Semi-artificial photosynthesis interfacing catalytic protein machinery with synthetic photocatalysts exhibits great potential in solar-to-chemical energy conversion. However, characterizing and manipulating the molecu...Semi-artificial photosynthesis interfacing catalytic protein machinery with synthetic photocatalysts exhibits great potential in solar-to-chemical energy conversion. However, characterizing and manipulating the molecular integration structure at the biotic-abiotic interface remain a challenging task. Herein,the biointerface molecular integration details of photosystem II(PSII)-semiconductor hybrids, including the PSII orientation, interfacial microdomains, and overall structure modulation, are systematically interrogated by lysine reactivity profiling mass spectrometry. We demonstrate the semiconductor surface biocompatibility is essential to the PSII self-assembly with uniform orientation and electroactive structure.Highly directional localization of PSII onto more hydrophilic Ru/Sr Ti O_(3):Rh surface exhibits less disturbance on PSII structure and electron transfer chain, beneficial to the high water splitting activity.Further, rational modification of hydrophobic Ru_(2)S_(3)/Cd S surface with biocompatible protamine can improve the hybrid O_(2)-evolving activity 83.3%. Our results provide the mechanistic understanding to the structure–activity relationship of PSII-semiconductor hybrids and contribute to their rational design in the future.展开更多
Calorie restriction(CR)or a fasting regimen is considered one of the most potent non-pharmacological interventions to prevent chronic metabolic disorders,ameliorate autoimmune diseases,and attenuate aging.Despite effo...Calorie restriction(CR)or a fasting regimen is considered one of the most potent non-pharmacological interventions to prevent chronic metabolic disorders,ameliorate autoimmune diseases,and attenuate aging.Despite efforts,the mechanisms by which CR improves health,particularly brain health,are still not fully understood.Metabolic homeostasis is vital for brain function,and a detailed metabolome atlas of the brain is essential for understanding the networks connecting different brain regions.展开更多
Metal nanoclusters are promising nanomaterials with unique properties, but only a few ones with specific numbers of metal atoms can be obtained and studied up to now. In this study, we establish a new paradigm of in-s...Metal nanoclusters are promising nanomaterials with unique properties, but only a few ones with specific numbers of metal atoms can be obtained and studied up to now. In this study, we establish a new paradigm of in-situ generation and global study of metal nanoclusters with different sizes, constitutions, and charge states, including both accurate constitution characterization and global activity profiling. The complex mixtures of metal nanoclusters are produced by employing single-pulsed 193-nm laser dissociation of monolayer-protected cluster(MPC) precursors within a high-resolution mass spectrometry(HRMS). More than400 types of bare gold nanoclusters including novel multiply charged(2+ and 3+), S-/P-doped, and silver alloy ones can be efficiently generated and accurately characterized. A distinct size(1 to 142 atoms)-and charge(1+ to 3+)-hierarchy reactivity is clearly observed for the first time. This global cluster study might greatly promote the developments and applications of novel metal nanoclusters.展开更多
Ultraviolet photodissociation is a high-energy fast excitation method in mass spectrometry and has beensuccessfully applied for the elucidation of sequences and structures of biomolecules. However, its abilityto disti...Ultraviolet photodissociation is a high-energy fast excitation method in mass spectrometry and has beensuccessfully applied for the elucidation of sequences and structures of biomolecules. However, its abilityto distinguish the phosphorylation sites isomers of multi-phosphopeptides has been not systematicallyinvestigated until now. A 193-nm ultraviolet laser dissociation mass spectrometry system wasestablished in this study and applied to elucidate the complex multi-phosphorylation statuses mimickingthe functional regions of Sicl, Gli3 and Tau. The numbers of matched fragment ions and phosphorylationsite-determining ions were improved on average 123% and 104%, respectively, by utilizing the ultravioletphotodissociation strategy, comparing to the typically utilized collision induced dissociation strategy.Finally. 94% phosphorylation sites within various statuses were unambiguously elucidated.展开更多
Photosystem II(PSII),as a multiple-subunit chloroplast membrane-associated pigment-protein complex on the thylakoid membrane,is a primary target of light-induced photodamage.However,the overall molecular details of th...Photosystem II(PSII),as a multiple-subunit chloroplast membrane-associated pigment-protein complex on the thylakoid membrane,is a primary target of light-induced photodamage.However,the overall molecular details of the conformation and composition dynamics of PSII photodamage are still controversial.In this study,we investigated systematically the dynamic conformation,degradation,and oxidation processes of PSII photodamage by integrating chemical cross-linking and top-down proteomics strategies.展开更多
基金the financial supported by National Key R&D Program of China,China(2019YFE0119300)the National Natural Science Foundation of China,China(32088101,91853101,and 22075280)+2 种基金the Original Innovation Project of CAS,China(ZDBSLY-SLH032)the Excellent Young Scientist Grant of Liaoning Province,China(2019-YQ-07)the grant from DICP(DICPI202007)。
文摘Semi-artificial photosynthesis interfacing catalytic protein machinery with synthetic photocatalysts exhibits great potential in solar-to-chemical energy conversion. However, characterizing and manipulating the molecular integration structure at the biotic-abiotic interface remain a challenging task. Herein,the biointerface molecular integration details of photosystem II(PSII)-semiconductor hybrids, including the PSII orientation, interfacial microdomains, and overall structure modulation, are systematically interrogated by lysine reactivity profiling mass spectrometry. We demonstrate the semiconductor surface biocompatibility is essential to the PSII self-assembly with uniform orientation and electroactive structure.Highly directional localization of PSII onto more hydrophilic Ru/Sr Ti O_(3):Rh surface exhibits less disturbance on PSII structure and electron transfer chain, beneficial to the high water splitting activity.Further, rational modification of hydrophobic Ru_(2)S_(3)/Cd S surface with biocompatible protamine can improve the hybrid O_(2)-evolving activity 83.3%. Our results provide the mechanistic understanding to the structure–activity relationship of PSII-semiconductor hybrids and contribute to their rational design in the future.
基金This work was supported by the National Natural Science Foundation of China(NSFC 22004013,82271524,and 21934006)Doctoral Scientific Research Foundation of the Liaoning Science and Technology Department(2020-BS-200)the Central Guidance on Local Science and Technology Development Fund of Dalian Science and Technology Bureau.
文摘Calorie restriction(CR)or a fasting regimen is considered one of the most potent non-pharmacological interventions to prevent chronic metabolic disorders,ameliorate autoimmune diseases,and attenuate aging.Despite efforts,the mechanisms by which CR improves health,particularly brain health,are still not fully understood.Metabolic homeostasis is vital for brain function,and a detailed metabolome atlas of the brain is essential for understanding the networks connecting different brain regions.
基金supported by the National Natural Science Foundation of China (32088101, 21872145 and 22172167)the Original Innovation Project of CAS (ZDBS-LY-SLH032)+1 种基金Chinese National Innovation Foundation (18-163-14-ZT-002-001-02)the grant from DICP (DICP I202007)。
文摘Metal nanoclusters are promising nanomaterials with unique properties, but only a few ones with specific numbers of metal atoms can be obtained and studied up to now. In this study, we establish a new paradigm of in-situ generation and global study of metal nanoclusters with different sizes, constitutions, and charge states, including both accurate constitution characterization and global activity profiling. The complex mixtures of metal nanoclusters are produced by employing single-pulsed 193-nm laser dissociation of monolayer-protected cluster(MPC) precursors within a high-resolution mass spectrometry(HRMS). More than400 types of bare gold nanoclusters including novel multiply charged(2+ and 3+), S-/P-doped, and silver alloy ones can be efficiently generated and accurately characterized. A distinct size(1 to 142 atoms)-and charge(1+ to 3+)-hierarchy reactivity is clearly observed for the first time. This global cluster study might greatly promote the developments and applications of novel metal nanoclusters.
基金Financial supports are gratefully acknowledged for the China State Key Research Grant(No.2016YFF0200504)China State Key Basic Research Program Grant(No.2013CB911203)+2 种基金the National Natural Science Foundation of China(No.21675152)the Youth Innovation Promotion Association CAS(No.2014164)grant from DICP(No.ZZBS201603)
文摘Ultraviolet photodissociation is a high-energy fast excitation method in mass spectrometry and has beensuccessfully applied for the elucidation of sequences and structures of biomolecules. However, its abilityto distinguish the phosphorylation sites isomers of multi-phosphopeptides has been not systematicallyinvestigated until now. A 193-nm ultraviolet laser dissociation mass spectrometry system wasestablished in this study and applied to elucidate the complex multi-phosphorylation statuses mimickingthe functional regions of Sicl, Gli3 and Tau. The numbers of matched fragment ions and phosphorylationsite-determining ions were improved on average 123% and 104%, respectively, by utilizing the ultravioletphotodissociation strategy, comparing to the typically utilized collision induced dissociation strategy.Finally. 94% phosphorylation sites within various statuses were unambiguously elucidated.
基金The authors gratefully acknowledged the financial supports from the National Key R&D Program of China(nos.2016YFF0200504,2017YFA0503700,and 2018YFA0900702)the National Natural Science Foundation of China(nos.91853101 and 31470339)+3 种基金grants from the Chinese Academy of Sciences(nos.ZDBS-LYSLH032 and XDB17000000)the Liaoning Province(no.2019-YQ-07)the Dalian Institute of Chemical Physics(DICPno.DICP I202007).
文摘Photosystem II(PSII),as a multiple-subunit chloroplast membrane-associated pigment-protein complex on the thylakoid membrane,is a primary target of light-induced photodamage.However,the overall molecular details of the conformation and composition dynamics of PSII photodamage are still controversial.In this study,we investigated systematically the dynamic conformation,degradation,and oxidation processes of PSII photodamage by integrating chemical cross-linking and top-down proteomics strategies.
基金supported by the National Natural Science Foundation of China(21890753,21988101 to Dehui Deng,91853101 to Fangjun Wang,and 91845106 to Liang Yu)the Strategic PriorityResearch Program of the Chinese Academy of Sciences(XDB36030200 to Dehui Deng)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Y201936 to Dehui Deng,Y201750 to Yangbo Hu)。