Background: Dry eye and glaucoma are two common pathologies in the elderly, and are very often associated. This association suggests a link between them and between their treatments. Our purpose for this study is to d...Background: Dry eye and glaucoma are two common pathologies in the elderly, and are very often associated. This association suggests a link between them and between their treatments. Our purpose for this study is to determine the prevalence of dry eye in our glaucoma patients treated with eye drops and deduce the factors associated with it. Patients and Methods: We conducted a cross-sectional, analytical study from October 2022 to September 2023 in the ophthalmology department of Garoua Regional Hospital in glaucoma patients aged over 15 years able to answer the Ocular Surface Disease Index (OSDI) questionnaires and treated with antiglaucoma eye drops for more than 3 months. These patients underwent a complete ophthalmological examination and a tear film break-up time test. Results: A total of 73 patients (146 eyes) were examined. The average age of the patients was 47.2 ± 16.5 years, with a male predominance of 54.8%. The prevalence of dry eye syndrome in our patients according to the OSDI score was 56.2% (95% CI) (44.8;67.6). The prevalence of dry eye syndrome on clinical examination of the BUT in the right eye was 83.7% (95% CI) (75.1;92.1) and 79.4% (70.2;88.7) in the left eye. The duration of antiglaucoma treatment was the factor associated with dry eye syndrome (p < 0.05) in glaucoma patients in our setting. Conclusion: Dry Eye Syndrome is common in glaucoma patients on drops in our setting. Treatment duration of more than 1 year seems to be associated with dry eyes.展开更多
Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectr...Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectroscopic techniques, single crystal X-ray diffraction,super conducting quantum interference device(SQUID) measurements and theoretical calculations. The dications have triplet ground states with ferromagnetic interaction exceeding the thermal energy at room temperature. The solid-state structures of these species were tunable by substituent effect, with 1^(2+) as a monomer and 2^(2+) as a dimer.展开更多
The Raman spectra of poly(3-methylthiophene) (PMeT) films with different thicknesses, which have been electrochemically deposited on a flat stainless steel electrode surface by direct oxidation of 3-methylthiophene in...The Raman spectra of poly(3-methylthiophene) (PMeT) films with different thicknesses, which have been electrochemically deposited on a flat stainless steel electrode surface by direct oxidation of 3-methylthiophene in boron trifluoride diethyl etherate (BFEE) at a constant applied potential of 1.38 V (versus SCE), have been investigated by excitation with a 633-nm laser beam. The spectroscopic results demonstrated that the doping level of PMeT film was increasing during film growth. This finding was also confirmed by electrochemical examination. Moreover, the Raman bands assigned to radical cations and dications in doped PMeT films were found approximately at 1420 and 1400 cm(-1), respectively. Radical cations and dications coexist on the backbone of PMeT as conductive species and their concentrations increase with the increase of doping level. Successive cyclic voltammetry was proved to be an effective approach to improving the doping level of as-grown thin compact PMeT film.展开更多
Doubly charged positive ions(dications)are an important component of planetary ionospheres because of the large energy required for their formation.Observations of these ions are exceptionally difficult due to their l...Doubly charged positive ions(dications)are an important component of planetary ionospheres because of the large energy required for their formation.Observations of these ions are exceptionally difficult due to their low abundances;until now,only atomic dications have been detected.The Neutral Gas and Ion Mass Spectrometer(NGIMS)measurements made on board the recent Mars Atmosphere and Volatile Evolution mission provide the first opportunity for decisive detection of molecular dications,CO2^++in this case,in a planetary upper atmosphere.The NGIMS data reveal a dayside averaged CO2^++distribution declining steadily from 5.6 cm^−3 at 160 km to below 1 cm^−3 above 200 km.The dominant CO2^++production mechanisms are double photoionization of CO2 below 190 km and single photoionization of CO2^+at higher altitudes;CO2++destruction is dominated by natural dissociation,but reactions with atmospheric CO2 and O become important below 160 km.Simplified photochemical model calculations are carried out and reasonably reproduce the data at low altitudes within a factor of 2 but underestimate the data at high altitudes by a factor of 4.Finally,we report a much stronger solar control of the CO2^++density than of the CO2+density.展开更多
Motivated by the search for ways of a more efficient usage of the ubiquitous, and unexploited resources of methane, recent progress in the gas-phase activation of methane by metal dication complex ion is discussed. Th...Motivated by the search for ways of a more efficient usage of the ubiquitous, and unexploited resources of methane, recent progress in the gas-phase activation of methane by metal dication complex ion is discussed. The gas phase theoretical and experimental analysis on [Pb(Benzene)2]2+ was conducted. The [Pb(Benzene)2]2+ complex ions were prepared using a combination of the pick-up technique and high energy electron impact, and then held in a cold ion trap. Excitation with tuneable UV radiation resulted in the formation of [Pb(Benzene)2(H2O)]2+, [Pb(Benzene)2(H2O)2]2+, [Pb(Benzene)]+, Pb+ and Benzene+ ions when the experimental results were analysed. The two optimised geometries of [Pb(Benzene)2]2+ namely the C2V eclipse and C2 staggered were observed. Methane activation of [Pb(Benzene)2]2+ complex ion yielded [Pb(Benzene)2(Me)]2+. [Pb(Benzene)2(H2O)(Me)2]2+,? [Pb(Benzene)2(H2O)(Me)]2+, [PbBenzene(Me)3]2+ and [Pb(Benzene)(Me)]2+. The PEC calculated binding energy of methane to lead benzene dication complex ion was approximately 25.45% higher than the value recorded on DFT calculation. This difference was due to the charge differences on the lead metal centre. While the actual calculated charge on the Pb metal in the optimised geometry was 1.68 the charge of +2 on the Pb metal was considered in the PEC calculation.展开更多
The VUV double photoionizations of small molecules (NO, CO, CO2, CS2, OSC and NH3) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules we...The VUV double photoionizations of small molecules (NO, CO, CO2, CS2, OSC and NH3) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO^2+,CO^2+,CO2^2+, CS2^2+, OSC^2+and NH^2+) were calculated using the Gaussian O3 program and Gaussian 2 (NO^2+, CO^2+, CO2^2+,CS2^2+,OSC^2+ and NH3^2+) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then, the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.展开更多
Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromo- allenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.
The incorporation of heteroatoms into carbon nanohoops can significantly overcome aromatic stabilization energy and enrich their physicochemical properties depending on the positions and numbers of the doped atoms.Uti...The incorporation of heteroatoms into carbon nanohoops can significantly overcome aromatic stabilization energy and enrich their physicochemical properties depending on the positions and numbers of the doped atoms.Utilizing a V-shaped dipyreneo[c,e]dihydrophenazine as the building block,herein we report a novel kind of axially N-embedded quasi-carbon nanohoops by integratingπ-extended dihydropyrazine and para-phenylene subunits.Singlecrystal X-ray diffraction analyses revealed that their geometrical structures varied from droplet-shaped geometry for DPP-M and suppressed elliptical cross-section configuration for DPP-D to triangularly prismatic configuration for DPP-T.Spectroscopic measurements confirmed rich electronic properties,especially multioxidation behaviors due to the embedding of graphitic-N atoms,which are not observed in carbonaceous nanohoops and other analogs.Further investigations,including electron spin resonance spectroscopy,theoretical calculations,and single-crystal structure analyses,on the oxidized species of both DPP-D and DPP-T demonstrated their tunable open-shell ground states for the dications.This work provides a new synthetic strategy to axially N-embedded quasi-carbon nanohoops and gives insights into the design of structure-precise segments of graphitic-N-doped single-walled carbon nanotubes.展开更多
Recent years have witnessed breakthroughs in the study of zigzag hydrocarbon belts.However,the synthesis of heterocycle-containing zigzag molecular belts remains very rare and challenging despite their interesting str...Recent years have witnessed breakthroughs in the study of zigzag hydrocarbon belts.However,the synthesis of heterocycle-containing zigzag molecular belts remains very rare and challenging despite their interesting structures and potential applications in chemistry and materials science.Here,we report the expeditious construction of a highly strained belt[4]arene[4](1,4-dihydropyridine)structure using the fjords-stitching strategy.The synthesis comprised four-fold abnormal m-bromination of four Npivaloylaniline units and Pd_(2)(dba)_(3)/4-Me_(2)NC_(6)H_(4)Pt Bu_(2)-catalyzed intramolecular C-N bond-forming reactions.Subsequent functionalization through Narylations produced a variety of tetraza-embedded octahydrobelt[8]arenes.Further oxidation of p-methoxyphenyl-substituted belt[4]arene[4](1,4-dihydropyridine)with Ag[Al(O^(t)Bu^(F))^(4)]yielded a singlet diradical dication N-doped zigzag belt.展开更多
A cadmium tetracyanoplatinate host clathrate,(MV)[Cd_(2){Pt(CN)_(4)}_(3)]·2(H_(2)O)(1),including a methylviologen dication (MV^(2+)) was synthesized,and the crystal structures,photochromic and photoluminescence p...A cadmium tetracyanoplatinate host clathrate,(MV)[Cd_(2){Pt(CN)_(4)}_(3)]·2(H_(2)O)(1),including a methylviologen dication (MV^(2+)) was synthesized,and the crystal structures,photochromic and photoluminescence properties were investigated.In 1,the alternatively parallel stacking between the MV^(2+)dications as electron acceptors in the channels and the electron donors[Pt1(CN)_(4)]^(2-) units in the host frameworks give a unique donor-acceptor (DA) system.Under UV irradiation,the electron transfer between MV^(2+) and[Pt(CN)_(4)]^(2-) ions generates MV^(·+)radicals with a photochromic behavior from pale-yellow to blue.This process occurs through single-crystal-to-single-crystal (SCSC) transformation and obvious structure variation of viologen cations is successfully observed.Moreover,the spectral overlap between the emission bands of 1 and the absorption around 623 nm for the MV^(·+) radicals leads to a modulation of the photoluminescence.展开更多
Herein,we conceptualized a transient mediator approach that has the capability of para-selective C–H functionalization of monosubstituted aromatics.This approach is enabled by in situ generation of a versatile sulfon...Herein,we conceptualized a transient mediator approach that has the capability of para-selective C–H functionalization of monosubstituted aromatics.This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride.Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate.The versatility of this approach was demonstrated via paraborylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.展开更多
文摘Background: Dry eye and glaucoma are two common pathologies in the elderly, and are very often associated. This association suggests a link between them and between their treatments. Our purpose for this study is to determine the prevalence of dry eye in our glaucoma patients treated with eye drops and deduce the factors associated with it. Patients and Methods: We conducted a cross-sectional, analytical study from October 2022 to September 2023 in the ophthalmology department of Garoua Regional Hospital in glaucoma patients aged over 15 years able to answer the Ocular Surface Disease Index (OSDI) questionnaires and treated with antiglaucoma eye drops for more than 3 months. These patients underwent a complete ophthalmological examination and a tear film break-up time test. Results: A total of 73 patients (146 eyes) were examined. The average age of the patients was 47.2 ± 16.5 years, with a male predominance of 54.8%. The prevalence of dry eye syndrome in our patients according to the OSDI score was 56.2% (95% CI) (44.8;67.6). The prevalence of dry eye syndrome on clinical examination of the BUT in the right eye was 83.7% (95% CI) (75.1;92.1) and 79.4% (70.2;88.7) in the left eye. The duration of antiglaucoma treatment was the factor associated with dry eye syndrome (p < 0.05) in glaucoma patients in our setting. Conclusion: Dry Eye Syndrome is common in glaucoma patients on drops in our setting. Treatment duration of more than 1 year seems to be associated with dry eyes.
基金supported by the National Natural Science Foundation of China(21525102,21690062)the Natural Science Foundation of Jiangsu Province(BK20140014)
文摘Two tetraazacyclophane dications(1^(2+) and 2^(2+)) with different remote substituents have been synthesized, isolated and characterized.Their electronic structures and physical property were studied by various spectroscopic techniques, single crystal X-ray diffraction,super conducting quantum interference device(SQUID) measurements and theoretical calculations. The dications have triplet ground states with ferromagnetic interaction exceeding the thermal energy at room temperature. The solid-state structures of these species were tunable by substituent effect, with 1^(2+) as a monomer and 2^(2+) as a dimer.
基金This work was supported by the National Natual Science Foundation of China (No. 50073012 & No. 50133010).
文摘The Raman spectra of poly(3-methylthiophene) (PMeT) films with different thicknesses, which have been electrochemically deposited on a flat stainless steel electrode surface by direct oxidation of 3-methylthiophene in boron trifluoride diethyl etherate (BFEE) at a constant applied potential of 1.38 V (versus SCE), have been investigated by excitation with a 633-nm laser beam. The spectroscopic results demonstrated that the doping level of PMeT film was increasing during film growth. This finding was also confirmed by electrochemical examination. Moreover, the Raman bands assigned to radical cations and dications in doped PMeT films were found approximately at 1420 and 1400 cm(-1), respectively. Radical cations and dications coexist on the backbone of PMeT as conductive species and their concentrations increase with the increase of doping level. Successive cyclic voltammetry was proved to be an effective approach to improving the doping level of as-grown thin compact PMeT film.
基金supported by the B-type Strategic Priority Program No.XDB41000000funded by the Chinese Academy of Sciences,and the pre-research projects on Civil Aerospace Technologies No.D020105 and D020103+1 种基金funded by China's National Space Administrationthe National Science Foundation of China through grants 41525015 and 41774186 to JC,41904154 to WXS,and 41525016 to YW.
文摘Doubly charged positive ions(dications)are an important component of planetary ionospheres because of the large energy required for their formation.Observations of these ions are exceptionally difficult due to their low abundances;until now,only atomic dications have been detected.The Neutral Gas and Ion Mass Spectrometer(NGIMS)measurements made on board the recent Mars Atmosphere and Volatile Evolution mission provide the first opportunity for decisive detection of molecular dications,CO2^++in this case,in a planetary upper atmosphere.The NGIMS data reveal a dayside averaged CO2^++distribution declining steadily from 5.6 cm^−3 at 160 km to below 1 cm^−3 above 200 km.The dominant CO2^++production mechanisms are double photoionization of CO2 below 190 km and single photoionization of CO2^+at higher altitudes;CO2++destruction is dominated by natural dissociation,but reactions with atmospheric CO2 and O become important below 160 km.Simplified photochemical model calculations are carried out and reasonably reproduce the data at low altitudes within a factor of 2 but underestimate the data at high altitudes by a factor of 4.Finally,we report a much stronger solar control of the CO2^++density than of the CO2+density.
文摘Motivated by the search for ways of a more efficient usage of the ubiquitous, and unexploited resources of methane, recent progress in the gas-phase activation of methane by metal dication complex ion is discussed. The gas phase theoretical and experimental analysis on [Pb(Benzene)2]2+ was conducted. The [Pb(Benzene)2]2+ complex ions were prepared using a combination of the pick-up technique and high energy electron impact, and then held in a cold ion trap. Excitation with tuneable UV radiation resulted in the formation of [Pb(Benzene)2(H2O)]2+, [Pb(Benzene)2(H2O)2]2+, [Pb(Benzene)]+, Pb+ and Benzene+ ions when the experimental results were analysed. The two optimised geometries of [Pb(Benzene)2]2+ namely the C2V eclipse and C2 staggered were observed. Methane activation of [Pb(Benzene)2]2+ complex ion yielded [Pb(Benzene)2(Me)]2+. [Pb(Benzene)2(H2O)(Me)2]2+,? [Pb(Benzene)2(H2O)(Me)]2+, [PbBenzene(Me)3]2+ and [Pb(Benzene)(Me)]2+. The PEC calculated binding energy of methane to lead benzene dication complex ion was approximately 25.45% higher than the value recorded on DFT calculation. This difference was due to the charge differences on the lead metal centre. While the actual calculated charge on the Pb metal in the optimised geometry was 1.68 the charge of +2 on the Pb metal was considered in the PEC calculation.
基金supported by the National Natural Science Foundation of China (Grant No. 10874167)the Knowledge Innovation Foundation of the Chinese Academy of Sciences (Grant No. KJCX2-YW-N24)
文摘The VUV double photoionizations of small molecules (NO, CO, CO2, CS2, OSC and NH3) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO^2+,CO^2+,CO2^2+, CS2^2+, OSC^2+and NH^2+) were calculated using the Gaussian O3 program and Gaussian 2 (NO^2+, CO^2+, CO2^2+,CS2^2+,OSC^2+ and NH3^2+) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then, the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.
基金We are grateful to the National Natural Science Foundation of China(No.20472072,20332060).
文摘Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromo- allenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.
基金financially supported by the National Natural Science Foundation of China(grant nos.22235005,21871084,and 21790361)the Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03)+3 种基金the Fundamental Research Funds for the Central Universities,the Programme of Introducing Talents of Discipline to Universities(grant no.B16017)the Program of Shanghai Academic/Technology Research Leader(grant no.19XD1421100)the Shanghai Science and Technology Committee(grant no.17520750100)the China Postdoctoral Science Foundation(grant no.2020M671018).
文摘The incorporation of heteroatoms into carbon nanohoops can significantly overcome aromatic stabilization energy and enrich their physicochemical properties depending on the positions and numbers of the doped atoms.Utilizing a V-shaped dipyreneo[c,e]dihydrophenazine as the building block,herein we report a novel kind of axially N-embedded quasi-carbon nanohoops by integratingπ-extended dihydropyrazine and para-phenylene subunits.Singlecrystal X-ray diffraction analyses revealed that their geometrical structures varied from droplet-shaped geometry for DPP-M and suppressed elliptical cross-section configuration for DPP-D to triangularly prismatic configuration for DPP-T.Spectroscopic measurements confirmed rich electronic properties,especially multioxidation behaviors due to the embedding of graphitic-N atoms,which are not observed in carbonaceous nanohoops and other analogs.Further investigations,including electron spin resonance spectroscopy,theoretical calculations,and single-crystal structure analyses,on the oxidized species of both DPP-D and DPP-T demonstrated their tunable open-shell ground states for the dications.This work provides a new synthetic strategy to axially N-embedded quasi-carbon nanohoops and gives insights into the design of structure-precise segments of graphitic-N-doped single-walled carbon nanotubes.
基金We thank the National Natural Science Foundation of China(grant nos.22050005,21732004,and 21821001)the Tsinghua University Initiative Scientific Research Program(grant no.2019Z07L01004)for generous financial support.
文摘Recent years have witnessed breakthroughs in the study of zigzag hydrocarbon belts.However,the synthesis of heterocycle-containing zigzag molecular belts remains very rare and challenging despite their interesting structures and potential applications in chemistry and materials science.Here,we report the expeditious construction of a highly strained belt[4]arene[4](1,4-dihydropyridine)structure using the fjords-stitching strategy.The synthesis comprised four-fold abnormal m-bromination of four Npivaloylaniline units and Pd_(2)(dba)_(3)/4-Me_(2)NC_(6)H_(4)Pt Bu_(2)-catalyzed intramolecular C-N bond-forming reactions.Subsequent functionalization through Narylations produced a variety of tetraza-embedded octahydrobelt[8]arenes.Further oxidation of p-methoxyphenyl-substituted belt[4]arene[4](1,4-dihydropyridine)with Ag[Al(O^(t)Bu^(F))^(4)]yielded a singlet diradical dication N-doped zigzag belt.
文摘A cadmium tetracyanoplatinate host clathrate,(MV)[Cd_(2){Pt(CN)_(4)}_(3)]·2(H_(2)O)(1),including a methylviologen dication (MV^(2+)) was synthesized,and the crystal structures,photochromic and photoluminescence properties were investigated.In 1,the alternatively parallel stacking between the MV^(2+)dications as electron acceptors in the channels and the electron donors[Pt1(CN)_(4)]^(2-) units in the host frameworks give a unique donor-acceptor (DA) system.Under UV irradiation,the electron transfer between MV^(2+) and[Pt(CN)_(4)]^(2-) ions generates MV^(·+)radicals with a photochromic behavior from pale-yellow to blue.This process occurs through single-crystal-to-single-crystal (SCSC) transformation and obvious structure variation of viologen cations is successfully observed.Moreover,the spectral overlap between the emission bands of 1 and the absorption around 623 nm for the MV^(·+) radicals leads to a modulation of the photoluminescence.
基金supported by Shanghai Institute of Organic Chemistry,State Key Laboratory of Organometallic Chemistry,the National Natural Science Foundation of China(21890722,21702109,11811530637)the Natural Science Foundation of Tianjin City(18JCYBJC21400)the Fundamental Research Funds for the Central Universities(63191515,63196021,63191523).
文摘Herein,we conceptualized a transient mediator approach that has the capability of para-selective C–H functionalization of monosubstituted aromatics.This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride.Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate.The versatility of this approach was demonstrated via paraborylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.