The deprotonation of an amphiphilic porphyrin, meso-tetra (p-hydroxylphenyl)porphyrin with a hexadecyl chain(THPPH2), has been observed by means of UV-Visspectroscopy in CTAB micellar solutions. With increasing of PH ...The deprotonation of an amphiphilic porphyrin, meso-tetra (p-hydroxylphenyl)porphyrin with a hexadecyl chain(THPPH2), has been observed by means of UV-Visspectroscopy in CTAB micellar solutions. With increasing of PH values, the Soret band shiftsfrom 424 nm to 441nm, and the four-Q bands (520 nm, 560 nm, 595nm, 655 nm) aredisappeared while two new Q-bands are appeared at 585 nm and 675 nm, which is similar tometal-porphyrin, means that the deprotonation of porphyrin takes place. Comparing withthe spectra in an other solutions, the spectral characteration of THPPH2 in neutral and inbasic CTAB solutions is similar to that in CHCI3 and basic aqueous solutions respectively,suggesting that the solubilizing location of THPPH2 takes a change from inner to the outer of theCTAB micellars with the PH value of solutions increasing between 6. 20 and 11. 19.展开更多
Aqueous rechargeable batteries using abundant multi-ion cations have receivedincreasing attention in the energy storage field for their high safety and low cost.Layered double hydroxides(LDHs)possess a two-dimensional...Aqueous rechargeable batteries using abundant multi-ion cations have receivedincreasing attention in the energy storage field for their high safety and low cost.Layered double hydroxides(LDHs)possess a two-dimensional structure andexhibit great potential as cathodes for multi-ion intercalation.However,theinsufficient active sites of LDHs result in low capacities in the discharging process.Interestingly,the LDHs after the deprotonation process exhibit favorable electrochemicalperformance of multi-cation intercalation.The deprotonation process ofLDHs has been widely found in the oxygen evolution reaction and energy storagefield,where LDHs lose H in laminates and converts to deprotonatedγ-phaseMOOHs(MOOs).Herein,we take a comprehensive overview of the dynamicsstructure transformation of the deprotonation process of LDHs.Furthermore,thedevelopment of advanced aqueous battery cathode and metal battery anode basedon deprotonated LDHs for energy storage is explored and summarized.Finally,theperspective of deprotonated LDHs in the energy storage field is discussed.展开更多
The title compound, 1,2-bis-（p-nitro-phenylsulfonamido）-4,5-dinitrobenzene, was synthesized and characterized by elemental analysis, IR and 1H NMR. A pale yellow prism crystal of C23H26N8O13S2 （Mr = 686.64） was ob...The title compound, 1,2-bis-（p-nitro-phenylsulfonamido）-4,5-dinitrobenzene, was synthesized and characterized by elemental analysis, IR and 1H NMR. A pale yellow prism crystal of C23H26N8O13S2 （Mr = 686.64） was obtained in DMF solution and determined by single-crystal X-ray diffraction method. It crystallizes in triclinic system, space group P1 with a = 10.346（4）, b = 12.210（5）, c = 12.976（5）A , α = 108.220（8）, β = 99.482（4）, γ = 95.490（4）°, V = 1516.7（10） A^3, Z = 2, Dc = 1.504 g/cm^3, F（000） = 712, μ = 0.254, Mr = 686.64, the final R = 0.0561 and wR = 0.1487. One sulfonamido group of the title compound is deprotoned and forms N（3）=C（13）. The crystal involves N,N-dimethylamine from the decomposition of DMF and the proton is transferred to N,N- dimethylamine. It is a strong proof for the characterization of deprotoned recognition compound by X-ray single-crystal structure.展开更多
Mannich-type reactions are a widely used method for the synthesis of amines due to the readily availability of nucleophiles and electrophiles.However,the inclusion of alkylarenes instead of active carbon pronucleophil...Mannich-type reactions are a widely used method for the synthesis of amines due to the readily availability of nucleophiles and electrophiles.However,the inclusion of alkylarenes instead of active carbon pronucleophiles such as aldehydes and ketones in these addition reactions has been a challenge due to the inherent difficulty of benzylic deprotonation.In this study,we present a novel approach for the construction of N-sulfonyl amines via rhodium-catalyzed addition of unbiased benzylic C–H bonds to cyclic N-sulfonyl ketamines throughπ-coordination.This strategy enables the synthesis of a diverse range of N-sulfonyl amines,and subsequent diversification of the addition products showcases the synthetic potential of this protocol.展开更多
The development of a highly efficient noniridium-based oxygen evolution reaction catalyst is the key to realizing large-scale commercial application of the proton-exchange membrane water electrolyzer.RuO_(2)is the mos...The development of a highly efficient noniridium-based oxygen evolution reaction catalyst is the key to realizing large-scale commercial application of the proton-exchange membrane water electrolyzer.RuO_(2)is the most promising alternative to IrO_(2),but if usually suffers from lattice-oxygenmediated corrosion and sluggish proton transfer kinetics under acidic media.Herein,we propose an effective strategy of embedding RuO_(2)nanoparticles into a N-doped carbon support,termed as RuO_(2)-NC,to simultaneously prevent Ru dissolution and accelerate the bridging-oxygen-assisted deprotonation process.The obtained RuO_(2)-NC electrocatalyst presents high activity with an overpotential of 159 mV to reach 10 mA cm^(−2) and remarkable stability for over 240 h.Structural investigation and theoretical calculations reveal that the electron-rich NC substrate,as an electron donor,provides a buffered charge compensation to protect RuO_(2)from excessive oxidation and lattice oxygen loss by switching into a conventional adsorbate evolution mechanism(AEM).More importantly,the activated bridging oxygen(Obri)sites can facilitate the deprotonation of*OOH intermediates,leading to an optimized bridging-oxygen-assisted deprotonation AEM pathway.展开更多
Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence ...Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence responses around 550--750 nm towards the hydrogen ions. The pKa of the probe 1a is 8.29, while that of the probe lb increases to 12.1 because of the hydrogen bond inside it. Selective and competitive experiments indicated that both common ions and amino acids did not interfere their emission with hydrogen ions. Moreover, confocal fluorescent imaging showed that the probe la could be served as mitochondria biomarker in HeLa and Ges-1 cells.展开更多
Raman spectra of 1,2,4-triazole-3-carboxylate (TC- anion) and its ring-deprotonated deriva- tive (dpTC2- dianion) in aqueous solutions were measured respectively. The density func- tional theory calculations were perf...Raman spectra of 1,2,4-triazole-3-carboxylate (TC- anion) and its ring-deprotonated deriva- tive (dpTC2- dianion) in aqueous solutions were measured respectively. The density func- tional theory calculations were performed using MN15 functional and PCM solvent model to investigate their structures, as well as the vibrational frequencies and Raman intensi- ties. With the aid of the calculated spectra, all the observed Raman bands of dpTC2- were clearly assigned, with taking into account the deuteration shifts. Moreover, various protonic tautomers of TC- anion were compared in the present theoretical calculations, and 2H- tautomer was found more stable. The experimental Raman spectrum of TC- solution was roughly consistent with the calculated spectrum of the monomeric 2H-tautomer of TC-, but some splits existed for a few bands when compared to the calculated spectra, which might be contributed by the hydrogen-bonding dimers of TC-.展开更多
The on-chip fabrication of a carbon nanoparticle-chitosan composite membrane （i.e. a sorbent membrane or a mixed matrix membrane） using laminar flow-based interfacial deprotonation technology was presented in this p...The on-chip fabrication of a carbon nanoparticle-chitosan composite membrane （i.e. a sorbent membrane or a mixed matrix membrane） using laminar flow-based interfacial deprotonation technology was presented in this paper. In addition, the effects of carbon nanoparticles and reactant flow rates on membrane formation were investigated. Finally, the permeability and adsorption capacities of the membrane were discussed. During fabrication, an acidic chitosan solution and a basic buffer solution that contained carbon nanoparticles were introduced into a microchannel. At the flow interface, a freestanding composite membrane with embedded carbon nanoparticles was formed due to the deprotonation of the chitosan molecules. The membrane growth gradually stopped with time from upstream to downstream and the thickness of the membrane increased rapidly and then slowly along the reactant flow direction. The formation of the membrane was divided into two stages. The average growth rate in the first stage was significantly larger than the average growth rate in the second stage. Carbon nanoparticles in the basic solution acted as nucleating agents and made the membrane formation much easier. As the flow rate of the chitosan solution increased, the averaged membrane thickness and the membrane hydraulic permeability initially increased and then decreased. Because of the addition of carbon nanoparticles, the formed membrane had adsorption abilities. The carbon nanoparticle-chitosan composite membrane that was fabricated in this study could be employed for simultaneous adsorption and dialysis in microdevices in the future.展开更多
Reaction of the N-heterocyclic borane [MeCCHC（CHe）（NAr）2]Btt （1, Ar=2,6-Me2C6H3） with B（C6F5）3 af- forded the zwitterionic hydroborane [MeCCHC（CHz）B（C6F5）3（NAr）2]BH, in which the β-methyl group can be d...Reaction of the N-heterocyclic borane [MeCCHC（CHe）（NAr）2]Btt （1, Ar=2,6-Me2C6H3） with B（C6F5）3 af- forded the zwitterionic hydroborane [MeCCHC（CHz）B（C6F5）3（NAr）2]BH, in which the β-methyl group can be deprotonated with LiN（SiMe3）2 to yield an anionic zwitterionic borenium.展开更多
A series of dye molecules was designed theoretically.Particularly,azoles and their derivatives were chosen as the modifying groups linking to ancillary ligands of [Ru（dcbpyH2）2（NCS）2]（N3,dcbpy=4,4＇-dicarboxy2,2...A series of dye molecules was designed theoretically.Particularly,azoles and their derivatives were chosen as the modifying groups linking to ancillary ligands of [Ru（dcbpyH2）2（NCS）2]（N3,dcbpy=4,4＇-dicarboxy2,2＇-bipyridine;NCS=thiocyanato）.Density functional theory（DFT） based approaches were applied to exploring the electronic structures and properties of all these systems.The dye molecule with 1,2,4-triazole groups which exhibits a very high intensity of absorption in visible region,was obtained.Time-dependent DFT（TD-DFT） results indicate that the ancillary ligand dominates the molecular orbital（MO） energy levels and masters the absorption transition nature to a certain extent.The deprotonation of anchoring ligand not only affects the frontier MO energy levels but also controls the energy gaps of the highest occupied MO（HOMO） to the lowest unoccupied MO（LUMO） and LUMO to LUMO＋1 orbital.If the gap between LUMO-LUMO＋1 is small enough,the higher efficiency of dye-sensitized solar cell（DSSC） should be expected.展开更多
文摘The deprotonation of an amphiphilic porphyrin, meso-tetra (p-hydroxylphenyl)porphyrin with a hexadecyl chain(THPPH2), has been observed by means of UV-Visspectroscopy in CTAB micellar solutions. With increasing of PH values, the Soret band shiftsfrom 424 nm to 441nm, and the four-Q bands (520 nm, 560 nm, 595nm, 655 nm) aredisappeared while two new Q-bands are appeared at 585 nm and 675 nm, which is similar tometal-porphyrin, means that the deprotonation of porphyrin takes place. Comparing withthe spectra in an other solutions, the spectral characteration of THPPH2 in neutral and inbasic CTAB solutions is similar to that in CHCI3 and basic aqueous solutions respectively,suggesting that the solubilizing location of THPPH2 takes a change from inner to the outer of theCTAB micellars with the PH value of solutions increasing between 6. 20 and 11. 19.
基金support from the National Natural Science Foundation of China(22090031,22090030,22288102),Qinghai Salt Lake Industry Group Co.,Ltd.
文摘Aqueous rechargeable batteries using abundant multi-ion cations have receivedincreasing attention in the energy storage field for their high safety and low cost.Layered double hydroxides(LDHs)possess a two-dimensional structure andexhibit great potential as cathodes for multi-ion intercalation.However,theinsufficient active sites of LDHs result in low capacities in the discharging process.Interestingly,the LDHs after the deprotonation process exhibit favorable electrochemicalperformance of multi-cation intercalation.The deprotonation process ofLDHs has been widely found in the oxygen evolution reaction and energy storagefield,where LDHs lose H in laminates and converts to deprotonatedγ-phaseMOOHs(MOOs).Herein,we take a comprehensive overview of the dynamicsstructure transformation of the deprotonation process of LDHs.Furthermore,thedevelopment of advanced aqueous battery cathode and metal battery anode basedon deprotonated LDHs for energy storage is explored and summarized.Finally,theperspective of deprotonated LDHs in the energy storage field is discussed.
基金This work was supported by the National Natural Science Foundation of China (No. 20371028, 20671052)the Natural Science Foundation of Tianjin (No. 023605811)
文摘The title compound, 1,2-bis-（p-nitro-phenylsulfonamido）-4,5-dinitrobenzene, was synthesized and characterized by elemental analysis, IR and 1H NMR. A pale yellow prism crystal of C23H26N8O13S2 （Mr = 686.64） was obtained in DMF solution and determined by single-crystal X-ray diffraction method. It crystallizes in triclinic system, space group P1 with a = 10.346（4）, b = 12.210（5）, c = 12.976（5）A , α = 108.220（8）, β = 99.482（4）, γ = 95.490（4）°, V = 1516.7（10） A^3, Z = 2, Dc = 1.504 g/cm^3, F（000） = 712, μ = 0.254, Mr = 686.64, the final R = 0.0561 and wR = 0.1487. One sulfonamido group of the title compound is deprotoned and forms N（3）=C（13）. The crystal involves N,N-dimethylamine from the decomposition of DMF and the proton is transferred to N,N- dimethylamine. It is a strong proof for the characterization of deprotoned recognition compound by X-ray single-crystal structure.
基金the National Natural Science Foundation of China(Nos.22271235,22071198)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2022SDXHDX0006)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2020R01004)for research support。
文摘Mannich-type reactions are a widely used method for the synthesis of amines due to the readily availability of nucleophiles and electrophiles.However,the inclusion of alkylarenes instead of active carbon pronucleophiles such as aldehydes and ketones in these addition reactions has been a challenge due to the inherent difficulty of benzylic deprotonation.In this study,we present a novel approach for the construction of N-sulfonyl amines via rhodium-catalyzed addition of unbiased benzylic C–H bonds to cyclic N-sulfonyl ketamines throughπ-coordination.This strategy enables the synthesis of a diverse range of N-sulfonyl amines,and subsequent diversification of the addition products showcases the synthetic potential of this protocol.
基金financially supported by the National Natural Science Foundation of China(grant nos.22272121 and 21972107)We thank the core facility of Wuhan University for the measurement of XPS.We also thank the Core Research Facilities of the College of Chemistry and Molecular Sciences for the measurement of TEM.DFT calculations in this paper have been done on the supercomputing system in the Supercomputing Center of Wuhan University.W.L.conceived and supervised the project.H.J.and Z.L.synthesized the electrocatalysts and performed the catalytic tests and characterization.J.Z.performed the DFT calculations.W.L.and H.J.wrote the manuscript.All the authors discussed the results and assisted during the manuscript preparation.
文摘The development of a highly efficient noniridium-based oxygen evolution reaction catalyst is the key to realizing large-scale commercial application of the proton-exchange membrane water electrolyzer.RuO_(2)is the most promising alternative to IrO_(2),but if usually suffers from lattice-oxygenmediated corrosion and sluggish proton transfer kinetics under acidic media.Herein,we propose an effective strategy of embedding RuO_(2)nanoparticles into a N-doped carbon support,termed as RuO_(2)-NC,to simultaneously prevent Ru dissolution and accelerate the bridging-oxygen-assisted deprotonation process.The obtained RuO_(2)-NC electrocatalyst presents high activity with an overpotential of 159 mV to reach 10 mA cm^(−2) and remarkable stability for over 240 h.Structural investigation and theoretical calculations reveal that the electron-rich NC substrate,as an electron donor,provides a buffered charge compensation to protect RuO_(2)from excessive oxidation and lattice oxygen loss by switching into a conventional adsorbate evolution mechanism(AEM).More importantly,the activated bridging oxygen(Obri)sites can facilitate the deprotonation of*OOH intermediates,leading to an optimized bridging-oxygen-assisted deprotonation AEM pathway.
基金This work was financially supported by the National Natural Science Foundation of China （51273136）, Natural Science Fund of Jiangsu Province （BK20151262）, a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions （PAPD）, the Project of Scientific and Technologic Infrastructure of Suzhou （SZS201708） and Collaborative Innovation Center of Radiological Medicine of Jiangsu Higher Education Institutions.
文摘Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence responses around 550--750 nm towards the hydrogen ions. The pKa of the probe 1a is 8.29, while that of the probe lb increases to 12.1 because of the hydrogen bond inside it. Selective and competitive experiments indicated that both common ions and amino acids did not interfere their emission with hydrogen ions. Moreover, confocal fluorescent imaging showed that the probe la could be served as mitochondria biomarker in HeLa and Ges-1 cells.
基金supported by the National Natural Science Foundation of China (No.21573208, No.21573210, and No.21873089)the National Key Basic Research Foundation of China (No.2013CB834602)
文摘Raman spectra of 1,2,4-triazole-3-carboxylate (TC- anion) and its ring-deprotonated deriva- tive (dpTC2- dianion) in aqueous solutions were measured respectively. The density func- tional theory calculations were performed using MN15 functional and PCM solvent model to investigate their structures, as well as the vibrational frequencies and Raman intensi- ties. With the aid of the calculated spectra, all the observed Raman bands of dpTC2- were clearly assigned, with taking into account the deuteration shifts. Moreover, various protonic tautomers of TC- anion were compared in the present theoretical calculations, and 2H- tautomer was found more stable. The experimental Raman spectrum of TC- solution was roughly consistent with the calculated spectrum of the monomeric 2H-tautomer of TC-, but some splits existed for a few bands when compared to the calculated spectra, which might be contributed by the hydrogen-bonding dimers of TC-.
基金supported by the Natural Science Foundation of Anhui Province,China(No.1408085ME96)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20133402120033)the Fundamental Research Funds for the Central Universities of China(No.WK2100000001)
文摘The on-chip fabrication of a carbon nanoparticle-chitosan composite membrane （i.e. a sorbent membrane or a mixed matrix membrane） using laminar flow-based interfacial deprotonation technology was presented in this paper. In addition, the effects of carbon nanoparticles and reactant flow rates on membrane formation were investigated. Finally, the permeability and adsorption capacities of the membrane were discussed. During fabrication, an acidic chitosan solution and a basic buffer solution that contained carbon nanoparticles were introduced into a microchannel. At the flow interface, a freestanding composite membrane with embedded carbon nanoparticles was formed due to the deprotonation of the chitosan molecules. The membrane growth gradually stopped with time from upstream to downstream and the thickness of the membrane increased rapidly and then slowly along the reactant flow direction. The formation of the membrane was divided into two stages. The average growth rate in the first stage was significantly larger than the average growth rate in the second stage. Carbon nanoparticles in the basic solution acted as nucleating agents and made the membrane formation much easier. As the flow rate of the chitosan solution increased, the averaged membrane thickness and the membrane hydraulic permeability initially increased and then decreased. Because of the addition of carbon nanoparticles, the formed membrane had adsorption abilities. The carbon nanoparticle-chitosan composite membrane that was fabricated in this study could be employed for simultaneous adsorption and dialysis in microdevices in the future.
基金We are grateful to the National Natural Science Foundation of China （Grant Nos. 21390401 and 21472098） and 973 Program （Grant No. 2012CB821600） for support of this work.
文摘Reaction of the N-heterocyclic borane [MeCCHC（CHe）（NAr）2]Btt （1, Ar=2,6-Me2C6H3） with B（C6F5）3 af- forded the zwitterionic hydroborane [MeCCHC（CHz）B（C6F5）3（NAr）2]BH, in which the β-methyl group can be deprotonated with LiN（SiMe3）2 to yield an anionic zwitterionic borenium.
基金Supported by the National Natural Science Foundation of China(Nos.20973076,21003057)the Specialized Research Fund for the Doctoral Program of Higher Education,China(No.20110061110018)
文摘A series of dye molecules was designed theoretically.Particularly,azoles and their derivatives were chosen as the modifying groups linking to ancillary ligands of [Ru（dcbpyH2）2（NCS）2]（N3,dcbpy=4,4＇-dicarboxy2,2＇-bipyridine;NCS=thiocyanato）.Density functional theory（DFT） based approaches were applied to exploring the electronic structures and properties of all these systems.The dye molecule with 1,2,4-triazole groups which exhibits a very high intensity of absorption in visible region,was obtained.Time-dependent DFT（TD-DFT） results indicate that the ancillary ligand dominates the molecular orbital（MO） energy levels and masters the absorption transition nature to a certain extent.The deprotonation of anchoring ligand not only affects the frontier MO energy levels but also controls the energy gaps of the highest occupied MO（HOMO） to the lowest unoccupied MO（LUMO） and LUMO to LUMO＋1 orbital.If the gap between LUMO-LUMO＋1 is small enough,the higher efficiency of dye-sensitized solar cell（DSSC） should be expected.
