Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify t...The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.展开更多
Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were ...Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were isolated from the aqueous extracts of Gastrodia elata.Compounds 1 and 4 are 4-hydroxy-3-(4′-hydroxybenzyl)benzyl-substituted sulfoxide and sulfide, respectively, which are unprecedented in natural products. Compound 3 represents a rare sulfinate. Several isolates and their sulfone and disulfide analogs(10-13) were synthesized to evaluate their anti-inflammatory activity. Notably, the synthesized sulfone 10 demonstrated significant alleviation of symptoms in multiple in vivo inflammatory models.展开更多
Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-con...Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.展开更多
α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to syn...α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.展开更多
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid ...The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task.State-of-the-art approaches mainly relied on the transition metal-catalyzed C-H deuteration via the assistance of directing groups(DGs),which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG.Herein,we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core.Through capture of aryne-derived 1,3-zwitterion with heavy water,we synthesized an array of ortho-deuterated aryl sulfonium salts.These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles,but also served as aryl radical reservoirs under photochemical or electrochemical conditions,enabling facile and precise access to structurally diverse deuterated aromatics.Moreover,we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation,further expanding the utility of our platform approach.展开更多
Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating p...Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating packed bed(RPB)in premixing and crystallization on crystallinity and RE utilization rate was further investigated.The results indicate that lanthanide(La)cations are successfully introduced into the sodalite cage of Y-type zeolite.The optimized conditions are that the molar ratio of Si/La is 150,premixing for 5 h,crystallization at 90℃ for 18 h,and calcination at 550℃ for 3.5 h.At this stage,the RE utilization rate reaches 74.5%.Compared with the conventional stirred tank reactor(STR),RPB can effectively shorten the premixing time and crystallization time by 4.3 h and 6 h,improve the crystallinity by 23%and RE utilization rate by 7.5%.The RE utilization rate is more than 80%by RPB,surpassing the effectiveness of using the one-exchange one-calcination process in the traditional liquid ion exchange process.It is expected to provide a reference for the in-situ efficient and green synthesis of RE zeolite.展开更多
High temperature stress (HT) significantly reduces maize yield by impairing starch accumulation in kernels.However,the mechanism by which HT affects starch synthesis remains controversial-whether through reduced assim...High temperature stress (HT) significantly reduces maize yield by impairing starch accumulation in kernels.However,the mechanism by which HT affects starch synthesis remains controversial-whether through reduced assimilate supply or direct inhibition on kernel metabolism.To clarify these mechanisms,a heat-sensitive maize hybrid,Xianyu 335 (XY),was exposed to 30℃/20℃ (maximum/minimum temperature,control) and 40℃/30℃ for seven consecutive days during the seed setting stage.Synchronous pollination (SP),apical pollination (AP),and shading treatments were applied to manipulate the inherent source–sink ratio in maize plants.Results showed that apical kernel weight decreased by 11.9%under 40℃ in the SP treatment.The ^(13)C content,starch accumulation,and cell-wall invertase (CWIN) activity also declined by 15.9,36.7,and 16.4%,respectively,under HT.In the shading treatment,40℃/30℃ caused even greater reductions in^(13)C content,starch accumulation,and CWIN activity due to diminished assimilate supply.Conversely,in the AP treatment,starch content and CWIN activity increased by 22.0 and 18.5%,respectively,under 40℃/30℃,resulting in kernel weight and ^(13)C content similar to those in SP and shading treatments regardless of temperature.Consistent with apical kernels under AP,HT did not negatively affect middle kernels in either SP or shading treatments,as kernel weight and starch content remained unchanged under HT.Although all kernels were exposed to the same HT or control environment,their responses varied a lot.The impaired starch synthesis in apical kernels under HT was rescued by increasing carbon supply via AP treatment.The contrasting performance among middle kernels,apical kernels under AP,and apical kernels under SP or shading indicates that reduced carbon supply is a critical factor underlying inhibited starch accumulation.Our findings provide a theoretical basis for further understanding kernel abortion under HT.展开更多
Post-exercise whey protein isolate(WPI)supplement is beneficial for skeletal muscle recovery due to the stimulation of branched chain amino acids(BCAAs).This implies us that intake slow digestion rate of protein to su...Post-exercise whey protein isolate(WPI)supplement is beneficial for skeletal muscle recovery due to the stimulation of branched chain amino acids(BCAAs).This implies us that intake slow digestion rate of protein to sustain BCAAs releasing rate may facilitate muscle protein synthesis.To examine this hypothesis,we conducted a series of protein supplements including modified slow-digesting whey(SDW),whey,hydrolyzed whey and casein,orally to mice undergoing endurance running.Our results showed that the SDW gavage constant supplied BCAAs in the serum of mice within 6 h and significantly enhanced(P<0.01)endurance exercise capacity,compared to other groups.In addition,the SDW supplementation increased the crosssectional area of mice gastrocnemius fibers,as well as their muscle and liver glycogen content.It also increased the testosterone/cortisol ratio in serum and interleukin-6(IL-6)levels in muscle,while it decreased the tumor necrosis factor-alpha(TNF-α)levels and oxidative stress in muscle.Moreover,it may activate mechanistic target of rapamycin signaling by upregulating mRNA(bcat-1 and pgc-1α)expression.Thus,our findings illustrate that prolonged BCAAs supply duration promotes mice endurance running capacity and skeletal muscle growth,contributing to the advancement of sports nutrition practices.展开更多
For decades,the central dogma of oncology has been that a cancer’s identity is inextricably linked to its anatomical origin.This principle underpins the entire diagnostic and therapeutic framework,from histology-base...For decades,the central dogma of oncology has been that a cancer’s identity is inextricably linked to its anatomical origin.This principle underpins the entire diagnostic and therapeutic framework,from histology-based classification to site-specific treatment guidelines.Yet,this framework catastrophically fails for a substantial population of patients diagnosed with cancer of unknown primary(CUP).These patients present metastatic disease,yet their primary tumors remain elusive despite exhaustive clinical workup1.CUP,accounting for 1%-3%of all cancer diagnoses,is an enigma with devastating consequences;the median overall survival is only 2-12 months2-4.The inability to pinpoint an origin forces clinicians to rely on broad-spectrum empirical chemotherapy,such as taxane-carboplatin regimens,which have limited efficacy and exclude patients from the promise of targeted therapies and clinical trials5.CUP is not only a diagnostic challenge but also an indictment of the siloed approach to understanding malignancy:this cancer highlights the limitations of origin-based diagnostic frameworks.However,the confluence of high-dimensional biological data and advanced artificial intelligence(AI)is now poised to address this long-standing diagnostic limitation and to herald a new era for not only CUP but also oncology as a whole(Figure 1).展开更多
Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug...Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug discovery but also inspire innovative strategies in drug development.The biomimetic synthesis of natural products employs principles from biomimicry,applying inspiration from biogenetic processes to design synthetic strategies that mimic biosynthetic processes.Biomimetic synthesis is a highly efficient approach in synthetic chemistry,as it addresses critical challenges in the synthesis of structurally complex natural products with significant biological and medicinal importance.It has gained widespread attention from researchers in chemistry,biology,pharmacy,and related fields,underscoring its interdisciplinary impact.In this perspective,we present recent advances and challenges in the biomimetic synthesis of natural products,along with the significance and prospects of this field,highlighting the transformative potential of biomimetic synthesis strategies for both chemical and biosynthetic approaches to natural product synthesis in the pursuit of novel therapeutic agents.展开更多
Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis...Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.展开更多
Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its...Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its industrial maturity and high yield,suffers from high energy consumption,carbon emissions,safety risks,and reliance on precious metals[2].Despite ongoing optimizations,a more sustainable alternative is urgently needed.The direct synthesis of hydrogen peroxide from water and oxygen has long been considered as an ideal alternative due to its theoretical 100%atom efficiency and environmental sustainability.展开更多
By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthi...By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols.The observed differences are attributed to variations in thioester bond strength and steric hindrance.These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-SPh(4-NO_(2))and Ala-S-Ph(2,6-diCH_(3)).This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization,thereby significantly simplifying the protein synthesis process.展开更多
Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating a...Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating and cooling rates on the order of milliseconds,facilitating nonequilibrium phase transitions,defect modulation,and tailored nanostructural evolution.This technique offers unprecedented control over material synthesis and has been successfully applied to a broad spectrum of functional property-driven materials,including graphene,single-atom catalysts,transition metal carbides,oxides,nitrides,phosphides,and chalcogenides,as well as complex multicomponent frameworks such as high-entropy alloys.This review systematically explores the principles governing JH,highlights recent advances in its application to diverse materials systems,and critically assesses current limitations related to process uniformity,scalability,and mechanistic understanding.Particular attention is given to its intrinsic advantages,including energy efficiency,fast rate,environmental sustainability,and compatibility with sustainable manufacturing.Finally,we propose guidance for expanding the utility of JH for new materials discovery,including integration with in-situ diagnostics,theoretical compatibility and data-driven optimization of synthesis to effectively correlate structure-property relationships.展开更多
A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional poly...A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.展开更多
With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk che...With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).展开更多
Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Ove...Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Over the past few years,a variety of homogeneous and heterogeneous photocatalysts have been applied in the photoredox catalysis.Heterogeneous photoredox catalysis offers advantages such as easy separation and superior recyclability compared to homogeneous counterparts,although homogenous catalysts are usually associated with higher activities and selectivity.From a practical perspective,an optimal photoredox catalytic system would integrate the advantages of both homogeneous and heterogeneous cases.展开更多
Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge....Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金supported by the National Natural Science Foundation of China[Grant No.21977083].
文摘The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.
基金supported by the National Natural Science Foundation of China (No. 82293680)the National Science and CAMS Innovation Fund for Medical Science (No. 2021-I2M-1-028)the Nonprofit Central Research Institute Fund of Chinese Academy of Medical Sciences (No. 2021-RC350-009)。
文摘Five novel sulfur-containing benzyl metabolites, designated as gastrabenzylsulfoxides A and B(1 and 2), gastrabenzylsulfinate A(3) and gastrabenzylsulfides A and B(4 and 5), along with four known compounds(6-9), were isolated from the aqueous extracts of Gastrodia elata.Compounds 1 and 4 are 4-hydroxy-3-(4′-hydroxybenzyl)benzyl-substituted sulfoxide and sulfide, respectively, which are unprecedented in natural products. Compound 3 represents a rare sulfinate. Several isolates and their sulfone and disulfide analogs(10-13) were synthesized to evaluate their anti-inflammatory activity. Notably, the synthesized sulfone 10 demonstrated significant alleviation of symptoms in multiple in vivo inflammatory models.
基金supported by the King Khalid University,Abha,Saudi Arabiathe Deanship of Scientific Research at King Khalid University for funding this work through Large Groups Project under grant number(R.G.P.2/335/46)the Guangdong Office of Research Projects at the Provincial University(No.2024KCXTD064)。
文摘Conjugated microporous polymers(CMPs)are a unique class of organic porous materials characterized byπ-conjugated structures and permanent micropores,distinguishing them from non-porous polymers and conventionalπ-conjugated polymers.CMPs offer extensive versatility in synthetic approaches,enabling the synthesis of cross-linked and mesoporous structures.Advances in chemical processes,structural design,and synthesis methodologies have been developed,resulting in a diverse range of CMPs with unique configurations and properties,contributing to the fast expansion of the field.CMPs are particularly notable for their ability to enable the competitive utilization ofπ-conjugated structures within mesoporous configurations,making them valuable for investigations across various domains.They have shown considerable promise in addressing fuel and environmental challenges,demonstrated by their exceptional performance in applications such as vapor adsorption,heterogeneous catalysis,light emission,light harvesting,and energy generation.This review examines the chemical engineering principles underlying CMPs,including synthesis approaches,systemic research advancements,multifunctional investigations boundaries,potential applications,and progress in synthesis,dimensionality,and morphology studies.Specifically,it offers a comparative analysis of CMPs and linear polymeric materials,aiding in the development of functional polymers.Furthermore,this review explores the primary fundamental limitations of CMPs in fuel-related domains and discusses alternative strategies,including novel synthesis methods incorporating interactions and morphologies,to address these challenges.Ultimately,this assessment aims to provide a valuable and inspiring resource for professionals in the field of fuel management,guiding future research and development efforts.
基金the National Natural Science Foundation of China(Nos.22150410339,W2432012,22301233 and 22171218)the Ministry of Science and Technology China(No.wgxz2022188)。
文摘α-Chiral amides are common in pharmaceuticals,agrochemicals,natural products,and peptides,prompting the need for new synthetic methods.Here,we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesizeα-chiral amides from benzyl ammonium salts and isocyanates.The key to success is using a chiral 2,2-bipyridine ligand(-)-Ph-SBpy,enabling high yield(up to 95%)and enantiomeric ratio(up to 98:2 er)under mild conditions.Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate,enhancing selectivity and efficiency.The synthetic utility is showcased through transformations of the enantioenriched amides,and the mechanism and enantioselectivity are supported by experimental and computational studies.
基金supported by the National Natural Science Foundation of China (Nos.22271010 and 21702013)。
文摘The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties.However,despite its pharmaceutical value,the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task.State-of-the-art approaches mainly relied on the transition metal-catalyzed C-H deuteration via the assistance of directing groups(DGs),which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG.Herein,we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core.Through capture of aryne-derived 1,3-zwitterion with heavy water,we synthesized an array of ortho-deuterated aryl sulfonium salts.These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles,but also served as aryl radical reservoirs under photochemical or electrochemical conditions,enabling facile and precise access to structurally diverse deuterated aromatics.Moreover,we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation,further expanding the utility of our platform approach.
基金supported by the NationalKey Research and Development Program of China(2023YFA1507701)National Natural Science Foundation of China(U22B6011,22288102)“Announcement and Challenge”Science and Technology Project of Xinjiang Uygur Autonomous Region(XJKJTJBGS-2023).
文摘Rare earth(RE)Y-type zeolite was synthesized in situ by acidic co-hydrolysis route and hydrothermal method.The key process parameters were optimized based on the RE utilization rate.The effect of inducing a rotating packed bed(RPB)in premixing and crystallization on crystallinity and RE utilization rate was further investigated.The results indicate that lanthanide(La)cations are successfully introduced into the sodalite cage of Y-type zeolite.The optimized conditions are that the molar ratio of Si/La is 150,premixing for 5 h,crystallization at 90℃ for 18 h,and calcination at 550℃ for 3.5 h.At this stage,the RE utilization rate reaches 74.5%.Compared with the conventional stirred tank reactor(STR),RPB can effectively shorten the premixing time and crystallization time by 4.3 h and 6 h,improve the crystallinity by 23%and RE utilization rate by 7.5%.The RE utilization rate is more than 80%by RPB,surpassing the effectiveness of using the one-exchange one-calcination process in the traditional liquid ion exchange process.It is expected to provide a reference for the in-situ efficient and green synthesis of RE zeolite.
基金financially supported by the National Natural Science Foundation of China (32071978)the National Key Research and Development Program of China (2022YFD2300901 and 2022YFD2300905)。
文摘High temperature stress (HT) significantly reduces maize yield by impairing starch accumulation in kernels.However,the mechanism by which HT affects starch synthesis remains controversial-whether through reduced assimilate supply or direct inhibition on kernel metabolism.To clarify these mechanisms,a heat-sensitive maize hybrid,Xianyu 335 (XY),was exposed to 30℃/20℃ (maximum/minimum temperature,control) and 40℃/30℃ for seven consecutive days during the seed setting stage.Synchronous pollination (SP),apical pollination (AP),and shading treatments were applied to manipulate the inherent source–sink ratio in maize plants.Results showed that apical kernel weight decreased by 11.9%under 40℃ in the SP treatment.The ^(13)C content,starch accumulation,and cell-wall invertase (CWIN) activity also declined by 15.9,36.7,and 16.4%,respectively,under HT.In the shading treatment,40℃/30℃ caused even greater reductions in^(13)C content,starch accumulation,and CWIN activity due to diminished assimilate supply.Conversely,in the AP treatment,starch content and CWIN activity increased by 22.0 and 18.5%,respectively,under 40℃/30℃,resulting in kernel weight and ^(13)C content similar to those in SP and shading treatments regardless of temperature.Consistent with apical kernels under AP,HT did not negatively affect middle kernels in either SP or shading treatments,as kernel weight and starch content remained unchanged under HT.Although all kernels were exposed to the same HT or control environment,their responses varied a lot.The impaired starch synthesis in apical kernels under HT was rescued by increasing carbon supply via AP treatment.The contrasting performance among middle kernels,apical kernels under AP,and apical kernels under SP or shading indicates that reduced carbon supply is a critical factor underlying inhibited starch accumulation.Our findings provide a theoretical basis for further understanding kernel abortion under HT.
基金financially supported by the Fundamental Research Funds for the Central Universities(JUSRP622014)Collaborative Innovation Center of Food Safety and Quality Control in Jiangsu Province,Jiangnan University(2022-3-2)National Key Research and Development Program of China(2022YFF1100300).
文摘Post-exercise whey protein isolate(WPI)supplement is beneficial for skeletal muscle recovery due to the stimulation of branched chain amino acids(BCAAs).This implies us that intake slow digestion rate of protein to sustain BCAAs releasing rate may facilitate muscle protein synthesis.To examine this hypothesis,we conducted a series of protein supplements including modified slow-digesting whey(SDW),whey,hydrolyzed whey and casein,orally to mice undergoing endurance running.Our results showed that the SDW gavage constant supplied BCAAs in the serum of mice within 6 h and significantly enhanced(P<0.01)endurance exercise capacity,compared to other groups.In addition,the SDW supplementation increased the crosssectional area of mice gastrocnemius fibers,as well as their muscle and liver glycogen content.It also increased the testosterone/cortisol ratio in serum and interleukin-6(IL-6)levels in muscle,while it decreased the tumor necrosis factor-alpha(TNF-α)levels and oxidative stress in muscle.Moreover,it may activate mechanistic target of rapamycin signaling by upregulating mRNA(bcat-1 and pgc-1α)expression.Thus,our findings illustrate that prolonged BCAAs supply duration promotes mice endurance running capacity and skeletal muscle growth,contributing to the advancement of sports nutrition practices.
基金supported by the National Natural Science Foundation of China(Grant Nos.32270688,31801117,and 82430107 to X.L.,and 32500589 to H.S.)the China Postdoctoral Science Foundation(Grant Nos.BX20240253 and 2024M762384 to H.S.)+1 种基金the Natural Science Foundation of Tianjin(Grant No.24JCQNJC01280 to H.S.)Tianjin Key Medical Discipline(Specialty)Construction Project(Grant No.TJYXZDXK-3-003A).
文摘For decades,the central dogma of oncology has been that a cancer’s identity is inextricably linked to its anatomical origin.This principle underpins the entire diagnostic and therapeutic framework,from histology-based classification to site-specific treatment guidelines.Yet,this framework catastrophically fails for a substantial population of patients diagnosed with cancer of unknown primary(CUP).These patients present metastatic disease,yet their primary tumors remain elusive despite exhaustive clinical workup1.CUP,accounting for 1%-3%of all cancer diagnoses,is an enigma with devastating consequences;the median overall survival is only 2-12 months2-4.The inability to pinpoint an origin forces clinicians to rely on broad-spectrum empirical chemotherapy,such as taxane-carboplatin regimens,which have limited efficacy and exclude patients from the promise of targeted therapies and clinical trials5.CUP is not only a diagnostic challenge but also an indictment of the siloed approach to understanding malignancy:this cancer highlights the limitations of origin-based diagnostic frameworks.However,the confluence of high-dimensional biological data and advanced artificial intelligence(AI)is now poised to address this long-standing diagnostic limitation and to herald a new era for not only CUP but also oncology as a whole(Figure 1).
基金financially supported by the National Key Research and Development Program of China(2023YFC3503902)the National Natural Science Foundation of China(82430108,82293681(82293680),and 82321004)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(2022B1515120015 and 2024A1515030103)the Guangdong Major Project of Basic and Applied Basic Research(2023B0303000026)the Science and Technology Projects in Guangzhou(202102070001)。
文摘Natural products,with their remarkable structural and biological diversity,have historically served as a vital bridge between chemistry,the life sciences,and medicine.They not only provide essential scaffolds for drug discovery but also inspire innovative strategies in drug development.The biomimetic synthesis of natural products employs principles from biomimicry,applying inspiration from biogenetic processes to design synthetic strategies that mimic biosynthetic processes.Biomimetic synthesis is a highly efficient approach in synthetic chemistry,as it addresses critical challenges in the synthesis of structurally complex natural products with significant biological and medicinal importance.It has gained widespread attention from researchers in chemistry,biology,pharmacy,and related fields,underscoring its interdisciplinary impact.In this perspective,we present recent advances and challenges in the biomimetic synthesis of natural products,along with the significance and prospects of this field,highlighting the transformative potential of biomimetic synthesis strategies for both chemical and biosynthetic approaches to natural product synthesis in the pursuit of novel therapeutic agents.
基金financially supported by the National Natural Science Foundation of China(Nos.22322801,22108010,22278124)Fundamental Research Funds for the Central Universities(No.buctrc202135)。
文摘Covalent organic frameworks(COFs),as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions.However,the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel,and also requires a large amount of poisonous solvents,which is generally not available for scaling-up production and commercial application.In recent years,great efforts have been made to explore simple,green,and efficient approaches for COFs synthesis.In this comprehensive review,we summarized the advances in emergent strategies by highlighting their distinct features.Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
文摘Hydrogen peroxide(H_(2)O_(2)),as a green oxidant,plays a vital role in various applications,including environmental remediation,disinfection,and chemical synthesis[1].The conventional anthraquinone process,despite its industrial maturity and high yield,suffers from high energy consumption,carbon emissions,safety risks,and reliance on precious metals[2].Despite ongoing optimizations,a more sustainable alternative is urgently needed.The direct synthesis of hydrogen peroxide from water and oxygen has long been considered as an ideal alternative due to its theoretical 100%atom efficiency and environmental sustainability.
基金CAMS Innovation Fund for Medical Sciences(CIFMS,No.2021-I2M-1-026)the National Key R&D Program of China(No.2018YFE0111400)+6 种基金the NIH Research Project Grant Program(No.R01 EB025892)the National Natural Science Foundation of China(the Training Program of the Major Research Plan,No.91853120)the National Major Scientific and Technological Special Project of China(Nos.2018ZX09711001-005 and 2018ZX09711001-013)the State Key Laboratory of Bioactive Substance and Function of Natural Medicines,Institute of Materia Medicathe Biomedical High Performance Computing Platform,Chinese Academy of Medical Sciencesthe Chinese Academy of Medical SciencesPeking Union Medical College for funding and support.
文摘By investigating 17 peptide arylthioesters that were previously challenging to produce,this study reveals a clear correlation between increased ligation activity and decreased pKa values of their corresponding arylthiols.The observed differences are attributed to variations in thioester bond strength and steric hindrance.These insights have led to the development of an improved one-pot chemical protein synthesis approach that leverages the reactivity differences between peptide arylthioesters with C-terminal Ala-SPh(4-NO_(2))and Ala-S-Ph(2,6-diCH_(3)).This approach eliminates the need for thiol-thioester exchange and additive removal steps while enabling in situ desulfurization,thereby significantly simplifying the protein synthesis process.
基金supported by the National Natural Science Foundation of China(Grant No.22402030)the Fujian Province Young and Middle-Aged Teacher Education Research Project(JZ240012)+1 种基金I.S.A.acknowledges funding support from Research Ireland under the SFI-IRC Pathway Program(Grant no:22/PATH-S/10725)the SFI Industry RD&I Fellowship Program(Grant no:21/IRDIF/9876).
文摘Ultrafast Joule heating(JH)has emerged as a powerful and scalable platform for rapid thermal processing of advanced nanomaterials.By delivering transient,high-intensity electrical pulses,JH induces ultrafast heating and cooling rates on the order of milliseconds,facilitating nonequilibrium phase transitions,defect modulation,and tailored nanostructural evolution.This technique offers unprecedented control over material synthesis and has been successfully applied to a broad spectrum of functional property-driven materials,including graphene,single-atom catalysts,transition metal carbides,oxides,nitrides,phosphides,and chalcogenides,as well as complex multicomponent frameworks such as high-entropy alloys.This review systematically explores the principles governing JH,highlights recent advances in its application to diverse materials systems,and critically assesses current limitations related to process uniformity,scalability,and mechanistic understanding.Particular attention is given to its intrinsic advantages,including energy efficiency,fast rate,environmental sustainability,and compatibility with sustainable manufacturing.Finally,we propose guidance for expanding the utility of JH for new materials discovery,including integration with in-situ diagnostics,theoretical compatibility and data-driven optimization of synthesis to effectively correlate structure-property relationships.
基金the National Natural Science Foundation of China(No.22471224)。
文摘A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms.Compared to traditional polycyclic diterpenoids,their biosynthetic pathways are quite unique and diverse.Chemists have pinpointed a range of this type of unusual diterpenoids:cycloamphilectanes and isocycloamphilectanes,kempenes and rippertanes,hydropyrene and hydropyrenol,along with recently disclosed cephalotanes.This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.
基金supported by the National Natural Science Foundation of China(Nos.22175174 and 52332007).
文摘With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).
基金the National Natural Science Foundation of China(No.22271060),The Department of Chemistry at Fudan University and College of Chemistry and Chemical Engineering at Ningxia University is gratefully acknowledged.
文摘Photoredox catalysis has made significant advances in stateof-the-art chemical synthesis,drawing energy from inexhaustible light and enabling various organic transformations to occur under mild reaction conditions.Over the past few years,a variety of homogeneous and heterogeneous photocatalysts have been applied in the photoredox catalysis.Heterogeneous photoredox catalysis offers advantages such as easy separation and superior recyclability compared to homogeneous counterparts,although homogenous catalysts are usually associated with higher activities and selectivity.From a practical perspective,an optimal photoredox catalytic system would integrate the advantages of both homogeneous and heterogeneous cases.
基金supported by National Natural Science Foundation of China(52302034,52402060,52202201,52021006)Beijing National Laboratory for Molecular Sciences(BNLMS-CXTD202001)+1 种基金Shenzhen Science and Technology Innovation Commission(KQTD20221101115627004)China Postdoctoral Science Foundation(2024T170972)。
文摘Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
