystal.The appearance of spectral peaks at 1203 cm^-1,1033 cm^-1 and their red shift indicated the formation and aggregation of xanthate at the surface of α-PbO.According to 1R intensity changes after rinsing with deionized water and a NaOH solution,the adsorption was proved to be a chemisorption type.The competition between xanthate and OH^- for the surfaces leads to desorption of xanthate at higher pH.The technique of 2D correlation ATR-FTIR spectroscopy was used to evaluate the changing order of spectral intensities in the adsorption process,and the results indicated that xanthate micelles were formed at the surfaces.The adsorption kinetics of butyl xanthate was found to be a pseudo-second-order reaction model and the adsorption capacity of butyl xanthate at α-PbO was as high as 281 mg g^-1 after 150 min.展开更多
This paper reports the pH-induced structural changes in the surface immobilized poly（L-lysine）（PLL）film.Two-dimensional（2D） correlation analysis was applied to the Fourier transform infrared（FTIR）spectra of th...This paper reports the pH-induced structural changes in the surface immobilized poly（L-lysine）（PLL）film.Two-dimensional（2D） correlation analysis was applied to the Fourier transform infrared（FTIR）spectra of the surface-immobilized PLL film to examine the spectral changes induced by the alternations of the protonation state of the amino group in the side chain.Significant spectral changes in the FTIR spectra of the PLL film were observed between pH 7 and 8.The decrease in the protonation state of the amino group in the side chain induced spectral changes in the amino group as well as conformational changes in the alky]group in the side chain.From pH 1-8,the spectral changes in the amino and alkyl groups in the side chain occurred before those of the amide group in the main chain of the surface immobilized PLL film.展开更多
Lanthanum modified materials have been widely used for the removal of hazardous anions.In this study,in situ ATR-FTIR and two-dimensional correlation analysis were employed to investigate the adsorption mechanism of a...Lanthanum modified materials have been widely used for the removal of hazardous anions.In this study,in situ ATR-FTIR and two-dimensional correlation analysis were employed to investigate the adsorption mechanism of arsenate（As（V）） on lanthanum-impregnated activated alumina（LAA）.Our results showed that electrostatic interaction attracted As（V） anions to the LAA surface,and then As（V） could form monodentate configuration on the LAA surface at pH 5-9.The result of 2D-COS showed that two coexistent adsorbed As（V） species,H2AsO4^- and HAsO4^2-,were adsorbed on the LAA surface without specific sequence at different pH conditions,indicating a negligible role of the incorporated protons of As（V） on the adsorption affinity to LAA surface.The results of this study reveal insights into LAA surface complexes on the molecular scale and provide theoretical support to new metal oxides design for efficient arsenic removal.展开更多
To consider the reliability and performance of electronic devices based on polyimide derivatives, dynamic water sorption and diffusion behavior in a polyimide derivative： poly（4＇4 oxydiphenylene pyromellitimide） ...To consider the reliability and performance of electronic devices based on polyimide derivatives, dynamic water sorption and diffusion behavior in a polyimide derivative： poly（4＇4 oxydiphenylene pyromellitimide） （PMDA-ODA）/silica nanocomposite was investigated by two-dimensional ATR-FTIR spectroscopy, by which three states of water molecules owning different H-bonding strength were distinguished. The amounts and strength of H-bonding also played a significant role in determining the diffusion rate of the different states of water molecules. The type of aggregated water molecules which also formed H-bonding with silicic acid （residues） or polyimide system was the last one diffusing to the polymer side in contact with the ATR crystal element because the polymeric matrix blocked their diffusion to a great extent. The diffusion coefficient was also estimated to gain the information of the dynamic diffusion behavior.展开更多
Antifungal resistance is the leading cause of antifungal treatment failure in invasive candidiasis.Metabolic rewiring could become a new insight to account for antifungal resistance as to find innovative clinical ther...Antifungal resistance is the leading cause of antifungal treatment failure in invasive candidiasis.Metabolic rewiring could become a new insight to account for antifungal resistance as to find innovative clinical therapies.Here,we show that dynamic surface-enhanced Raman spectroscopy is a promising tool to identify the metabolic differences between fluconazole(Diflucan)-resistant and fluconazole(Diflucan)-sensitive Candida albicans through the signatures of biochemical components and complemented with machine learning algorithms and two-dimensional correlation spectroscopy,an underlying resistance mechanism,that is,the change of purine metabolites induced the resistance of Candida albicans has been clarified yet never reported anywhere.We hope the integrated methodology introduced in this work could be beneficial for the interpretation of cellular regulation,propelling the development of targeted antifungal therapies and diagnostic tools for more efficient management of severe antifungal resistance.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21274030,51473038 and 21604024)the Natural Science Foundation of Shanghai(No.17ZR1440400)+1 种基金the Open Project of State Key Laboratory of Chemical Engineering(No.SKL-Ch E-16C02)“Chenguang Plan”
文摘Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.
文摘A number of useful techniques associated with two-dimensional correlation spectroscopy(2DCOS)to improve its performance and utility have been developed in the last 30years.Evolution of these 2DCOS techniques,including some of the very recent developments,is reviewed with examples.Topics include merged or modified asynchronous 2Dcorrelation spectrum,two-dimensional codistribution spectroscopy(2DCDS),Pareto scaling,and null-space projection treatment of spectral dataset.
文摘In the present study,thermal behavior and crystal transition of pure poly(butylene adipate)(PBA)upon heating process were investigated by FTIR spectroscopy.To gain further insight into the thermal behavior alteration and the phase transition of PBA,we performed two-dimensional(2D)correlation analysis.We found thatβ-form PBA crystal undergoes not only the melting process but also crystal transition upon the heating process.
基金Project supported by the National Natural Science Foundation of China(Grant No.12127804).
文摘We present a comprehensive electron momentum spectroscopy study on the electronic structure of trifluorobromomethane.The binding energy spectrum and electron momentum profiles of the entire outer-valence orbitals and the first inner-valence orbital along with several shake-up states were measured by using a high-sensitivity(e,2e)apparatus at an electron impact energy of 1213 eV.Theoretical calculations employing the density functional theory with B3LYP hybrid functional and the symmetry-adapted cluster configuration-interaction method were performed to interpret the experimental results.Important effects of electron correlations in the initial neutral and final ionic states on the electron momentum profiles have been observed.
基金supported by the National Key Technology Support Program(No.2014BAC13B06)the National Natural Science Foundation of China(Nos.51378414,51178376)+1 种基金the Program for Innovative Research Team in Shaanxi(No.2013KCT-13)the Program for New Century Excellent Talents in the University of Ministry of Education of China(No.NCET-12-1043)
文摘In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al（OH）3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH〉 COO-〉NH deformation of amide Ⅱ〉 aliphatic hydroxyl C／OH at p H 5, and COO-〉aliphatic hydroxyl C／OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.
文摘Recent noteworthy developments in the field of two-dimensional（2D） correlation spectroscopy are reviewed.2D correlation spectroscopy has become a very popular tool due to its versatility and relative ease of use.The technique utilizes a spectroscopic or other analytical probe from a number of selections for a broad range of sample systems by employing different types of external perturbations to induce systematic variations in intensities of spectra.Such spectral intensity variations are then converted into2 D spectra by a form of correlation analysis for subsequent interpretation.Many different types of 2D correlation approaches have been proposed.In particular,2D hetero-correlation and multiple perturbation correlation analyses,including orthogonal sample design scheme,are discussed in this review.Additional references to other important developments in the field of 2D correlation spectroscopy,such as projection correlation and codistribution analysis,were also provided.
文摘Since the theory of generalized two-dimensional (2-D) correlation spectroscopy was proposed, it has been keenly concerned in scientific research and its analytical method has been widely applied in various analytical fields. The mathematical process to construct generalized 2-D correlation spectroscopy and the physical meaning of 2-D correlation spectral map are described, and three examples in the fields of chemical analysis and molecular biology are provided, such as the component analysis of organic solvent, the analysis of biological molecules in the solvent with different pH values and structural analysis of protein. The theory and analytical method of generalized 2-D correlation spectroscopy are also detailedly commented.
文摘Chinese liquor Moutai is the “National alcoholic drink” in China and plays a very important role of social activities in Chinese people’s life. In pursuit of high profits, some illegal counterfeit Moutai liquors have begun to appear in the market. Therefore, it is an urgent need for new techniques to discriminate the genuine and counterfeit Moutai liquor. In this work, the conventional Ultraviolet-Visible (UV-Vis) spectroscopy and two-dimensional correlation UV-Vis spectroscopy are applied to obtain the UV-Vis characteristic of Moutai liquor and counterfeit one, respectively. The experimental results reveal that the conventional UV-Vis spectra of the genuine and counterfeit Moutai liquor are similar. However, the two-dimensional correlation UV-Vis spectra of them are different and this method would be applied to differentiate the counterfeit Moutai liquor from the genuine Moutai liquor. Compared with conventional methods, this novel method has the advantages of easy operation, simple instrumentation and direct recognition, which make it a potential tool in the fields of food safety.
基金This work was supported by the Foundation of Education Committee of Fujian Province (K02028, JB04049), the State Key Laboratory of Structural Chemistry, and Science and Technology Foundation of Fuzhou University
文摘A novel compound, （4,4＇-Hbpy）3[NaMo8O26]（4,4＇-bpy）2（H2O）4 1 （bpy=bipydine）, was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system, space group C2/m with a=19.1921（5）, b=18.6931（6）, c=9.3821（3） A° β=104.8020（11）°, V=3254.22（17）A°^3 C50H51Mo8N10NaO30, Mr=2062.52, Z=2, F（000）=2016, μ=1.591 mm^-1 and Dc=2.105 g/cm^3. The final R=0.0283 and wR=0.0912 for 3118 observed reflections （I〉20（I））. Compound 1 contains the β-[Mo8O26]^4-anion, sodium ion, 4,4＇-bpy and lattice crystalline water molecules. The β-[MosO26] units link the sodium ion to form a chain structure. The infinitechains of [Na（Mo8O26）]^3- blocks are surrounded by protonized 4,4＇-bpy cations, 4,4＇-bpy and lattice crystalline water molecules. The 2D-IR correlation spectroscopy study indicates that the stretching vibrations of Mo=O occur more preferentially due to the thermal effect. The TGA analysis shows that compound 1 has high thermal stability.
基金financially supported by the National Natural Science Foundation of China(No.51373003)Beijing Natural Science Foundation(No.2122059)
文摘Two dimensional asynchronous spectra were used to characterize coordination between carbonyl group of butanone and metal ions by using an approach proposed in our recent paper.Spectral variation of n-π^＊transition band of carbonyl group is used to probe the coordination even if metal ions does not possess any characteristic peak in spectra.Experimental results indicate that Ca^2＋ and Al^3＋ show considerable ability to coordinate with the carbonyl group of butanone and bring about spectral variation of the n-π-＊transition band,which is manifested by cross peaks in 2D asynchronous spectra.
文摘A series of soy protein isolate(SPI)films plasticized by glycerol(Gly)were studied using attenuated total reflectance-Fourier transform infrared spectroscopy(ATR/FTIR).Perturbation-correlation movingwindow two-dimensional(PCMW2D)and two-dimensional correlation(2DCOS)analyses were applied to the amideⅠband and thus the hydrogen bond interaction between SPI and Gly was systematically investigated.When Gly concentrations were in the range 0~35%,the hydrogen bond amongβ-sheets was replaced by the one between SPI chain and Gly molecule,which caused these protein chains being changed toα-helix.However,the transformation ofβ-sheet toα-helix was saturated and both of them tend to change to random coil when Gly concentrations were in the range 35%~60%.
基金funded by the National Natural Science Foundation of China(Nos.51479187,51209192)the China Postdoctoral Science Foundation(Nos.2014T70505+1 种基金2013M 540438)the PAPD,and the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF13011)
文摘Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the binding of zinc with organic matters associated with cyanobacterial blooms,including dissolved organic matters（DOM） and attached organic matters（AOM）,were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy（2D-COS）.Metal-induced fluorescent quenching was obviously observed both for DOM and AOM,indicating the formation of metal-ligand complexes.Compared with the one-dimensional spectra,2D-COS revealed the sequences of metal-ligand interaction with the following orders：276 nm 〉 232 ran for DOM and232 nm 〉 276 nm for AOM.Furthermore,the modified Stern-Volmer model showed that the binding constant（logKM） of 276 nm in DOM was higher than that of 232 nm（4.93 vs.4.51）,while AOM was characterized with a high binding affinity for 232 nm（log KM：4.83）.The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples.Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction.
基金Project supported by the National Key R&D Program of China (Grant No. 2019YFA0307800)the National Natural Science Foundation of China (Grant No. 12074377)+2 种基金Fundamental Research Funds for the Central Universities,the International Partnership Program of Chinese Academy of Sciences (Grant No. 211211KYSB20210007)the China Postdoctoral Science Foundation (Grant No. 2024M753465)the Postdoctoral Fellowship Program (Grade C) of China Postdoctoral Science Foundation (Grant No. GZC20241893)。
文摘Moiré superlattices have revolutionized the study of two-dimensional materials, enabling unprecedented control over their electronic, magnetic, optical, and mechanical properties. This review provides a comprehensive analysis of the latest advancements in moiré physics, focusing on the formation of moiré superlattices due to rotational misalignment or lattice mismatch in two-dimensional materials. These superlattices induce flat band structures and strong correlation effects,leading to the emergence of exotic quantum phases, such as unconventional superconductivity, correlated insulating states,and fractional quantum anomalous Hall effects. The review also explores the underlying mechanisms of these phenomena and discusses the potential technological applications of moiré physics, offering insights into future research directions in this rapidly evolving field.
基金supported by the National Key R&D Program of China(Grant No.2021YFA1400500)New Cornerstone Science Foundation through the New Cornerstone Investigator Program,and the XPLORER Prize.
文摘The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are considered aspromising candidates due to their exceptional photovoltaic properties,good stability and low cost.The cooling rate of hotcarriers is a key parameter influencing the performance of hot-carrier solar cells.In this work,we successfully detected hotcarrier dynamics in operando LHP devices using the two-pulse photovoltage correlation technique.To enhance the signalto-noise ratio,we applied the delay-time modulation method instead of the traditional power modulation.This advancementallowed us to detect the intraband hot carrier cooling time for the organic LHP CH_(3)NH_(3)PbBr_(3),which is as short as 0.21 ps.In comparison,the inorganic Cs-based LHP CsPbBr_(3)exhibited a longer cooling time of around 0.59 ps due to differentphonon contributions.These results provide us new insights into the optimal design of hot-carrier solar cells and highlightthe potential of LHP materials in advancing solar cell technology.
基金supported by the National Key Technology Support Program (No.2014BAC13B06)the National Natural Science Foundation of China (Nos.51708443,51378414)+2 种基金the National Key Research and Development Program of China (No.2016YFC0400701)the China Postdoctoral Science Foundation (No.2017M623326XB)the Program for Innovative Research Teams in Shaanxi (No.2013KCT-13)
文摘The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy(FT-IR) and high-performance size exclusion chromatography(HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra(2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC.The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution(MWD). According to 2D-COS analysis, microbial humiclike substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence:phenolic and alcoholic C\O groups > aromatic structures containing C_C double bonds >aliphatic C\H. X-ray photoelectron spectroscopy(XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.
基金supported by the National Nature Science Foundation of China(Nos.51274104,50874052)National Key Basic Research Program of China(973,No.2011CB933700)
文摘The adsorption behavior of butyl xanthate on the surface of lead oxide was investigated using continuous online in situ attenuated total reflectance Fourier transform infrared（ATR-FTIR） spectroscopy technique and two dimensional（2D） correlation analysis.The adsorbed layer studied was prepared by coating α-PbO particles onto the surfaces of the ZnSe crystal.The appearance of spectral peaks at 1203 cm^-1,1033 cm^-1 and their red shift indicated the formation and aggregation of xanthate at the surface of α-PbO.According to 1R intensity changes after rinsing with deionized water and a NaOH solution,the adsorption was proved to be a chemisorption type.The competition between xanthate and OH^- for the surfaces leads to desorption of xanthate at higher pH.The technique of 2D correlation ATR-FTIR spectroscopy was used to evaluate the changing order of spectral intensities in the adsorption process,and the results indicated that xanthate micelles were formed at the surfaces.The adsorption kinetics of butyl xanthate was found to be a pseudo-second-order reaction model and the adsorption capacity of butyl xanthate at α-PbO was as high as 281 mg g^-1 after 150 min.
基金supported by Yeungnam University Research Grants in 2013a Human Resources Development Program of Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant(No.20104010100580) funded by the Korean Ministry of Knowledge Economy
文摘This paper reports the pH-induced structural changes in the surface immobilized poly（L-lysine）（PLL）film.Two-dimensional（2D） correlation analysis was applied to the Fourier transform infrared（FTIR）spectra of the surface-immobilized PLL film to examine the spectral changes induced by the alternations of the protonation state of the amino group in the side chain.Significant spectral changes in the FTIR spectra of the PLL film were observed between pH 7 and 8.The decrease in the protonation state of the amino group in the side chain induced spectral changes in the amino group as well as conformational changes in the alky]group in the side chain.From pH 1-8,the spectral changes in the amino and alkyl groups in the side chain occurred before those of the amide group in the main chain of the surface immobilized PLL film.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB14020201)the National Basic Research Program of China(No. 2014CB441102)+1 种基金the National Natural Science Foundation of China(No.21477144)the Young Scientists Fund of RCEES, RCEES-QN-20130017F
文摘Lanthanum modified materials have been widely used for the removal of hazardous anions.In this study,in situ ATR-FTIR and two-dimensional correlation analysis were employed to investigate the adsorption mechanism of arsenate（As（V）） on lanthanum-impregnated activated alumina（LAA）.Our results showed that electrostatic interaction attracted As（V） anions to the LAA surface,and then As（V） could form monodentate configuration on the LAA surface at pH 5-9.The result of 2D-COS showed that two coexistent adsorbed As（V） species,H2AsO4^- and HAsO4^2-,were adsorbed on the LAA surface without specific sequence at different pH conditions,indicating a negligible role of the incorporated protons of As（V） on the adsorption affinity to LAA surface.The results of this study reveal insights into LAA surface complexes on the molecular scale and provide theoretical support to new metal oxides design for efficient arsenic removal.
基金supported by the National Natural Science Foundation of China(No.20573022,No.20425415)the National Basic Research Pro-gram of China(2005CB623800),the PHD Program of M0E(20050246010)the"Qimingxing"Project(No.04QM1402)of Shanghai Municipal Science and Technology Commission,and the"Shuguang"Project(No.01SG05)of the Shanghai Municipal Education Commission and Shanghai Education Development Foundation.
文摘To consider the reliability and performance of electronic devices based on polyimide derivatives, dynamic water sorption and diffusion behavior in a polyimide derivative： poly（4＇4 oxydiphenylene pyromellitimide） （PMDA-ODA）/silica nanocomposite was investigated by two-dimensional ATR-FTIR spectroscopy, by which three states of water molecules owning different H-bonding strength were distinguished. The amounts and strength of H-bonding also played a significant role in determining the diffusion rate of the different states of water molecules. The type of aggregated water molecules which also formed H-bonding with silicic acid （residues） or polyimide system was the last one diffusing to the polymer side in contact with the ATR crystal element because the polymeric matrix blocked their diffusion to a great extent. The diffusion coefficient was also estimated to gain the information of the dynamic diffusion behavior.
基金supported by grants from the National Natural Science Foundation of China(Nos.22074015 and 82074428)Youth Talent Cultivation Initiation Fund of Zhongda Hospital,Southeast University(No.CZXM-GSP-RC110)to Hao Li+1 种基金Evidence-Based Capacity Building for TCM Specialty Therapies for Skin Diseases of National Administration of TCMInnovative Team Projects of Shanghai Municipal Commission of Health(No.2022CX011)to Fulun Li.
文摘Antifungal resistance is the leading cause of antifungal treatment failure in invasive candidiasis.Metabolic rewiring could become a new insight to account for antifungal resistance as to find innovative clinical therapies.Here,we show that dynamic surface-enhanced Raman spectroscopy is a promising tool to identify the metabolic differences between fluconazole(Diflucan)-resistant and fluconazole(Diflucan)-sensitive Candida albicans through the signatures of biochemical components and complemented with machine learning algorithms and two-dimensional correlation spectroscopy,an underlying resistance mechanism,that is,the change of purine metabolites induced the resistance of Candida albicans has been clarified yet never reported anywhere.We hope the integrated methodology introduced in this work could be beneficial for the interpretation of cellular regulation,propelling the development of targeted antifungal therapies and diagnostic tools for more efficient management of severe antifungal resistance.
