Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can...Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth.In this study,an improved approach of adsorbed hydrocarbons extraction from sediments was established.The improved thermal desorption approach,compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The isotopic compositions of the terminal position carbon of propane(δ^(13)C_(terminal))serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins.The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter(typeⅢkerogen)at an early mature stage.δ^(13)C_(terminal)values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks,suggesting their genetic relationship.Overall,the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.展开更多
Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite chall...Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite challenging in simultaneously achieving high activity and selectivity for target products under mild conditions,especially when synthesizing high-value C2t chemicals such as ethanol[2].The conversion of methane to ethanol by photocatalysis is promising for achieving transformation under ambient temperature and pressure conditions.Currently,the apparent quantum efficiency(AQE)of solar-driven methane-to-ethanol conversion is generally below 0.5%[3,4].Furthermore,the stability of photocatalysts remains inadequate,offering substantial potential for further improvement.展开更多
Photosensitizers constitute a crucial element in the process of triplet-triplet annihilation upconversion,necessitating robust absorption of visible or near-infrared light,high intersystem crossing efficiency,prolonge...Photosensitizers constitute a crucial element in the process of triplet-triplet annihilation upconversion,necessitating robust absorption of visible or near-infrared light,high intersystem crossing efficiency,prolonged triplet state lifetime,and minimal energy dissipation during intersystem crossing and vibrational relaxation.Nonetheless,conventional monomeric photosensitizers frequently fail to simultaneously meet these requirements.In recent years,researchers,including our group,have fabricated photosensitizers that incorporate multiple covalent linkages,such as dyads and triads,which are regarded more likely to achieve comprehensive performance optimization.This review article explores the design and characteristics of recently synthesized dyads and triads photosensitizers that operate on the principles of intramolecular singlet energy transfer and intramolecular triplet energy transfer,demonstrating their outstanding efficacy in high-efficiency triplet-triplet annihilation upconversion.We provide an exhaustive explanation of the design rationales,photophysical,and photochemical properties of these photosensitizers,along with suggestions for the creation of photosensitizers with enhanced performance.Moreover,we discuss potential avenues and opportunities for the future development of triplet-triplet annihilation upconversion technology.展开更多
Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADB...Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.展开更多
The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a clas...The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.展开更多
The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the ...The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.展开更多
Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient gratin...Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.展开更多
Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^...Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.展开更多
The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric ...The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.展开更多
A quinine-derived thiourea-catalyzed inter-/intramolecular Michael cycloaddition of chromoneoxindole/benzofuranone synthons with 3-substituted methylenebenzofuranones has been established,which constructed enantiomeri...A quinine-derived thiourea-catalyzed inter-/intramolecular Michael cycloaddition of chromoneoxindole/benzofuranone synthons with 3-substituted methylenebenzofuranones has been established,which constructed enantiomerically pure bispiro[benzofuran-oxindole/benzofuran-chromanone]s bearing five consecutive stereocenters including two spiro quaternary carton centers in good yields(up to 93%) with high diastereoselectivities(up to>20:1 dr) and good enantioselectivities(up to>99% ee).Moreover,this is the first example of bifunctional chromone-benzofuranone synthon directed organocatalytic tandem reaction,and also the first example of the bispiro[benzofuran-oxindole] and bispirobenzofuranone,potentially useful in medicinal chemistry.展开更多
To develop smart and efficient near-infrared(NIR)organic dyes for photothermal cancer therapy is of great challenge.Herein,a pH-sensitive NIR dye BTN with donor–acceptor–donor scaffold has been synthesized.Two perip...To develop smart and efficient near-infrared(NIR)organic dyes for photothermal cancer therapy is of great challenge.Herein,a pH-sensitive NIR dye BTN with donor–acceptor–donor scaffold has been synthesized.Two periphery electron-donating dimethylamine groups in BTN can not only promote the intramolecular photoinduced electron transfer(PET),but also bind protons to transform into electron-deficient ammonium cation for enhanced intramolecular charge transfer(ICT)under acidic circumstance.Through enveloping with amphiphilic polymeric 1,2-distearoyl-ras-glycerol-3-phosphatidyl ethanolamine-N-polyethyleneglycol-2000(DSPE-mPEG2000),BTN nanoparticles(NPs)were fabricated with robust NIR absorption covering 600–900 nm,excellent photothermal conversion efficiency(43.2%),and good photostability.Additionally,BTN NPs can selectively target lysosomes.Through tailing intravenous injection into tumor-bearing nude mice,BTN NPs demonstrate outstanding photoacoustic/photothermal/fluorescence imaging-guided photothermal therapy for tumor ablation.展开更多
An alternative construction of A-B-D ring-system of erythrinan and homoerythrinan alkaloids by TiCl4-mediated tandem semipinacol/intramolecular Schmidt reaction of α-siloxyepoxyazide was addressed and the unusual epo...An alternative construction of A-B-D ring-system of erythrinan and homoerythrinan alkaloids by TiCl4-mediated tandem semipinacol/intramolecular Schmidt reaction of α-siloxyepoxyazide was addressed and the unusual epoxidation stereoselectivity was observed in preparation of the substrate once again.展开更多
Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influenci...Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.展开更多
The triplet state energies of para aminobenzoic acid and nicotinic acid were determined by means of low temperature phosphorescence spectrometry. The energy matches between them and the resonant emitting energy l...The triplet state energies of para aminobenzoic acid and nicotinic acid were determined by means of low temperature phosphorescence spectrometry. The energy matches between them and the resonant emitting energy levels of Eu 3+ , Tb 3+ , Sm 3+ , Dy 3+ were studied. The intramolecular energy transfer processes from the two aromatic carboxylic acid ligands to rare earth ions were also discussed on the basis of the measurement results of luminescence intensities, lifetimes and quantum efficiencies.展开更多
In this paper, we estimate the rate of contact formation between two residues in the interior of the proteins using the Szabo, Schulten, and Schulten formula with the probability distribution P（r） based on 375 prote...In this paper, we estimate the rate of contact formation between two residues in the interior of the proteins using the Szabo, Schulten, and Schulten formula with the probability distribution P（r） based on 375 proteins from PDB （Protein Data Bank）. The probability distribution for residue pair in proteins is different from the Gaussian distribution, especially for short distance between two residues in proteins. The rate of contact formation in the interior of protein is discussed as a function of distance n （=｜j -i｜） between two residues, and it decreases monotonically with n and follows the scaling relationship of k ∝ n^-γ with γ= 1.43 for the contact radius a = 0.40 nm and γ=1.05 for a = 0.50 nm. The diffusion coefficient for the relative diffusion of two residues in the interior of proteins is estimated as D = 6.4 × 10^-6 cm^2/s, which is close to the result that is found for monomer diffusion.展开更多
Phase-transfer-catalyzed intramolecular cyclization reaction of forming benzo[b]furan and 3-methyleneisoin- doline-1-one derivatives has been developed. The cyclization reaction of propargylic carbonates was also de- ...Phase-transfer-catalyzed intramolecular cyclization reaction of forming benzo[b]furan and 3-methyleneisoin- doline-1-one derivatives has been developed. The cyclization reaction of propargylic carbonates was also de- scribed under metal-free condition and the reaction was reported by Pd and Ni before. The reaction condi- tions and the scope of the process are examined. The catalysts are cheap and environmentally friendly and the substrates are readily available and the procedure is simple, rapid, and general. The development of C-O and C-N bond formation processes via an overall structural isomerization represents the most atom-eco- nomical approach.展开更多
The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on ...The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on proton transfer.The mechanism of hydrogen bond enhancement is qualitatively elucidated by comparing the infrared spectra, the reduced density gradient, and the frontier molecular orbitals.The calculated electronic spectra are consistent with the experimental results.To quantify the proton transfer, the potential energy curves(PECs) of the four derivatives in S0 and S1 states are scanned.It is concluded that the ability of proton transfer follows the order: FM > BFM > BFBC > CCM.展开更多
Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their ...Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.展开更多
The dynamical correlation between quantum entanglement and intramolecular energy in realistic molecular vibrations is explored using the Lie algebraic approach. The explicit expression of entanglement measurement can ...The dynamical correlation between quantum entanglement and intramolecular energy in realistic molecular vibrations is explored using the Lie algebraic approach. The explicit expression of entanglement measurement can be achieved using algebraic operations. The common and different characteristics of dynamical entanglement in different molecular vibrations are also provided. The dynamical study of quantum entanglement and intramolecular energy in small molecular vibrations can be helpful for controlling the entanglement and further understanding the intramolecular dynamics.展开更多
Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctiona...Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctionalized 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylper- oxide gave above intermediates in high yields. The mild reaction conditions and easy purification procedures of this method provide a new approach for the synthesis of phenanthrenes.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.42102202)U.S.Department of Energy Geosciences program(DE-SC0016271)。
文摘Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth.In this study,an improved approach of adsorbed hydrocarbons extraction from sediments was established.The improved thermal desorption approach,compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The isotopic compositions of the terminal position carbon of propane(δ^(13)C_(terminal))serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins.The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter(typeⅢkerogen)at an early mature stage.δ^(13)C_(terminal)values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks,suggesting their genetic relationship.Overall,the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.
基金the support from the National Natural Science Foundation of China(52202306)Program from Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101 and RCTDPT-2020-001)+1 种基金Shenzhen Key Laboratory of Eco-materials and Renewable Energy(ZDSYS20200922160400001)the Provincial Talent Plan of Guangdong(2023TB0012).
文摘Methane(CH4),the predominant component of natural gas and shale gas,is regarded as a promising carbon feedstock for chemical synthesis[1].However,considering the extreme stability of CH4 molecules,it's quite challenging in simultaneously achieving high activity and selectivity for target products under mild conditions,especially when synthesizing high-value C2t chemicals such as ethanol[2].The conversion of methane to ethanol by photocatalysis is promising for achieving transformation under ambient temperature and pressure conditions.Currently,the apparent quantum efficiency(AQE)of solar-driven methane-to-ethanol conversion is generally below 0.5%[3,4].Furthermore,the stability of photocatalysts remains inadequate,offering substantial potential for further improvement.
基金supported by the National Natural Science Foundation of China(No.22203004 and No.21927814)the Anhui Normal University 2023 Scholarship and Supplementary Discipline Construction Project(No.2023GFXK160).
文摘Photosensitizers constitute a crucial element in the process of triplet-triplet annihilation upconversion,necessitating robust absorption of visible or near-infrared light,high intersystem crossing efficiency,prolonged triplet state lifetime,and minimal energy dissipation during intersystem crossing and vibrational relaxation.Nonetheless,conventional monomeric photosensitizers frequently fail to simultaneously meet these requirements.In recent years,researchers,including our group,have fabricated photosensitizers that incorporate multiple covalent linkages,such as dyads and triads,which are regarded more likely to achieve comprehensive performance optimization.This review article explores the design and characteristics of recently synthesized dyads and triads photosensitizers that operate on the principles of intramolecular singlet energy transfer and intramolecular triplet energy transfer,demonstrating their outstanding efficacy in high-efficiency triplet-triplet annihilation upconversion.We provide an exhaustive explanation of the design rationales,photophysical,and photochemical properties of these photosensitizers,along with suggestions for the creation of photosensitizers with enhanced performance.Moreover,we discuss potential avenues and opportunities for the future development of triplet-triplet annihilation upconversion technology.
基金supported by the National Natural Science Foundation of China (22279063 and 52001170)the Fundamental Research Funds for the Central Universities+2 种基金Tianjin Natural Science Foundation (No. 22JCYBJC00590)the financial support by the Ministry of Education, Singapore, under its Academic Research Fund Tier 1 Thematic (RT8/22)the Haihe Laboratory of Sustainable Chemical Transformations, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) for financial support
文摘Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.
基金the financial support by the National Natural Science Foundation of China (22371010, 21771017, and 51702009)the "Hundred Talents Program" of the Chinese Academy of Sciences, the Fundamental Research Funds for the Central Universities+1 种基金the Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ2021-0324123202008, JCYJ20210 324122803009 and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation (2021A1515110880)
文摘The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.61137005 and No.10974023）, the Program for Liaoning Excellent Talents in University （No.LJQ2012002）, and the Program for New Century Excellent Talents in University （No.NCET-12-0077）.
文摘The excited state intramolecular proton transfer （ESIPT） coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21003033 and 21203047)the Guangxi Provincial Natural Science Foundation,China(Grant Nos.2012GXNSFBA053012 and 2014GXNSFAA118019)the Research Foundation of Education Bureau of Guangxi Zhuang Autonomous Region,China(Grant No.ZD2014127)
文摘Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.
基金Project supported by the National Basic Research Program of China(Grant No.2013CB922204)the National Natural Science Foundation of China(Grant Nos.11574115 and 11704146)the Natural Science Foundation of Jilin Province,China(Grant No.20150101063JC)
文摘Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT.
文摘The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.
基金financial support from the National Nature Science Foundation of China(Nos.81760625,81660576 and81560563)Projects of Guizhou Province(Nos.[2016]5623,JG[2016]06,[2019]1402,[2017]5609 and[2018]5781)。
文摘A quinine-derived thiourea-catalyzed inter-/intramolecular Michael cycloaddition of chromoneoxindole/benzofuranone synthons with 3-substituted methylenebenzofuranones has been established,which constructed enantiomerically pure bispiro[benzofuran-oxindole/benzofuran-chromanone]s bearing five consecutive stereocenters including two spiro quaternary carton centers in good yields(up to 93%) with high diastereoselectivities(up to>20:1 dr) and good enantioselectivities(up to>99% ee).Moreover,this is the first example of bifunctional chromone-benzofuranone synthon directed organocatalytic tandem reaction,and also the first example of the bispiro[benzofuran-oxindole] and bispirobenzofuranone,potentially useful in medicinal chemistry.
基金The work was financially supported by the Natural Science Foundation of Jiangsu Province(Nos.BK20200092 and BK20200710).
文摘To develop smart and efficient near-infrared(NIR)organic dyes for photothermal cancer therapy is of great challenge.Herein,a pH-sensitive NIR dye BTN with donor–acceptor–donor scaffold has been synthesized.Two periphery electron-donating dimethylamine groups in BTN can not only promote the intramolecular photoinduced electron transfer(PET),but also bind protons to transform into electron-deficient ammonium cation for enhanced intramolecular charge transfer(ICT)under acidic circumstance.Through enveloping with amphiphilic polymeric 1,2-distearoyl-ras-glycerol-3-phosphatidyl ethanolamine-N-polyethyleneglycol-2000(DSPE-mPEG2000),BTN nanoparticles(NPs)were fabricated with robust NIR absorption covering 600–900 nm,excellent photothermal conversion efficiency(43.2%),and good photostability.Additionally,BTN NPs can selectively target lysosomes.Through tailing intravenous injection into tumor-bearing nude mice,BTN NPs demonstrate outstanding photoacoustic/photothermal/fluorescence imaging-guided photothermal therapy for tumor ablation.
文摘An alternative construction of A-B-D ring-system of erythrinan and homoerythrinan alkaloids by TiCl4-mediated tandem semipinacol/intramolecular Schmidt reaction of α-siloxyepoxyazide was addressed and the unusual epoxidation stereoselectivity was observed in preparation of the substrate once again.
文摘Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.
文摘The triplet state energies of para aminobenzoic acid and nicotinic acid were determined by means of low temperature phosphorescence spectrometry. The energy matches between them and the resonant emitting energy levels of Eu 3+ , Tb 3+ , Sm 3+ , Dy 3+ were studied. The intramolecular energy transfer processes from the two aromatic carboxylic acid ligands to rare earth ions were also discussed on the basis of the measurement results of luminescence intensities, lifetimes and quantum efficiencies.
基金This research was financially supported by the National Natural Science Foundation of China (No. 20574052)Program for New Century Excellent Talents in University,and Natural Science Foundation of Zhejiang Province (No. R404047)
文摘In this paper, we estimate the rate of contact formation between two residues in the interior of the proteins using the Szabo, Schulten, and Schulten formula with the probability distribution P（r） based on 375 proteins from PDB （Protein Data Bank）. The probability distribution for residue pair in proteins is different from the Gaussian distribution, especially for short distance between two residues in proteins. The rate of contact formation in the interior of protein is discussed as a function of distance n （=｜j -i｜） between two residues, and it decreases monotonically with n and follows the scaling relationship of k ∝ n^-γ with γ= 1.43 for the contact radius a = 0.40 nm and γ=1.05 for a = 0.50 nm. The diffusion coefficient for the relative diffusion of two residues in the interior of proteins is estimated as D = 6.4 × 10^-6 cm^2/s, which is close to the result that is found for monomer diffusion.
文摘Phase-transfer-catalyzed intramolecular cyclization reaction of forming benzo[b]furan and 3-methyleneisoin- doline-1-one derivatives has been developed. The cyclization reaction of propargylic carbonates was also de- scribed under metal-free condition and the reaction was reported by Pd and Ni before. The reaction condi- tions and the scope of the process are examined. The catalysts are cheap and environmentally friendly and the substrates are readily available and the procedure is simple, rapid, and general. The development of C-O and C-N bond formation processes via an overall structural isomerization represents the most atom-eco- nomical approach.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11874241,11847224,and 11804195)the Shandong Province Higher Educational Science and Technology Program,China(Grant No.J15LJ03)+1 种基金the Taishan Scholar Project of Shandong Province,China,China Post-Doctoral Foundation(Grant No.2018M630796)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2018BA034)
文摘The excited state intramolecular proton transfer of four derivatives(FM, BFM, BFBC, CCM) of 3-hydroxychromone is investigated.The geometries of different substituents are optimized to study the substituent effects on proton transfer.The mechanism of hydrogen bond enhancement is qualitatively elucidated by comparing the infrared spectra, the reduced density gradient, and the frontier molecular orbitals.The calculated electronic spectra are consistent with the experimental results.To quantify the proton transfer, the potential energy curves(PECs) of the four derivatives in S0 and S1 states are scanned.It is concluded that the ability of proton transfer follows the order: FM > BFM > BFBC > CCM.
基金supported by the Research Grants Council General Research Fund (No. 17301314)
文摘Furans bearing epoxy enolsilane units via a tether that incorporates a nitrogen heteroatom,undergo intramolecular(4+3)cycloadditions to generate bis-heteroatomic polycyclic adducts having piperidine moieties in their frameworks.The cycloadducts,ultimately derived from furfural,a renewal chemical feedstock,are obtained with up to 4:1 dr and with ee retained from the epoxide.
基金supported by the National Natural Science Foundation of China(Grant Nos.11147019 and 91021009)
文摘The dynamical correlation between quantum entanglement and intramolecular energy in realistic molecular vibrations is explored using the Lie algebraic approach. The explicit expression of entanglement measurement can be achieved using algebraic operations. The common and different characteristics of dynamical entanglement in different molecular vibrations are also provided. The dynamical study of quantum entanglement and intramolecular energy in small molecular vibrations can be helpful for controlling the entanglement and further understanding the intramolecular dynamics.
基金Sichuan Provincial Education Department(No.12ZA141)Key Laboratory of Advanced Functional Materials of Sichuan Province Higher Education System (No.KFKT2013-01)Sichuan Normal University(No.XYZ201314-37)for financial support
文摘Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctionalized 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylper- oxide gave above intermediates in high yields. The mild reaction conditions and easy purification procedures of this method provide a new approach for the synthesis of phenanthrenes.
