Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testifie...Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard stu...Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard study accuracy and the wel-fare of lab rodents.Our study team developed a novel,standardized apparatus to induce CSDS in rodents and assessed the model's practical adaptability.Methods:An innovative CSDS cage apparatus and water bottle was designed.To evaluate the effectiveness of the newly developed tools,a variety of animal models,including the tail suspension test(TST),sucrose preference test,forced swimming test(FST),novelty-suppressed feeding test,female urine sniffing test,and open field test(OFT),were adopted to assess depressive-like behaviors in mice.Fluoxetine treat-ment was also administered to observe the reversal effect,as part of the validation.Results:The CSDS cage apparatus resulted in the manifestation of depressive-like behaviors in the model mice.Significant reductions in sucrose preference and urine sniffing time were observed,while the OFT revealed decreased central zone total distance,residence time,and frequency of entry.Moreover,increased immobility was found in the FST and TST.Fluoxetine treatment was found to successfully reverse the modeling effect.Conclusion:The CSDS cage apparatus was validated for enhanced usability and ad-dressed the previous challenges of water bottle leakage and lab rodent welfare is-sues.The consistent results from multiple behavioral tests also supported real-world application of the apparatus,offering researchers a promising alternative to conven-tional rodent cages.展开更多
Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a ke...Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a key area for cage aquaculture in China;however,this region faces significant challenges from biofouling organisms.Here,we employed an experimental approach in a filed mesocosm in a net cage aquaculture area in the Yellow Sea,with weekly monitoring of changes in macrofouling species on mesh nets and in the seawater,to assess the utility of water eDNA metabarcoding for identifying macrofoulers.We compared the temporal variation patterns in the composition and diversity of macrofouling communities identified through morphological method as well as COI and 18S rRNA metabarcoding.The results showed that metabarcoding detected the majority of macrofoulers identified through morphological method(64%),and revealed additional species that were overlooked by traditional monitoring approach.Furthermore,the changes in diversity and community composition over sampling dates in COI data were generally consistent with those in morphological identification,although a temporal lag existed between these two approaches.A notable shift in the fouling community occurred at the end of June with the appearance of Ectopleura crocea and Caprella sp.,marking a pivotal change in its structure.Future research could focus on developing targeted primers for these key fouling species,which would enhance the efficiency of monitoring efforts.展开更多
Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in ...Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.展开更多
Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side rea...Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).展开更多
[Objectives]To assess the carbon sink capacity in seawater suspension cage aquaculture of shellfish in Tianjin from 2015 to 2022.[Methods]The carbon sink capacity of different shellfish species was evaluated using bot...[Objectives]To assess the carbon sink capacity in seawater suspension cage aquaculture of shellfish in Tianjin from 2015 to 2022.[Methods]The carbon sink capacity of different shellfish species was evaluated using both physical and value assessment methods.[Results]The shellfish cultivated in seawater suspension cages in Tianjin exhibited a significant capacity for carbon sinks.The amounts of carbon removed by suspension cage aquaculture of Rapana venosa,Crassostrea gigas,Scapharca subcrenata,Scapharca broughtonii and Argopectens irradias were 448.297,403.398,89.463,40.657,and 106.719 t,respectively.Furthermore,the total volume of shellfish cultivated in seawater exhibited a consistent upward trend over time,correlating with an annual increase in the amount of carbon removed.Among the shellfish cultivated in seawater suspension cages,the order of carbon sink capacity was as follows:C.gigas>R.venosa>A.irradias>S.subcrenata and S.broughtonii.In terms of the carbon sink capacity of soft tissues,the ranking was as follows:A.irradias>R.venosa>C.gigas>S.subcrenata and S.broughtonii.The structural and yield factors associated with seawater suspension cage aquaculture of shellfish significantly influenced the enhancement of the total carbon sink of cultivated shellfish.Notably,structural factors had a greater impact on the increase in the carbon sink of cultivated shellfish compared to total yield factors.[Conclusions]The findings will serve as a reference for enhancing the carbon sink potential of fisheries and achieving sustainable development in seawater aquaculture in Tianjin.展开更多
The desensitization of nitramine explosives while maintaining energetic performance is challenging.A highly efficient desensitizer is the key to solving the antinomy.This study focuses on using porous organic cages(PO...The desensitization of nitramine explosives while maintaining energetic performance is challenging.A highly efficient desensitizer is the key to solving the antinomy.This study focuses on using porous organic cages(POCs),specifically CC3 and RCC3,to desensitize RDX.By coating 0.1 wt%–5 wt%of POCs on RDX particles,a series of composite energetic materials were prepared.Characterization results show that POCs change the surface morphology of RDX,and there are interfacial interactions between them.The RDX@POCs composites exhibit enhanced stabilities in terms of heat,impact,friction,and electrostatic spark.For the RDX@RCC3-5%composite,the impact sensitivity(E_(IS)),friction sensitivity(E_(FS)),and electrostatic sensitivity(EES)were significantly reduced by 66.7%,68.8%,and 56.5%,respectively,while the detonation velocity decreased by merely 3.1%.These findings indicate that POCs,especially RCC3,are promising desensitizers for nitramine explosives,and their desensitization mechanisms likely involve barrier and buffering effects.The distinct desensitization behavior of RDX@RCC3 highlights the effectiveness of POCs in reducing the sensitivity of RDX without significantly compromising its energetic properties.展开更多
Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in...Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.展开更多
Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the cla...Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.展开更多
Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-a...Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-assembly of a water-soluble Pd_(2)L_(2) cage 1 with a large hydrophobic cavity,formed from novel macrocyclic ligands(L)and cis-Pd(Ⅱ).Cage 1 can selectively encapsulate PHE instead of ANT.Based on host-vip recognition followed by extraction,we achieve a remarkable 99%purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution.Importantly,the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles,demonstrating its robustness.This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-vip strategy.展开更多
Interbody fusion is recognized as the golden standard of surgical intervention for degenerative disc disease(DDD).Interbody fusion cage made of polyetheretherketone(PEEK)is commonly used in lumbar interbody fusion sur...Interbody fusion is recognized as the golden standard of surgical intervention for degenerative disc disease(DDD).Interbody fusion cage made of polyetheretherketone(PEEK)is commonly used in lumbar interbody fusion surgery in the treatment of DDD worldwide.However,there are some limitations of PEEK including their bio-inert nature and impediment to host bone integration.This study aimed to evaluate the degradation profile and osteoinductive potential of biodegradable Mg-Zn-Nd-Zr cages with/without micro-arc oxidation(MAO)coatings.The Mg-Zn-Nd-Zr alloy cages,whether coated with MAO or not,demonstrated commendable biocompatibility and biomechanical properties.Immersion and electrochemical tests show better corrosion resistance of MAO coatings in vitro.mRNA sequencing,RT-qPCR and Western blotting revealed that Mg-Zn-Nd-Zr and Mg-Zn-Nd-Zr/MAO had a better effectiveness on osteoinductivity.In vivo evaluations in ovine models over 12 weeks and 24 weeks post-implantation revealed radiological and histological evidence of enhanced bone formation adjacent to the Mg-Zn-Nd-Zr alloy cages compared to PEEK counterparts.Moreover,the MAO-coated cages exhibited a reduced propensity for gas formation.The Mg-Zn-Nd-Zr alloy is as a superior osteoinductive material compared with PEEK,with the MAO coating offering an advantage in mitigating gas production.Nonetheless,further research is warranted to refine the alloy's composition or surface treatments,particularly to address the challenges associated with rapid gas evolution during the early post-implantation period.展开更多
Photocycloaddition affords opportunities to engage in advanced fuels with high-strained cyclobutyl-containing structures.Herein,the one-step route for the synthesis of high-energy-density caged fuel,tetracyclo[4.2.1.0...Photocycloaddition affords opportunities to engage in advanced fuels with high-strained cyclobutyl-containing structures.Herein,the one-step route for the synthesis of high-energy-density caged fuel,tetracyclo[4.2.1.0^(2.5).0^(3,7)]nonane(TCN)with high-strained four-membered structure,has been developed via photosensitized[2+2]cycloaddition of 5-vinyl-2-norbornene(VNB).The reaction conditions are optimized to obtain a high conversion of VNB of 91.9%.The triplet quenching and Stern-Volmer quenching studies indicate that[2+2]photocycloaddition follows the triplet-triplet energy transfer process,and a kinetic model is expressed as a reaction rate equation correlated with the incident light flux.Importantly,the obtained TCN shows a high density of 1.003 g·cm^(-3)and volumetric net heat of combustion of 42.31 MJ·L^(-1),which can serve as an excellent high-energy additive for blending with liquid fuels.展开更多
Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to d...Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to dynamically adjust their structures to accommodate functional needs.Mimicking this adaptability in synthetic systems is an ongoing challenge in supramolecular chemistry.展开更多
目的探讨基于MRI的椎体骨质量评分(vertebral bone quality score,VBQ)和终板骨质量评分(endplate bone quality score,EBQ)在经椎间孔腰椎椎间融合(transforaminal lumbar interbody fusion,TLIF)术后cage沉降中的预测价值。方法因腰...目的探讨基于MRI的椎体骨质量评分(vertebral bone quality score,VBQ)和终板骨质量评分(endplate bone quality score,EBQ)在经椎间孔腰椎椎间融合(transforaminal lumbar interbody fusion,TLIF)术后cage沉降中的预测价值。方法因腰椎退行性疾病在我院行TLIF手术的226例患者,根据术后有无cage沉降将患者分为沉降组和非沉降组,比较两组患者VBQ和EBQ评分。通过多元回归分析cage沉降的危险因素,并根据受试者工作特征曲线下面积(AUC)评估VBQ和EBQ预测TLIF术后cage沉降的能力。结果226例患者中30例出现术后cage沉降。沉降组VBQ(3.8±0.4)分,EBQ(5.1±0.7)分,明显高于非沉降组(3.1±0.6)分和(4.2±1.0)分,差异有统计学意义(P<0.001)。多元回归分析显示VBQ(OR=4.258,95%CI:1.983~9.142,P<0.001)和EBQ(OR=1.971,95%CI:1.212~3.203,P=0.006)评分越高,发生cage沉降风险也越大。受试者工作特征曲线结果显示VBQ的AUC为0.843,EBQ的AUC是0.864。VBQ和EBQ预测cage沉降的最佳阈值分别为3.480(敏感性90%;特异性75.5%)和4.620(敏感性96.7%;特异性74.5%)。结论术前VBQ或EBQ评分越高,TLIF术后发生cage沉降风险越大。其中EBQ可能是一个更好的预测融合术后cage沉降的指标。展开更多
基金supported by the National Natural Science Foundation of China(No.92372123)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515012057,2022B1515020005,2023B1515130004)Guangzhou Basic and Applied Basic Research Foundation(No.202201011342).
文摘Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
基金National Natural Science Foundation of China,Grant/Award Number:82204958 and 82305065Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2020ZD17+2 种基金Traditional Chinese Medicine Emotional Disease and Brain Steady State Regulation Innovation Team,Grant/Award Number:2023KJ191Medical and Health Science and Technology Development Plan Project of Shandong Province,Grant/Award Number:202105010467Traditional Chinese Medicine Science and Technology Project of Shandong Province,Grant/Award Number:Q-2022059。
文摘Background:Previously,a chronic social defeat stress(CSDS)model has been widely-adopted for assessing depressive-like behaviors in animals.However,there is still room for improvement in the CSDS model to safeguard study accuracy and the wel-fare of lab rodents.Our study team developed a novel,standardized apparatus to induce CSDS in rodents and assessed the model's practical adaptability.Methods:An innovative CSDS cage apparatus and water bottle was designed.To evaluate the effectiveness of the newly developed tools,a variety of animal models,including the tail suspension test(TST),sucrose preference test,forced swimming test(FST),novelty-suppressed feeding test,female urine sniffing test,and open field test(OFT),were adopted to assess depressive-like behaviors in mice.Fluoxetine treat-ment was also administered to observe the reversal effect,as part of the validation.Results:The CSDS cage apparatus resulted in the manifestation of depressive-like behaviors in the model mice.Significant reductions in sucrose preference and urine sniffing time were observed,while the OFT revealed decreased central zone total distance,residence time,and frequency of entry.Moreover,increased immobility was found in the FST and TST.Fluoxetine treatment was found to successfully reverse the modeling effect.Conclusion:The CSDS cage apparatus was validated for enhanced usability and ad-dressed the previous challenges of water bottle leakage and lab rodent welfare is-sues.The consistent results from multiple behavioral tests also supported real-world application of the apparatus,offering researchers a promising alternative to conven-tional rodent cages.
基金supported by grants from the National Key Research and Development Program of China(No.2023YFD2401103)the Fundamental Research Funds for the Central Universities.
文摘Evaluating species composition and dynamic shifts within fouling communities is essential for developing effective strate-gies to manage biofouling in marine fish aquaculture.The coastal area in the Yellow Sea is a key area for cage aquaculture in China;however,this region faces significant challenges from biofouling organisms.Here,we employed an experimental approach in a filed mesocosm in a net cage aquaculture area in the Yellow Sea,with weekly monitoring of changes in macrofouling species on mesh nets and in the seawater,to assess the utility of water eDNA metabarcoding for identifying macrofoulers.We compared the temporal variation patterns in the composition and diversity of macrofouling communities identified through morphological method as well as COI and 18S rRNA metabarcoding.The results showed that metabarcoding detected the majority of macrofoulers identified through morphological method(64%),and revealed additional species that were overlooked by traditional monitoring approach.Furthermore,the changes in diversity and community composition over sampling dates in COI data were generally consistent with those in morphological identification,although a temporal lag existed between these two approaches.A notable shift in the fouling community occurred at the end of June with the appearance of Ectopleura crocea and Caprella sp.,marking a pivotal change in its structure.Future research could focus on developing targeted primers for these key fouling species,which would enhance the efficiency of monitoring efforts.
基金supported by the National Natural Science Foundation of China(Grant Nos.22271164 and U20A20259 and 22371147)the Fundamental Research Funds for the Central Universities,the NCC Fund(Grant No.NCC2020FH04)+1 种基金the Tianshan Innovation Team Plan of Xinjiang Uygur Autonomous Region(Grant No.2023D14002)Nankai University(NKU).
文摘Covalent organic cages(COCs)are three-dimensional organic molecules with permanent cavities,known for their ordered pore structures,excellent processability,and modular design.They have shown significant potential in applications such as gas adsorption,molecular separation,and catalysis.Introducing chiral elements into COCs results in chiral COCs with confined chiral cavities,which endows them with unique chiral functions and expands their application prospects.This review summarizes the research progress on chiral covalent organic cages,focusing on strategies for incorporating chiral elements,the structures and synthesis methods of representative chiral COCs,and advancements in their chiral functions.Additionally,we provide perspectives on future research directions.We hope this review will inspire further interest and creativity among researchers in the field of chiral molecular cages,leading to the development of materials with unique structures and functions.
基金funded by the National Natural Science Foundation of China(22478632)Key Scientific and Technological Project of Henan Province(242102321032).
文摘Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).
基金Supported by Science and Technology Commissioner Project of Tianjin Science and Technology Bureau(22ZYCGSN00630).
文摘[Objectives]To assess the carbon sink capacity in seawater suspension cage aquaculture of shellfish in Tianjin from 2015 to 2022.[Methods]The carbon sink capacity of different shellfish species was evaluated using both physical and value assessment methods.[Results]The shellfish cultivated in seawater suspension cages in Tianjin exhibited a significant capacity for carbon sinks.The amounts of carbon removed by suspension cage aquaculture of Rapana venosa,Crassostrea gigas,Scapharca subcrenata,Scapharca broughtonii and Argopectens irradias were 448.297,403.398,89.463,40.657,and 106.719 t,respectively.Furthermore,the total volume of shellfish cultivated in seawater exhibited a consistent upward trend over time,correlating with an annual increase in the amount of carbon removed.Among the shellfish cultivated in seawater suspension cages,the order of carbon sink capacity was as follows:C.gigas>R.venosa>A.irradias>S.subcrenata and S.broughtonii.In terms of the carbon sink capacity of soft tissues,the ranking was as follows:A.irradias>R.venosa>C.gigas>S.subcrenata and S.broughtonii.The structural and yield factors associated with seawater suspension cage aquaculture of shellfish significantly influenced the enhancement of the total carbon sink of cultivated shellfish.Notably,structural factors had a greater impact on the increase in the carbon sink of cultivated shellfish compared to total yield factors.[Conclusions]The findings will serve as a reference for enhancing the carbon sink potential of fisheries and achieving sustainable development in seawater aquaculture in Tianjin.
文摘The desensitization of nitramine explosives while maintaining energetic performance is challenging.A highly efficient desensitizer is the key to solving the antinomy.This study focuses on using porous organic cages(POCs),specifically CC3 and RCC3,to desensitize RDX.By coating 0.1 wt%–5 wt%of POCs on RDX particles,a series of composite energetic materials were prepared.Characterization results show that POCs change the surface morphology of RDX,and there are interfacial interactions between them.The RDX@POCs composites exhibit enhanced stabilities in terms of heat,impact,friction,and electrostatic spark.For the RDX@RCC3-5%composite,the impact sensitivity(E_(IS)),friction sensitivity(E_(FS)),and electrostatic sensitivity(EES)were significantly reduced by 66.7%,68.8%,and 56.5%,respectively,while the detonation velocity decreased by merely 3.1%.These findings indicate that POCs,especially RCC3,are promising desensitizers for nitramine explosives,and their desensitization mechanisms likely involve barrier and buffering effects.The distinct desensitization behavior of RDX@RCC3 highlights the effectiveness of POCs in reducing the sensitivity of RDX without significantly compromising its energetic properties.
基金supported by the National Natural Science Foundation of China(Nos.92261108 and 2022YFA1503303)the STS Project of Fujian-CAS(No.2023T3054)。
文摘Although many racemic M4L6cages have been synthesized,little attention has been paid to the resolution of M4L6cages because resolution of these cages is very difficult.To explore the use of optically pure M4L6cages in chiral applications,it is important to obtain a single enantiomer.In this work,the anionicΛΛΛΛ-Zr_(4)L_(6)andΛΛΛΛ-Zr_(4)L_(6)(L=embonate)cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN,respectively,and the active vertex of homochiral Zr_(4)L_(6)cage trapsπ-conjugated coordination silver cations(such as[Ag_(2)(DPPM)_(2)]^(2+),chiral[Ag_(2)(PPh_(3))_(2)(DPEN)]^(2+)and[Ag(PPh_(3))(DPEN)]^(+)),obtaining two pair of pure enantiomers(PTC-375(Λ/Λ)and PTC-376(Λ/Λ)).Interestingly,the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence(CPL)response,and PTC-376 enantiomers show a CPL output with glumvalues up to~1.4×10^(-2).This work not only provides a new resolution strategy for metal-organic cages,but also expands their chiral application especially in CPL field.
基金supported by National Natural Science Foundation of China(Nos.22201046,22371054)Local Innovation Research Team Project of Guangdong Pearl River Talent Plan(No.2017BT01Z032)。
文摘Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.
基金supported by the National Key Research and Development Program of China(Nos.2022YFA1503300 and 2021YFA1500400)the National Natural Science Foundation of China(Nos.22171262,21825107 and 22171264)the Science Foundation of Fujian Province(Nos.2021J01516 and 2021J02016)。
文摘Selective separation of phenanthrene(PHE)from aromatic isomer mixtures poses a significant challenge in industry due to the similar physical properties of PHE and its isomer anthracene(ANT).Herein,we report the self-assembly of a water-soluble Pd_(2)L_(2) cage 1 with a large hydrophobic cavity,formed from novel macrocyclic ligands(L)and cis-Pd(Ⅱ).Cage 1 can selectively encapsulate PHE instead of ANT.Based on host-vip recognition followed by extraction,we achieve a remarkable 99%purity of PHE separation from an equimolar mixture of PHE and ANT using cage 1 in aqueous solution.Importantly,the separation performance of PHE using cage 1 remains unaffected even after five extraction cycles,demonstrating its robustness.This work highlights the potential of supramolecular cages for efficient and cost-effective PHE separation from the isomer ANT in aqueous solutions using such promising host-vip strategy.
基金supported by the National Natural Science Foundation of China(82172392)the National Natural Science Foundation of China(82372401)+1 种基金the Beijing Natural Science Foundation(L202033)the Basic Applied Research Program of Liaoning Province of China(2022020347-JH2/1013)。
文摘Interbody fusion is recognized as the golden standard of surgical intervention for degenerative disc disease(DDD).Interbody fusion cage made of polyetheretherketone(PEEK)is commonly used in lumbar interbody fusion surgery in the treatment of DDD worldwide.However,there are some limitations of PEEK including their bio-inert nature and impediment to host bone integration.This study aimed to evaluate the degradation profile and osteoinductive potential of biodegradable Mg-Zn-Nd-Zr cages with/without micro-arc oxidation(MAO)coatings.The Mg-Zn-Nd-Zr alloy cages,whether coated with MAO or not,demonstrated commendable biocompatibility and biomechanical properties.Immersion and electrochemical tests show better corrosion resistance of MAO coatings in vitro.mRNA sequencing,RT-qPCR and Western blotting revealed that Mg-Zn-Nd-Zr and Mg-Zn-Nd-Zr/MAO had a better effectiveness on osteoinductivity.In vivo evaluations in ovine models over 12 weeks and 24 weeks post-implantation revealed radiological and histological evidence of enhanced bone formation adjacent to the Mg-Zn-Nd-Zr alloy cages compared to PEEK counterparts.Moreover,the MAO-coated cages exhibited a reduced propensity for gas formation.The Mg-Zn-Nd-Zr alloy is as a superior osteoinductive material compared with PEEK,with the MAO coating offering an advantage in mitigating gas production.Nonetheless,further research is warranted to refine the alloy's composition or surface treatments,particularly to address the challenges associated with rapid gas evolution during the early post-implantation period.
基金the support from the National Natural Science Foundation of China(22408272,22222808,U24A20547)the Aeronautical Science Foundation of China(2023Z073048003)+1 种基金the China National Postdoctoral Program for Innovative Talents(BX20240251)the China Postdoctoral Science Foundation(2023M742592)。
文摘Photocycloaddition affords opportunities to engage in advanced fuels with high-strained cyclobutyl-containing structures.Herein,the one-step route for the synthesis of high-energy-density caged fuel,tetracyclo[4.2.1.0^(2.5).0^(3,7)]nonane(TCN)with high-strained four-membered structure,has been developed via photosensitized[2+2]cycloaddition of 5-vinyl-2-norbornene(VNB).The reaction conditions are optimized to obtain a high conversion of VNB of 91.9%.The triplet quenching and Stern-Volmer quenching studies indicate that[2+2]photocycloaddition follows the triplet-triplet energy transfer process,and a kinetic model is expressed as a reaction rate equation correlated with the incident light flux.Importantly,the obtained TCN shows a high density of 1.003 g·cm^(-3)and volumetric net heat of combustion of 42.31 MJ·L^(-1),which can serve as an excellent high-energy additive for blending with liquid fuels.
基金the Natural Science Foundation of China(No.22301131)the Natural Science Foundation of Jiangsu Province(Nos.BK20220781,BK20240679)the National Key Research and Development Program of China(No.2024YFB3815700)are greatly acknowledged.
文摘Dynamic adaptability is a key feature in biological macromolecules,enabling selective binding and catalysis[1].From DNA supercoiling to enzyme conformational changes,biological systems have evolved intricate ways to dynamically adjust their structures to accommodate functional needs.Mimicking this adaptability in synthetic systems is an ongoing challenge in supramolecular chemistry.
文摘目的探讨基于MRI的椎体骨质量评分(vertebral bone quality score,VBQ)和终板骨质量评分(endplate bone quality score,EBQ)在经椎间孔腰椎椎间融合(transforaminal lumbar interbody fusion,TLIF)术后cage沉降中的预测价值。方法因腰椎退行性疾病在我院行TLIF手术的226例患者,根据术后有无cage沉降将患者分为沉降组和非沉降组,比较两组患者VBQ和EBQ评分。通过多元回归分析cage沉降的危险因素,并根据受试者工作特征曲线下面积(AUC)评估VBQ和EBQ预测TLIF术后cage沉降的能力。结果226例患者中30例出现术后cage沉降。沉降组VBQ(3.8±0.4)分,EBQ(5.1±0.7)分,明显高于非沉降组(3.1±0.6)分和(4.2±1.0)分,差异有统计学意义(P<0.001)。多元回归分析显示VBQ(OR=4.258,95%CI:1.983~9.142,P<0.001)和EBQ(OR=1.971,95%CI:1.212~3.203,P=0.006)评分越高,发生cage沉降风险也越大。受试者工作特征曲线结果显示VBQ的AUC为0.843,EBQ的AUC是0.864。VBQ和EBQ预测cage沉降的最佳阈值分别为3.480(敏感性90%;特异性75.5%)和4.620(敏感性96.7%;特异性74.5%)。结论术前VBQ或EBQ评分越高,TLIF术后发生cage沉降风险越大。其中EBQ可能是一个更好的预测融合术后cage沉降的指标。
