A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional s...A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional sensing signals.Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sen-sitivity and selectivity.This study aimed to elucidate the modification of an indium tin oxide(ITO)electrode with a viologen monolayer with an ordered orientation.Novel methods were developed to immobilize a viologen molecule bearing a car-boxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-car-bodiimide with N-hydroxy-succinimide(EDC/NHS).In the two methods of immobilization,one utilizes a two-step process to firstly form an aromatic siloxane base layer and subsequently attach the viologen derivative through an amide linkage by post-amidation.The other employs a direct ester linkage between the hydroxyl groups of the ITO surface and the car-boxyl group of the viologen derivative.The latter method was also applied to immobilize a ferrocenyl group at a very short distance from the ITO surface.Potential-modulated UV-visible transmission absorption spectral measurement techniques with oblique incidence of plane-polarized light were employed to determine the orientation of the longitudinal axis of the reduced form of the viologen.The frequency dependence data of the potential-modulated transmission absorption signals were utilized to analyze the electron transfer kinetics.The performance of the two viologen-modified electrodes was com-pared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.展开更多
This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of...This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.展开更多
N,N'-bis(4-methoxysalicylidene)ethylenediamine is proposed as analytical reagent for the direct determination of chromium in original matrix of liquid oils.The method is based on the complexation of N,N'-bis(4...N,N'-bis(4-methoxysalicylidene)ethylenediamine is proposed as analytical reagent for the direct determination of chromium in original matrix of liquid oils.The method is based on the complexation of N,N'-bis(4-methoxysalicylidene)ethylenediamine and chromium in n-hexane∶acetone(1∶4)medium and spectrophotometric determination at 355 nm against reagent blank.Complexation of MSE and chromium is completed in20 seconds at molar ratio 1∶1.The molar absorptivity and the formation constant of the complex are determined as 9 740L·mol^(-1)·cm^(-1) and 3.6(±0.1)×10~5,respectively.Beer's law is obeyed in range 0.02~1.50mg·L^(-1) chromium concentration.Limits of detection and quantification of the suggested method were7.5 and 25.11μg·kg-,respectively.The accuracy and precision of the method was checked by finding mean recovery and relative standard deviation by oil-based chromium standard analysis as 96.4%±1.4%and 1.5%,respectively.The practical applicability of elaborate method was tested using oil-based chromium standard spiked and unspiked corn,sunflower,soybean,olive and canola oils.展开更多
Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus （S. metallicus） at 65 ℃ was investigated by X-ray diffraction （XRD）, diffuse re...Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus （S. metallicus） at 65 ℃ was investigated by X-ray diffraction （XRD）, diffuse reflectance Fourier transform infrared spectroscopy （FT-IR） and sulfur K-edge X-ray absorption near edge structure spectroscopy （XANES）. The results show that the presence of S. metallicus effectively enhances the dissolution of the mineral. The yield of zinc increases from 0.5 g/L in sterile control to 2.7 g/L in bioleaching. The pyrite in the concentrate facilitates zinc dissolution in the early stage, but has hindrance role in the late stage for the formation of jarosite. Sulfur speciation analyses show that jarosite and elemental sulfur are main products in bioleaching process, and the accumulation ofjarosite is mainly responsible for the decline of leaching efficiency.展开更多
基金supports by the Grant-in-Aid of Scientific Research of Challenging Research(Exploratory)(JP23K17738)to TS from MEXT of Japanthe 41st grant of research from Nippon Sheet Glass Foundation for Materials Science and Engineering to TS.
文摘A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing.The necessity for its sophistication arises from the availability of multi-dimensional sensing signals.Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sen-sitivity and selectivity.This study aimed to elucidate the modification of an indium tin oxide(ITO)electrode with a viologen monolayer with an ordered orientation.Novel methods were developed to immobilize a viologen molecule bearing a car-boxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-car-bodiimide with N-hydroxy-succinimide(EDC/NHS).In the two methods of immobilization,one utilizes a two-step process to firstly form an aromatic siloxane base layer and subsequently attach the viologen derivative through an amide linkage by post-amidation.The other employs a direct ester linkage between the hydroxyl groups of the ITO surface and the car-boxyl group of the viologen derivative.The latter method was also applied to immobilize a ferrocenyl group at a very short distance from the ITO surface.Potential-modulated UV-visible transmission absorption spectral measurement techniques with oblique incidence of plane-polarized light were employed to determine the orientation of the longitudinal axis of the reduced form of the viologen.The frequency dependence data of the potential-modulated transmission absorption signals were utilized to analyze the electron transfer kinetics.The performance of the two viologen-modified electrodes was com-pared to that of an ITO modified by post-amidation to the most commonly used base layer prepared with 3-aminopropyl triethoxysilane.
基金This research was funded by Discovery Grants from the Natural Sciences and Engineering Research Council of Canada(JL:RGPIN-2022-03958AC:RGPIN-2022-04238).
文摘This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.
基金the Scientific and Technological Research Council of Turkey(TUBITAK-TBAG project number 105T153)
文摘N,N'-bis(4-methoxysalicylidene)ethylenediamine is proposed as analytical reagent for the direct determination of chromium in original matrix of liquid oils.The method is based on the complexation of N,N'-bis(4-methoxysalicylidene)ethylenediamine and chromium in n-hexane∶acetone(1∶4)medium and spectrophotometric determination at 355 nm against reagent blank.Complexation of MSE and chromium is completed in20 seconds at molar ratio 1∶1.The molar absorptivity and the formation constant of the complex are determined as 9 740L·mol^(-1)·cm^(-1) and 3.6(±0.1)×10~5,respectively.Beer's law is obeyed in range 0.02~1.50mg·L^(-1) chromium concentration.Limits of detection and quantification of the suggested method were7.5 and 25.11μg·kg-,respectively.The accuracy and precision of the method was checked by finding mean recovery and relative standard deviation by oil-based chromium standard analysis as 96.4%±1.4%and 1.5%,respectively.The practical applicability of elaborate method was tested using oil-based chromium standard spiked and unspiked corn,sunflower,soybean,olive and canola oils.
基金Project(50974140) supported by the National Natural Science Foundation of ChinaProject(VR-09157) supported by Beijing Synchrotron Radiation Facility (BSRF) Public User Program,China
文摘Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus （S. metallicus） at 65 ℃ was investigated by X-ray diffraction （XRD）, diffuse reflectance Fourier transform infrared spectroscopy （FT-IR） and sulfur K-edge X-ray absorption near edge structure spectroscopy （XANES）. The results show that the presence of S. metallicus effectively enhances the dissolution of the mineral. The yield of zinc increases from 0.5 g/L in sterile control to 2.7 g/L in bioleaching. The pyrite in the concentrate facilitates zinc dissolution in the early stage, but has hindrance role in the late stage for the formation of jarosite. Sulfur speciation analyses show that jarosite and elemental sulfur are main products in bioleaching process, and the accumulation ofjarosite is mainly responsible for the decline of leaching efficiency.
