Ethylene carbonate(EC) liquid and its vapor-liquid interface were investigated using a combination of molecular dynamics(MD)simulation and vibrational IR, Raman and sum frequency generation(SFG)spectroscopies. The MD ...Ethylene carbonate(EC) liquid and its vapor-liquid interface were investigated using a combination of molecular dynamics(MD)simulation and vibrational IR, Raman and sum frequency generation(SFG)spectroscopies. The MD simulation was performed with a flexible and polarizable model of the EC molecule newly developed for the computation of vibrational spectra. The internal vibration of the model was described on the basis of the harmonic couplings of vibrational modes, including the anharmonicity and Fermi resonance coupling of C=O stretching. The polarizable model was represented by the charge response kernel(CRK),which is based on ab initio molecular orbital calculations and can be readily applied to other systems. The flexible and polarizable model can also accurately reproduce the structural and thermodynamic properties of EC liquid. Meanwhile, a comprehensive set of vibrational spectra of EC liquid, including the IR and Raman spectra of the bulk liquid as well as the SFG spectra of the liquid interface, were experimentally measured and reported. The set of experimental vibrational spectra provided valuable information for validating the model, and the MD simulation using the model comprehensively elucidates the observed vibrational IR, Raman, and SFG spectra of EC liquid. Further MD analysis of the interface region revealed that EC molecules tend to orientate themselves with the C=O bond parallel to the interface. The MD simulation explains the positive Im[χ^((2))](ssp) band of the C=O stretching region in the SFG spectrum in terms of the preferential orientation of EC molecules at the interface. This work also elucidates the distinct lineshapes of the C=O stretching band in the IR, Raman, and SFG spectra. The lineshapes of the C=O band are split by the Fermi resonance of the C=O fundamental and the overtone of skeletal stretching. The Fermi resonance of C=O stretching was fully analyzed using the empirical potential parameter shift analysis(EPSA) method. The apparently different lineshapes of the C=O stretching band in the IR, Raman, and SFG spectra were attributed to the frequency shift of the C=O fundamental in different solvation environments in the bulk liquid and at the interface. This work proposes a systematic procedure for investigating the interface structure and SFG spectra, including general modeling procedure based on ab initio calculations, validation of the model using available experimental data, and simultaneous analysis of molecular orientation and SFG spectra through MD trajectories. The proposed procedure provides microscopic information on the EC interface in this study, and can be further applied to investigate other interface systems, such as liquid-liquid and solid-liquid interfaces.展开更多
Poly(ethylene- co -chlorotrifluoroethylene) with a 1∶1 molar ratio of ethylene and chlorotrifluoroethylene in composition, PECTFE, is a statistically alternating copolymer widely used in cable coating industry. PECTF...Poly(ethylene- co -chlorotrifluoroethylene) with a 1∶1 molar ratio of ethylene and chlorotrifluoroethylene in composition, PECTFE, is a statistically alternating copolymer widely used in cable coating industry. PECTFE has been commonly characterized as a semicrystalline polymer with crystals melting at 238 ℃. Differential scanning calorimetry, thermal mechanical analysis and dynamic mechanical analysis indicated that PECTFE undergoes a reversible solid-solid transition during cooling and heating in the temperature range between 100 ℃ and 200 ℃. Based on detailed structural analysis via wide angle X-ray diffraction and electron diffraction techniques, we proposed that PECTFE possesses a hexagonal phase above 200 ℃( a =0 60 nm, c =0 49 nm) and an orthorhombic phase( a =0 99 nm, b =0 57 nm, c =0 49 nm) at room temperature.展开更多
Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critica...Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.展开更多
Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxi...Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxification of CWAs are vital for the safety of first responders,military personnel,and civilians,driving significant research in this area.Herein,we designed and synthesized a poly(-diallyldimethylammonium chloride)(PDDA)mediated cupric oxide(CuO)functionalized activated carbon fabric(ACF),termed ACF@PDDA-CuO,as an adsorbent filter material for self-detoxifying chemical protective clothing.PDDA,a positively charged polyelectrolyte,effectively binds in-situ synthesized CuO to the negatively charged ACF surface,serving as a suitable binder.This study demonstrates the synergistic effects of PDDA-CuO functionalization on ACF,where PDDA treatment enhanced mechanical and comfort properties,and CuO crystal growth significantly improved detoxification efficacy against the CWA Nerve Agent Sarin.Comprehensive analyses,including FTIR,BET surface area analysis,SEM,EDS,TEM,STEM,TGA,XPS,and XRD,confirmed the uniform deposition of CuO and PDDA on the ACF surface.The Cu content on ACF@PDDA-CuO samples was measured via iodometric titration.The materials were evaluated for tensile strength,air permeability,water vapor permeability,nerve agent(Sarin)detoxification,and blister agent(Sulfur Mustard)breakthrough time to assess their applicability for protective clothing.The optimized PDDA-CuO on ACF detoxified 82.04%of Sarin within 18 h,compared to 25.22%by ACF alone,and enhanced tensile strength by 23.67%,air permeability by 24.63%,and water vapor permeability by 3.94%,while maintaining protection against Sulfur Mustard for 24 h.These findings indicate that ACF@PDDA-CuO is a promising candidate for CWA protective clothing,offering robust protection with enhanced comfort.展开更多
基金supported by Elements Strategy Initiative for Catalysts and Batteries,Kyoto University,Cooperative Research Program of Institute for Catalysis,Hokkaido University,Japan and the Grants-in-Aids(JP25104003,JP26288003)by the Japan Society for the Promotion of Science(JSPS)and Ministry of Education,Culture,Sports and Technology(MEXT),Japan
文摘Ethylene carbonate(EC) liquid and its vapor-liquid interface were investigated using a combination of molecular dynamics(MD)simulation and vibrational IR, Raman and sum frequency generation(SFG)spectroscopies. The MD simulation was performed with a flexible and polarizable model of the EC molecule newly developed for the computation of vibrational spectra. The internal vibration of the model was described on the basis of the harmonic couplings of vibrational modes, including the anharmonicity and Fermi resonance coupling of C=O stretching. The polarizable model was represented by the charge response kernel(CRK),which is based on ab initio molecular orbital calculations and can be readily applied to other systems. The flexible and polarizable model can also accurately reproduce the structural and thermodynamic properties of EC liquid. Meanwhile, a comprehensive set of vibrational spectra of EC liquid, including the IR and Raman spectra of the bulk liquid as well as the SFG spectra of the liquid interface, were experimentally measured and reported. The set of experimental vibrational spectra provided valuable information for validating the model, and the MD simulation using the model comprehensively elucidates the observed vibrational IR, Raman, and SFG spectra of EC liquid. Further MD analysis of the interface region revealed that EC molecules tend to orientate themselves with the C=O bond parallel to the interface. The MD simulation explains the positive Im[χ^((2))](ssp) band of the C=O stretching region in the SFG spectrum in terms of the preferential orientation of EC molecules at the interface. This work also elucidates the distinct lineshapes of the C=O stretching band in the IR, Raman, and SFG spectra. The lineshapes of the C=O band are split by the Fermi resonance of the C=O fundamental and the overtone of skeletal stretching. The Fermi resonance of C=O stretching was fully analyzed using the empirical potential parameter shift analysis(EPSA) method. The apparently different lineshapes of the C=O stretching band in the IR, Raman, and SFG spectra were attributed to the frequency shift of the C=O fundamental in different solvation environments in the bulk liquid and at the interface. This work proposes a systematic procedure for investigating the interface structure and SFG spectra, including general modeling procedure based on ab initio calculations, validation of the model using available experimental data, and simultaneous analysis of molecular orientation and SFG spectra through MD trajectories. The proposed procedure provides microscopic information on the EC interface in this study, and can be further applied to investigate other interface systems, such as liquid-liquid and solid-liquid interfaces.
文摘Poly(ethylene- co -chlorotrifluoroethylene) with a 1∶1 molar ratio of ethylene and chlorotrifluoroethylene in composition, PECTFE, is a statistically alternating copolymer widely used in cable coating industry. PECTFE has been commonly characterized as a semicrystalline polymer with crystals melting at 238 ℃. Differential scanning calorimetry, thermal mechanical analysis and dynamic mechanical analysis indicated that PECTFE undergoes a reversible solid-solid transition during cooling and heating in the temperature range between 100 ℃ and 200 ℃. Based on detailed structural analysis via wide angle X-ray diffraction and electron diffraction techniques, we proposed that PECTFE possesses a hexagonal phase above 200 ℃( a =0 60 nm, c =0 49 nm) and an orthorhombic phase( a =0 99 nm, b =0 57 nm, c =0 49 nm) at room temperature.
文摘Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.
基金Defence Research and Development Establishment(DRDE),DRDO,Gwalior-474002,(India)for his keen interestencouragement.The DRDE accession number for this manuscript is DRDE-IREC-130-28/03/2024.
文摘Chemical warfare agents(CWAs)are extremely lethal substances used in warfare and terrorism,capable of causing permanent damage even in small doses,despite medical intervention.Therefore,detection,protection,and detoxification of CWAs are vital for the safety of first responders,military personnel,and civilians,driving significant research in this area.Herein,we designed and synthesized a poly(-diallyldimethylammonium chloride)(PDDA)mediated cupric oxide(CuO)functionalized activated carbon fabric(ACF),termed ACF@PDDA-CuO,as an adsorbent filter material for self-detoxifying chemical protective clothing.PDDA,a positively charged polyelectrolyte,effectively binds in-situ synthesized CuO to the negatively charged ACF surface,serving as a suitable binder.This study demonstrates the synergistic effects of PDDA-CuO functionalization on ACF,where PDDA treatment enhanced mechanical and comfort properties,and CuO crystal growth significantly improved detoxification efficacy against the CWA Nerve Agent Sarin.Comprehensive analyses,including FTIR,BET surface area analysis,SEM,EDS,TEM,STEM,TGA,XPS,and XRD,confirmed the uniform deposition of CuO and PDDA on the ACF surface.The Cu content on ACF@PDDA-CuO samples was measured via iodometric titration.The materials were evaluated for tensile strength,air permeability,water vapor permeability,nerve agent(Sarin)detoxification,and blister agent(Sulfur Mustard)breakthrough time to assess their applicability for protective clothing.The optimized PDDA-CuO on ACF detoxified 82.04%of Sarin within 18 h,compared to 25.22%by ACF alone,and enhanced tensile strength by 23.67%,air permeability by 24.63%,and water vapor permeability by 3.94%,while maintaining protection against Sulfur Mustard for 24 h.These findings indicate that ACF@PDDA-CuO is a promising candidate for CWA protective clothing,offering robust protection with enhanced comfort.
