NEW DWELLERS OF MOUNTAINS Neweekly 15 September A growing number of people are turning towards the mountains,venturing into valleys and forests to explore a life as“new mountain dwellers”–a fresh way of mountain li...NEW DWELLERS OF MOUNTAINS Neweekly 15 September A growing number of people are turning towards the mountains,venturing into valleys and forests to explore a life as“new mountain dwellers”–a fresh way of mountain living.Immersed in the poetic scenery,they rest,hike,boat,read,attend valley concerts,or admire paintings in poetry halls.Everything blends with and respects nature.展开更多
On the evening of January 25,2025 Happy Chinese New Year global launch ceremony and gala was held in Kuala Lumpur,Malaysia.This year,the“Happy Chinese New Year”event will witness nearly 500 performances and exhibiti...On the evening of January 25,2025 Happy Chinese New Year global launch ceremony and gala was held in Kuala Lumpur,Malaysia.This year,the“Happy Chinese New Year”event will witness nearly 500 performances and exhibitions featuring diversified forms and rich contents across more than 100 countries and regions worldwide,including activities such as the New Year Concert,square celebration,the New Year Temple Fair,global lantern lighting,Walking Reunion Dinner on Chinese Lunar New Year s Eve,so as to have the people around the world sense the unique charm of the excellent Chinese traditional culture,and jointly celebrate and enjoy the happiness of the Chinese New Year.展开更多
The influence of the electronic and steric properties of bromoaromatic substrates on direct arylation polymerization for synthesizing high-molecular-weight conjugated polymers was investigated through a combination of...The influence of the electronic and steric properties of bromoaromatic substrates on direct arylation polymerization for synthesizing high-molecular-weight conjugated polymers was investigated through a combination of experiments and calculations.Bromo-aromatic substrates with electron-withdrawing fluoro substituents exhibited higher yields and degrees of polymerization under PPh3-assisted conditions compared to those with electron-donating or bulky methyl substituents.Additionally,excessive steric hindrance at ortho-sites or overly electrondeficient dibromoaromatic substrates leads to reaction inactivation.Calculations indicated that electron-withdrawing substituents enhanced the electrophilicity of arylpalladium-PPh3intermediates,facilitating the activation of electron-rich arylative substrates and promoting polymer growth.Furthermore,steric hindrance from the substituents can influence the preferred reaction pathway,thereby increasing the real reaction barriers.Both experimental and computational results suggest that bromoaromatic substrates with optimized electron-deficient characteristics significantly improve monomer conversion and polymerization efficiency with n-hexylmethylether-substituted EDOT.These findings clarify how the electronic and steric properties of bromo-aromatic substrates affect EDOT derivative activation and are expected to aid in optimizing the polymerization conditions for the preparation of high-molecular-weight conjugated polymers.展开更多
On April 6th,the"Silk Road People-to-People Connectivity"China-Cambodia Traditional Instrument Concert was successfully held in Phnom Penh.The event was attended by Li Ji,Cultural Counsellor of the Chinese E...On April 6th,the"Silk Road People-to-People Connectivity"China-Cambodia Traditional Instrument Concert was successfully held in Phnom Penh.The event was attended by Li Ji,Cultural Counsellor of the Chinese Embassy in Cambodia,officials from Ministry of Culture and Fine Arts of Cambodia and Ministry of Commerce of Cambodia,along with vips from various sectors.展开更多
THE BUSINESS OF EMOTION Neweekly 1 August From lucky charms promising safety to addictive blind boxes,from milk tea-fuelled social frenzies to concert tickets fetching 10 times their original price,a new wave of consu...THE BUSINESS OF EMOTION Neweekly 1 August From lucky charms promising safety to addictive blind boxes,from milk tea-fuelled social frenzies to concert tickets fetching 10 times their original price,a new wave of consumption is reshaping our daily lives.At the heart of this trend is the“emotion economy,”a rapidly expanding industry that turns feelings into marketable goods.展开更多
THE Waitan concert square is part of the new urban scene in Shanghai. With its unique location and fine performances, the concerts attract many people. Foreign merchants and ships pass Waitan (Outer Beach) as they ent...THE Waitan concert square is part of the new urban scene in Shanghai. With its unique location and fine performances, the concerts attract many people. Foreign merchants and ships pass Waitan (Outer Beach) as they enter the harbor on the Huangpu River at Shanghai. The scene at展开更多
To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a fle...To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.展开更多
The mitochondrial genome is a prominent research topic due to its indispensable role in organisms and its application in many research disciplines.However,few studies have investigated intraspecies mitogenomic variati...The mitochondrial genome is a prominent research topic due to its indispensable role in organisms and its application in many research disciplines.However,few studies have investigated intraspecies mitogenomic variation.In this study,69 mitogenomes of the Black-throated Tit(Aegithalos concinnus)were assembled and annotated from a large number of short reads generated using high-throughput sequencing technology.Comparative analyses revealed that mitogenomic characteristics such as length,gene and nucleotide composition,codon usage,and duplicated control regions were relatively conserved despite substantial intraspecies morphological changes.Yet,all the individuals from the subspecies A.c.iredalei had one more nucleotide in the 12S rRNA than the other studied subspecies.Phylogenetic analyses showed five distinct lineages based on the complete mitogenomes and the 13 combined protein-coding genes,whereas only four lineages were observed when using the duplicate control regions.Most interestingly,each lineage had both copies of the control regions of the comprising individuals,indicating that the paralogous control regions were more similar than the orthologous sequences from the distinct lineages.This suggested the control regions had undergone concerted evolution.The Black-throated Tit has complex evolutionary history and needs further investigating the taxonomic status of these lineages,as well as the underlying evolutionary processes.Our findings call for more research on intraspecies mitogenomic variation.展开更多
Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing S...Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing SEs with high ionic conductivities,it is extremely difficult to fully understand the ionic diffusion mechanisms in SEs through conventional experimental and theoretical methods.Herein,the temperature-dependent concerted diffusion mechanism of ions in SEs is explored through machinelearning molecular dynamics,taking Li_(10)GeP_(2)S_(12) as a prototype.Weaker diffusion anisotropy,more disordered Li distributions,and shorter residence time are observed at a higher temperature.Arrhenius-type temperature dependence is maintained within a wide temperature range,which is attributed to the linear temperature dependence of jump frequencies of various concerted diffusion modes.These results provide a theoretical framework to understand the ionic diffusion mechanisms in SEs and deepen the understanding of the chemical origin of temperature-dependent concerted diffusions in SEs.展开更多
Fully homomorphic encryption is faced with two problems now. One is candidate fully homomorphic encryption schemes are few. Another is that the efficiency of fully homomorphic encryption is a big question. In this pap...Fully homomorphic encryption is faced with two problems now. One is candidate fully homomorphic encryption schemes are few. Another is that the efficiency of fully homomorphic encryption is a big question. In this paper, we propose a fully homomorphic encryption scheme based on LWE, which has better key size. Our main contributions are： （1） According to the binary-LWE recently, we choose secret key from binary set and modify the basic encryption scheme proposed in Linder and Peikert in 2010. We propose a fully homomorphic encryption scheme based on the new basic encryption scheme. We analyze the correctness and give the proof of the security of our scheme. The public key, evaluation keys and tensored ciphertext have better size in our scheme. （2） Estimating parameters for fully homomorphic encryption scheme is an important work. We estimate the concert parameters for our scheme. We compare these parameters between our scheme and Bral2 scheme. Our scheme have public key and private key that smaller by a factor of about logq than in Bral2 scheme. Tensored ciphertext in our scheme is smaller by a factor of about log2q than in Bral2 scheme. Key switching matrix in our scheme is smaller by a factor of about log3q than in Bra12 scheme.展开更多
Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framewo...Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framework(COF)with largeπ-conjugated structures to prepare S-scheme BiOBr/COF photocat-alysts for H_(2)O_(2) synthesis.The highest photocatalytic H_(2)O_(2) production performance of the composite sample constituting the S-scheme heterojunction is 3749μmol g−1 h−1,which was 1.85 and 27 times the rates of COF and BiOBr,respectively.The construction of S-scheme heterojunction contributed to ef-ficient carrier transfer and separation in space and enhanced redox power.Moreover,the lying-down O_(2)-adsorption configuration on the COF surface favors the concerted two-electron O_(2) reduction process,which greatly reduced the reduction potential requirement for O_(2)-to-H_(2)O_(2) conversion.The synergy be-tween the S-scheme heterojunction and the unique O_(2)-COF interaction boosted photocatalytic H_(2)O_(2) pro-duction activity.展开更多
To develop efficient concerted companion(CC)dyes for fabricating high-performance DSSCs,three organic dyes XL1-XL3 have been designed by varying the position and number of theβ-hexylthiophene(HT)bridges,and these org...To develop efficient concerted companion(CC)dyes for fabricating high-performance DSSCs,three organic dyes XL1-XL3 have been designed by varying the position and number of theβ-hexylthiophene(HT)bridges,and these organic dye units are covalently linked with our previously reported porphyrin dye XW10 to construct the corresponding CC dyes XW74-XW76.Among the organic dyes,XL3 contains twoβ-hexylthiophene units at both the donor and acceptor parts and thus possesses stronger light-harvesting capability in the green light region.Because of the most complementary absorption between XL3 and XW10 as well as the excellent photovoltaic behavior of the individual XL3 dye,the corresponding CC dye XW76 affords the best PCE(10.78%)among all the CC dyes.Upon coadsorption with CDCA,XW76 affords a highest PCE of 11.35%,which outperforms the previous cosensitization system of XW10+WS-5.This work provides an approach for developing efficient DSSCs based on CC dyes composed of an organic dye unit with suitableπspacers inserted at appropriate positions.展开更多
A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol gr...A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol groups, respectively, of a new template monomer [1,3-bis（benzoyl-3-aminopropyl）-1,1,3,3-tetraethoxydisiloxane] （M）. The ordered ladder structure of LPBAS is manifested in： （1） the presence of two Bragg peaks representing the ladder width （d） and ladder thickness （t） in X-ray diffraction （XRD） pattern; （2） narrow base-line width （w = 6） of resonance absorption for -CH2SiO3/2 moiety in 29Si-NMR and （3） high glass transition temperature Tg = 1 12℃ in differential scanning calorimetry （DSC） analysis.展开更多
N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted additio...N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted addition mechanism was provided to explain the difference.展开更多
This paper reports a computational study elucidating reaction mechanism for amide bond formation from esters and amines catalyzed by acetic acid. Two optional mechanisms（namely, classic stepwise and concerted acyl su...This paper reports a computational study elucidating reaction mechanism for amide bond formation from esters and amines catalyzed by acetic acid. Two optional mechanisms（namely, classic stepwise and concerted acyl substitution mechanisms） have been studied. Calculation results establish the reaction energy profiles of both mechanisms and locate all the intermediates and transition states in both catalytic cycles. Our results propose that the concerted acyl substitution mechanism may be more likely wherein the formation of CààN bond and the cleavage of CààO bond occur concurrently without the need of rehybridization of the carbonyl carbon. This is also consistent with the fact that no significant racemization/epimerization were observed in the amide products when asymmetric esters and/or amines were used as the reactants, because concerted acyl substitution mechanism precludes the intermediacy of tetrahedral adducts and the accompanying generation/elimination of new chiral centers.Further discussion implies that the concerted acyl substitution mechanism may widely occur in related amidation reactions in the presence of different types of coupling reagents.展开更多
The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by ot...The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by other means. The rearrangement catalysed by trace of totuenesulfonic acid gave a negligible value of the Hammett reaction constant. Further experimental results show that the electronic effect of substituent on the aromatic ring for the rearrangement in neutral medium is much greater (Table 1). We propose sigmatropic migration展开更多
By exploring the space and the design techniques of roof garden in Frank Gehry's Walt Disney Concert Hall, this paper made further research on the combination of architectural functions and pedestrian fl ow lines,...By exploring the space and the design techniques of roof garden in Frank Gehry's Walt Disney Concert Hall, this paper made further research on the combination of architectural functions and pedestrian fl ow lines, and attempted to summarize the unique design techniques of Frank Gehry by analyzing his works, improve and develop design theories of roof garden, and attract more attention from the public to roof garden design.展开更多
文摘NEW DWELLERS OF MOUNTAINS Neweekly 15 September A growing number of people are turning towards the mountains,venturing into valleys and forests to explore a life as“new mountain dwellers”–a fresh way of mountain living.Immersed in the poetic scenery,they rest,hike,boat,read,attend valley concerts,or admire paintings in poetry halls.Everything blends with and respects nature.
文摘On the evening of January 25,2025 Happy Chinese New Year global launch ceremony and gala was held in Kuala Lumpur,Malaysia.This year,the“Happy Chinese New Year”event will witness nearly 500 performances and exhibitions featuring diversified forms and rich contents across more than 100 countries and regions worldwide,including activities such as the New Year Concert,square celebration,the New Year Temple Fair,global lantern lighting,Walking Reunion Dinner on Chinese Lunar New Year s Eve,so as to have the people around the world sense the unique charm of the excellent Chinese traditional culture,and jointly celebrate and enjoy the happiness of the Chinese New Year.
文摘The influence of the electronic and steric properties of bromoaromatic substrates on direct arylation polymerization for synthesizing high-molecular-weight conjugated polymers was investigated through a combination of experiments and calculations.Bromo-aromatic substrates with electron-withdrawing fluoro substituents exhibited higher yields and degrees of polymerization under PPh3-assisted conditions compared to those with electron-donating or bulky methyl substituents.Additionally,excessive steric hindrance at ortho-sites or overly electrondeficient dibromoaromatic substrates leads to reaction inactivation.Calculations indicated that electron-withdrawing substituents enhanced the electrophilicity of arylpalladium-PPh3intermediates,facilitating the activation of electron-rich arylative substrates and promoting polymer growth.Furthermore,steric hindrance from the substituents can influence the preferred reaction pathway,thereby increasing the real reaction barriers.Both experimental and computational results suggest that bromoaromatic substrates with optimized electron-deficient characteristics significantly improve monomer conversion and polymerization efficiency with n-hexylmethylether-substituted EDOT.These findings clarify how the electronic and steric properties of bromo-aromatic substrates affect EDOT derivative activation and are expected to aid in optimizing the polymerization conditions for the preparation of high-molecular-weight conjugated polymers.
文摘On April 6th,the"Silk Road People-to-People Connectivity"China-Cambodia Traditional Instrument Concert was successfully held in Phnom Penh.The event was attended by Li Ji,Cultural Counsellor of the Chinese Embassy in Cambodia,officials from Ministry of Culture and Fine Arts of Cambodia and Ministry of Commerce of Cambodia,along with vips from various sectors.
文摘THE BUSINESS OF EMOTION Neweekly 1 August From lucky charms promising safety to addictive blind boxes,from milk tea-fuelled social frenzies to concert tickets fetching 10 times their original price,a new wave of consumption is reshaping our daily lives.At the heart of this trend is the“emotion economy,”a rapidly expanding industry that turns feelings into marketable goods.
文摘THE Waitan concert square is part of the new urban scene in Shanghai. With its unique location and fine performances, the concerts attract many people. Foreign merchants and ships pass Waitan (Outer Beach) as they enter the harbor on the Huangpu River at Shanghai. The scene at
基金financially supported by the National Natural Science Foundation of China(Nos.22131005,22201074,22075077 and 21971063)the Fundamental Research Funds for the Central Universities,Program of Shanghai Academic Research Leader(No.20XD1401400)+1 种基金Shanghai Rising-Star Program(No.23QA1402100)Natural Science Foundation of Shanghai(Nos.23ZR1415600,22ZR1416100).
文摘To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.
基金financially supported by the National Natural Science Foundation of China(Grant No.32060310)a grant from the Department of Education of Guangxi.
文摘The mitochondrial genome is a prominent research topic due to its indispensable role in organisms and its application in many research disciplines.However,few studies have investigated intraspecies mitogenomic variation.In this study,69 mitogenomes of the Black-throated Tit(Aegithalos concinnus)were assembled and annotated from a large number of short reads generated using high-throughput sequencing technology.Comparative analyses revealed that mitogenomic characteristics such as length,gene and nucleotide composition,codon usage,and duplicated control regions were relatively conserved despite substantial intraspecies morphological changes.Yet,all the individuals from the subspecies A.c.iredalei had one more nucleotide in the 12S rRNA than the other studied subspecies.Phylogenetic analyses showed five distinct lineages based on the complete mitogenomes and the 13 combined protein-coding genes,whereas only four lineages were observed when using the duplicate control regions.Most interestingly,each lineage had both copies of the control regions of the comprising individuals,indicating that the paralogous control regions were more similar than the orthologous sequences from the distinct lineages.This suggested the control regions had undergone concerted evolution.The Black-throated Tit has complex evolutionary history and needs further investigating the taxonomic status of these lineages,as well as the underlying evolutionary processes.Our findings call for more research on intraspecies mitogenomic variation.
基金supported by the National Key Research and Development Program(2021YFB2500210)the Beijing Municipal Natural Science Foundation(Z20J00043)+4 种基金the National Natural Science Foundation of China(22109086 and 21825501)the China Postdoctoral Science Foundation(2021TQ0161 and 2021 M691709)the Guoqiang Institute at Tsinghua University(2020GQG1006)the support from the Shuimu Tsinghua Scholar Program of Tsinghua Universitythe support from the Tsinghua National Laboratory for Information Science and Technology for theoretical simulations。
文摘Solid-state batteries have received increasing attention in scientific and industrial communities,which benefits from the intrinsically safe solid electrolytes(SEs).Although much effort has been devoted to designing SEs with high ionic conductivities,it is extremely difficult to fully understand the ionic diffusion mechanisms in SEs through conventional experimental and theoretical methods.Herein,the temperature-dependent concerted diffusion mechanism of ions in SEs is explored through machinelearning molecular dynamics,taking Li_(10)GeP_(2)S_(12) as a prototype.Weaker diffusion anisotropy,more disordered Li distributions,and shorter residence time are observed at a higher temperature.Arrhenius-type temperature dependence is maintained within a wide temperature range,which is attributed to the linear temperature dependence of jump frequencies of various concerted diffusion modes.These results provide a theoretical framework to understand the ionic diffusion mechanisms in SEs and deepen the understanding of the chemical origin of temperature-dependent concerted diffusions in SEs.
基金The first author would like to thank for the Fund of Jiangsu Innovation Program for Graduate Education，the Fundamental Research Funds for the Central Universities,and Ningbo Natural Science Foundation，the Chinese National Scholarship fund,and also appreciate the benefit to this work from projects in science and technique of Ningbo municipal.The third author would like to thank for Ningbo Natural Science Foundation
文摘Fully homomorphic encryption is faced with two problems now. One is candidate fully homomorphic encryption schemes are few. Another is that the efficiency of fully homomorphic encryption is a big question. In this paper, we propose a fully homomorphic encryption scheme based on LWE, which has better key size. Our main contributions are： （1） According to the binary-LWE recently, we choose secret key from binary set and modify the basic encryption scheme proposed in Linder and Peikert in 2010. We propose a fully homomorphic encryption scheme based on the new basic encryption scheme. We analyze the correctness and give the proof of the security of our scheme. The public key, evaluation keys and tensored ciphertext have better size in our scheme. （2） Estimating parameters for fully homomorphic encryption scheme is an important work. We estimate the concert parameters for our scheme. We compare these parameters between our scheme and Bral2 scheme. Our scheme have public key and private key that smaller by a factor of about logq than in Bral2 scheme. Tensored ciphertext in our scheme is smaller by a factor of about log2q than in Bral2 scheme. Key switching matrix in our scheme is smaller by a factor of about log3q than in Bra12 scheme.
基金This work was supported by the National Natural Science Foundation of China(Nos.22278324,51932007,22238009,U1905215,52073223,52073034,and 22208332)the Postdoctoral Science Foundation of China(No.2022M712946)the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framework(COF)with largeπ-conjugated structures to prepare S-scheme BiOBr/COF photocat-alysts for H_(2)O_(2) synthesis.The highest photocatalytic H_(2)O_(2) production performance of the composite sample constituting the S-scheme heterojunction is 3749μmol g−1 h−1,which was 1.85 and 27 times the rates of COF and BiOBr,respectively.The construction of S-scheme heterojunction contributed to ef-ficient carrier transfer and separation in space and enhanced redox power.Moreover,the lying-down O_(2)-adsorption configuration on the COF surface favors the concerted two-electron O_(2) reduction process,which greatly reduced the reduction potential requirement for O_(2)-to-H_(2)O_(2) conversion.The synergy be-tween the S-scheme heterojunction and the unique O_(2)-COF interaction boosted photocatalytic H_(2)O_(2) pro-duction activity.
基金financially supported by the National Natural Science Foundation of China (Nos. 22131005, 21772041, 21971063 and 22075077)the Program of Shanghai Academic Research Leader (No. 20XD1401400)+1 种基金the Natural Science Foundation of Shanghai (No. 20ZR1414100)the Fundamental Research Funds for the Central Universities (No. 222201717003)
文摘To develop efficient concerted companion(CC)dyes for fabricating high-performance DSSCs,three organic dyes XL1-XL3 have been designed by varying the position and number of theβ-hexylthiophene(HT)bridges,and these organic dye units are covalently linked with our previously reported porphyrin dye XW10 to construct the corresponding CC dyes XW74-XW76.Among the organic dyes,XL3 contains twoβ-hexylthiophene units at both the donor and acceptor parts and thus possesses stronger light-harvesting capability in the green light region.Because of the most complementary absorption between XL3 and XW10 as well as the excellent photovoltaic behavior of the individual XL3 dye,the corresponding CC dye XW76 affords the best PCE(10.78%)among all the CC dyes.Upon coadsorption with CDCA,XW76 affords a highest PCE of 11.35%,which outperforms the previous cosensitization system of XW10+WS-5.This work provides an approach for developing efficient DSSCs based on CC dyes composed of an organic dye unit with suitableπspacers inserted at appropriate positions.
基金This work was financially supported by NSFC (Nos. 50073028, 29974036 and 20174047).
文摘A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol groups, respectively, of a new template monomer [1,3-bis（benzoyl-3-aminopropyl）-1,1,3,3-tetraethoxydisiloxane] （M）. The ordered ladder structure of LPBAS is manifested in： （1） the presence of two Bragg peaks representing the ladder width （d） and ladder thickness （t） in X-ray diffraction （XRD） pattern; （2） narrow base-line width （w = 6） of resonance absorption for -CH2SiO3/2 moiety in 29Si-NMR and （3） high glass transition temperature Tg = 1 12℃ in differential scanning calorimetry （DSC） analysis.
文摘N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted addition mechanism was provided to explain the difference.
基金supported by the National Natural Science Foundation of China (No. 21472068)Financial support from MOE & SAFEA for the 111 Project (No. B13025)is also gratefully acknowledged
文摘This paper reports a computational study elucidating reaction mechanism for amide bond formation from esters and amines catalyzed by acetic acid. Two optional mechanisms（namely, classic stepwise and concerted acyl substitution mechanisms） have been studied. Calculation results establish the reaction energy profiles of both mechanisms and locate all the intermediates and transition states in both catalytic cycles. Our results propose that the concerted acyl substitution mechanism may be more likely wherein the formation of CààN bond and the cleavage of CààO bond occur concurrently without the need of rehybridization of the carbonyl carbon. This is also consistent with the fact that no significant racemization/epimerization were observed in the amide products when asymmetric esters and/or amines were used as the reactants, because concerted acyl substitution mechanism precludes the intermediacy of tetrahedral adducts and the accompanying generation/elimination of new chiral centers.Further discussion implies that the concerted acyl substitution mechanism may widely occur in related amidation reactions in the presence of different types of coupling reagents.
文摘The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by other means. The rearrangement catalysed by trace of totuenesulfonic acid gave a negligible value of the Hammett reaction constant. Further experimental results show that the electronic effect of substituent on the aromatic ring for the rearrangement in neutral medium is much greater (Table 1). We propose sigmatropic migration
文摘By exploring the space and the design techniques of roof garden in Frank Gehry's Walt Disney Concert Hall, this paper made further research on the combination of architectural functions and pedestrian fl ow lines, and attempted to summarize the unique design techniques of Frank Gehry by analyzing his works, improve and develop design theories of roof garden, and attract more attention from the public to roof garden design.
