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
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
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
The stabilization of active molecules is significantly important for chemistry,especially for the bioactive molecules.In this work,we report the synthesis and characterization of three tetrahedral Fe_(4)L_(6) cages,wh...The stabilization of active molecules is significantly important for chemistry,especially for the bioactive molecules.In this work,we report the synthesis and characterization of three tetrahedral Fe_(4)L_(6) cages,which are water-soluble and functionalized with or without PEG chains.All cages can physically trap NO molecules in their cavities to prevent a reaction with O_(2).Single-crystal X-ray diffraction(SCXRD),Griess assay,electron paramagnetic resonance(EPR)spectroscopy,and fluorescence assay demonstrate that NO molecules were encapsulated and stabilized by these cage molecules through the formation of host-vip supramolecules.These NO-loaded cages show high antibacterial activities for inhibiting Staphylococcus aureus and Escherichia coli,providing a convenient method for making antibiotic agents.Moreover,these PEG-functionalized cages exhibit excellent biocompatibility,providing a new strategy for developing materials for NO delivery in biomedical applications.展开更多
The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential...The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.展开更多
Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules.The molecular cages were obtained starting from tetrayne monomers through alkyne metath...Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules.The molecular cages were obtained starting from tetrayne monomers through alkyne metathesis cyclooligomerization.We found these porphyrin-based rigid molecular cages can insert into the lipid bilayer and efficiently transport ions and small molecules(e.g.,calcein).Our study reveals longer hydrophobic alkyl chains on the cage molecule promote the channeling efficiency,while shorter and/or more polar side chains impair such activity.Kinetic analysis shows linear correlation between the rate of proton transport and the concentration of the cage,suggesting the active species is likely a monomeric cage.We found that C_(70)-encapsulated cages are nearly inactive for transmembrane ion transportation,indicating that ions are likely transported through the internal cavity of the cage.Discrete shape-persistent organic cages represent highly stable synthetic ion channels or pores,which could have interesting applications in biomimetic signaling and drug delivery.展开更多
The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-...The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The vip encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.展开更多
[Objective]The study was to monitor the indoor environmental parameters of broiler house with three-overlap cages and analyze the differences in winter and autumn. [Method] In the process of feeding,the same broiler h...[Objective]The study was to monitor the indoor environmental parameters of broiler house with three-overlap cages and analyze the differences in winter and autumn. [Method] In the process of feeding,the same broiler house in the same farm was chosen to determine indoor ambient temperature,humidity and air quality at 3-6 weeks age of broilers in different seasons. The measure points were distributed in four different positions in the house. [Result] There was no significant difference in ambient temperature between autumn and winter( P > 0. 05). The ambient temperature in the house in winter was slightly higher than that in autumn. The humidity in autumn was significantly higher than that in winter( P < 0. 05). The temperature and humidity in two seasons could meet the requirements of broiler growth. There was no significant difference( P > 0. 05) in ammonia concentration between autumn and winter,while ammonia concentration in winter was slightly higher than that in autumn. The carbon dioxide concentration of broiler house in winter was significantly higher than that in autumn( P < 0. 05).The total number of airborne bacteria in winter was significantly higher than that in autumn( P < 0. 05). [Conclusion]The indoor temperature kept constant in autumn and winter seasons in closed poultry house. In winter,the humidity was reduced,the carbon dioxide concentration was increased,and the total number of bacteria in the air was increased. The ventilation in winter should be increased in case of heat preservation.展开更多
pH responsive composite Janus cages of PS-silica-PEO are prepared using silica nanoparticles to crosslink two PAA contained di-block copolymers at an emulsion interface sequentially. Transverse channels are in situ cr...pH responsive composite Janus cages of PS-silica-PEO are prepared using silica nanoparticles to crosslink two PAA contained di-block copolymers at an emulsion interface sequentially. Transverse channels are in situ created across the shell, which facilitates mass transfer. Shell is pH responsive owing to the presence of residual PAA chains tethered onto the silica nanoparticles. The Janus cages are capable to preferentially capture oil from their aqueous surroundings. The saturation absorption capacity is determined by pH and oil property. Other composite Janus cages are expected by extension the method using other copolymers and functional nanoparticles.展开更多
Density functional theory calculations within the G03W package, with B3LYP exchange functional and applying basis set 6 - 31 G (d,p) are performed. The surface reactivity and electronic properties of endo-hydrogenatio...Density functional theory calculations within the G03W package, with B3LYP exchange functional and applying basis set 6 - 31 G (d,p) are performed. The surface reactivity and electronic properties of endo-hydrogenation and exo-hydrogenation fullerene cages are studied. It is found that the surface reactivity of mono-hydrogenation fullerene cages is larger than the surface reactivity of un-hydrogenation fullerene cages and the later is larger than the fully hydrogenation fullerene cages. In addition, the calculations show that the endo-hydrogenation fullerene cages possess the same band gaps as the un-hydrogenation fullerene cages, however, the exo-hydrogenation is reduced the band gaps of the un-hydrogenated fullerene cages form ~7 eV to ~5 eV.展开更多
To investigate the cage stability of high-speed oil-lubricated angular contact ball bearings, a dynamic model of cages is developed on the basis of Gupta’s and Meeks’ work. The model can simulate the cage motion und...To investigate the cage stability of high-speed oil-lubricated angular contact ball bearings, a dynamic model of cages is developed on the basis of Gupta’s and Meeks’ work. The model can simulate the cage motion under oil lubrication with all six degrees of freedom. Particularly, the model introduces oil-film damping and hysteresis damping, and deals with the collision contact as imperfect elastic contact. In addition, the effects of inner ring rotational speed, the ratio of pocket clearance to guiding clearance and applied load on the cage stability are investigated by simulating the cage motion with the model. The results can provide a theoretical basis for the design of ball bearing parameters.展开更多
Study on the microscopic structure of clathrate hydrate has made significant progress in the past decades.This review aims to summarize the state of the art of the experimental characterization of vip molecular occu...Study on the microscopic structure of clathrate hydrate has made significant progress in the past decades.This review aims to summarize the state of the art of the experimental characterization of vip molecular occupancy in clathrate hydrate cages,which is an important area of the microscopic structures.The characterizing method and features of different vip molecular,such as hydrocarbon,carbon dioxide,hydrogen and inhibitor/promoter,in different hydrate cages have been extensively reviewed.A comprehensive use of advanced technologies such as X-ray diffraction,Raman spectroscopy and nuclear magnetic resonance may provide better understanding on the compositions and microscopic mechanisms of clathrate hydrate.展开更多
The present study investigated the applicability of integrated polychaete-fish culture for fish waste removal to offset negative impact induced by organic benthic enrichment.A field study demonstrated that deposition ...The present study investigated the applicability of integrated polychaete-fish culture for fish waste removal to offset negative impact induced by organic benthic enrichment.A field study demonstrated that deposition rate was significantly higher underneath the fish farm than that in control area.The material settling under the farm was characterized by a high amount of fish feces(45%) and uneaten feed(27%).Both feeding rate(FR) and apparent digestibility rate(ADR) increased with decreasing body weight,as was indicated by significantly a higher rate observed for the groups containing smaller individuals in a lab study.The nutrient in fresh deposited material(De) was higher than that in sediments collected under the farm(Se),resulting in lower feces production but higher apparent digestibility rate for the De group as feeding rate was similar.Consequently,higher nutrient removal efficiency was observed in the De group.A mass balance approach indicated that approximately 400–500 individuals m^(-2) is required for removing all waste materials deposited underneath the fish farm,whereas abundance can be lower(about 300–350 individuals m^(-2)) when only the fish waste needs to be removed.The results showed that a significant amount of waste had been accumulated in the fish cages in Sanggou Bay.The integration of fish with P.aibuhitensis seems promising for preventing organic pollution in the sediment and therefore is an effective strategy for mitigating negative effect of fish farms.Thus such integration can become a new IMTA(integrated multi-trophic aquaculture) model in Sanggou Bay.展开更多
The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as...The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as MOC-Py-M(M=H,Cu,and Zn),are designed for PMDs by combining metalloporphyrin-based ligands with catalytically active Pd^(2+)centers.These metal-organic cages(MOCs)are first successfully hybridized with graphitic carbon nitride(g-C_(3)N_(4))to form direct Z-scheme heterogeneous MOC-Py-M/g-C_(3)N_(4)(M=H,Cu,and Zn)photocatalysts via π-πinteractions.Benefiting from its better light absorption ability,the MOC-Py-Zn/g-C_(3)N_(4) catalyst exhibits high H_(2) production activity under visible light(10348μmol g^(-1) h^(-1)),far superior to MOC-Py-H/g-C_(3)N_(4) and MOC-Py-Cu/g-C_(3)N_(4).Moreover,the MOC-Py-Zn/g-C_(3)N_(4) system obtains an enhanced turn over number(TON)value of 32616 within 100 h,outperforming the homogenous MOC-Py-Zn(TON of 507 within 100 h),which is one of the highest photochemical hybrid systems based on MOC for visible-light-driven hydrogen generation.This confirms the direct Z-scheme heterostructure can promote effective charge transfer,expand the visible light absorption region,and protect the cages from decomposition in MOC-Py-Zn/g-C_(3)N_(4).This work presents a creative example that direct Z-scheme PMD-based systems for effective and persistent hydrogen generation from water under visible light are obtained by heterogenization approach using homogeneous porphyrin-based MOCs and g-C_(3)N_(4) semiconductors.展开更多
Luminescent metal organic cages(MOCs)have attracted great interest as a unique class of sensing substrates.In this work,intrinsically fluorescent Zr-MOCs were successfully used as fluorescent probes for the sensitive ...Luminescent metal organic cages(MOCs)have attracted great interest as a unique class of sensing substrates.In this work,intrinsically fluorescent Zr-MOCs were successfully used as fluorescent probes for the sensitive and selective detection of phosphate anions in water and real samples.When the ligand and Zr ion clusters form a cage,the intrinsic fluorescence of the ligand was tuned from high to weak emission due to the ligand-to-metal charge transfer(LMCT)effect,and this weakened fluorescence can be restored by the addition of phosphate.The degree of fluorescence enhancement is positively correlated with the added phosphate concentration,and the efficacy of this strategy is demonstrated by a linear phosphate detection range of 5–500µmol/L and a detection limit of 1.06µmol/L.We discuss the interaction between phosphate and Zr in scattering spectrum and MS,respectively.In comparison to phosphate adsorption on Zr-metal organic frameworks(MOFs),where phosphate connects different numbers of cages,both blocking the LMCT effect and causing the cages to aggregate.We also found that the phosphate displaces the ligand from the cage when the phosphate concentration is further expanded,resulting in the formation of new derivatives.This derivative was shown to be useful as a Lewis acid catalyst and as a rare earth ion adsorbent.展开更多
The goal of this paper is to provide a comparative analysis of two commonly used approaches to discretize offshore fish cages： the lumped-mass approach and the finite element technique. Two case studies are chosen to...The goal of this paper is to provide a comparative analysis of two commonly used approaches to discretize offshore fish cages： the lumped-mass approach and the finite element technique. Two case studies are chosen to compare predictions of the LMA（lumped-mass approach） and FEA（finite element analysis） based numerical modeling techniques. In both case studies, we consider several loading conditions consisting of different uniform currents and monochromatic waves. We investigate motion of the cage, its deformation, and the resultant tension in the mooring lines. Both model predictions are sufficient close to the experimental data, but for the first experiment, the DUT-Flex Sim predictions are slightly more accurate than the ones provided by Aqua-FETM. According to the comparisons, both models can be successfully utilized to the design and analysis of the offshore fish cages provided that an appropriate safety factor is chosen.展开更多
Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-viny...Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.展开更多
Background: cervical spondylotic myelopathy is a common health problem that neurosurgeons face in Egypt. The aim of this study is to evaluate the efficacy of PEEK cage only in 4 levels anterior cervical discectomy as ...Background: cervical spondylotic myelopathy is a common health problem that neurosurgeons face in Egypt. The aim of this study is to evaluate the efficacy of PEEK cage only in 4 levels anterior cervical discectomy as one of surgical option other than anterior cervical corpectomy, fixation by plat or posterior approach for cervical laminectomy, and assessment of post spinal surgery pain. Methods: this prospective study on 28 patients with cervical spondylotic myelopathy (CSM) over a period of 3 years (between April 2012 and April 2015) with mean period of follow up 30 months. We have done anterior cervical discectomy with fixation by cage only for all cases with perioperative assessment and scoring clinically and radiologically (Japanese Orthopaedic Association [JOA] scores, Visual Analogue Scale [VAS] scores for assessment of neck and arm pain, perioperative parameters (hospital stay, blood loss, operative time), the European Myelopathy Scoring (EMS) and Odom’s criteria, and the incidence of complication,post spinal surgery pain assessment). Results: clinical outcome was excellent (28.55), good (50%) and fair (21.5) according to Odom criteria. The European Myelopathy Scoring (EMS), improved from 10 to 16. The mean JOA score improved from 10.1 ± 2.1 to 14.2 ± 2.3. Fusion failure had been seen in 4 patients in one level for each secondary to anterior displacement of the cage with no other major complications. Conclusion: 4 levels anterior cervical discectomy with PEEK cage only is an effective, save and less costly with less post operative complication and hospital stay and less post spinal surgery pain.展开更多
The synthesis of T_8, T_ 10 and T_ 12 silsesquioxane cages from a range of starting materials: phenyl-cis-tetrol, 1,3-divinyltetraethoxydisiloxane and cyclopentyl T resins by using tetra n-butylammonium fluoride(TBA...The synthesis of T_8, T_ 10 and T_ 12 silsesquioxane cages from a range of starting materials: phenyl-cis-tetrol, 1,3-divinyltetraethoxydisiloxane and cyclopentyl T resins by using tetra n-butylammonium fluoride(TBAF) as the catalyst is described in this paper. The reaction yields obtained viathe current route are better compared to those viathe literature routes. Some of the cage compounds have been characterized by X-ray crystallography.展开更多
A pair of selenanthrene-bridged molecular cages have been constructed through a one-step cyclization reaction of a tetrakis(iodo) crown ether with selenium powder. The tubular belt-shaped cage has an intrinsic cavity ...A pair of selenanthrene-bridged molecular cages have been constructed through a one-step cyclization reaction of a tetrakis(iodo) crown ether with selenium powder. The tubular belt-shaped cage has an intrinsic cavity which can adaptively transform to accommodate electron-deficient vips forming [2]pseudorotaxane complexes. The other product was determined to be an isomeric cage featuring a Mobius strip structure, which exhibits slower twist-migration dynamics than its thianthrene counterpart. The success of using selenanthrene as joints enables an alternative way to structural design and property regulation of molecular cages.展开更多
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.
基金supported by the National Natural Science Foundation of China(Nos.22171106,22431006,22150004 and 22375075)Guangdong Major Project of Basic and Applied Basic Research(Nos.2023B0303000013,2019B030302009)+1 种基金Guangdong Natural Science Foundation(No.2022A1515011937)Jinan University.
文摘The stabilization of active molecules is significantly important for chemistry,especially for the bioactive molecules.In this work,we report the synthesis and characterization of three tetrahedral Fe_(4)L_(6) cages,which are water-soluble and functionalized with or without PEG chains.All cages can physically trap NO molecules in their cavities to prevent a reaction with O_(2).Single-crystal X-ray diffraction(SCXRD),Griess assay,electron paramagnetic resonance(EPR)spectroscopy,and fluorescence assay demonstrate that NO molecules were encapsulated and stabilized by these cage molecules through the formation of host-vip supramolecules.These NO-loaded cages show high antibacterial activities for inhibiting Staphylococcus aureus and Escherichia coli,providing a convenient method for making antibiotic agents.Moreover,these PEG-functionalized cages exhibit excellent biocompatibility,providing a new strategy for developing materials for NO delivery in biomedical applications.
基金Project supported by the National Natural Science Foundation of China(52062034)the National Key Research and Development Program of China(2019YFC0605002)。
文摘The construction and functionalization of lanthanide-organic cages have been a research hotspot in coordination chemistry.Benefiting from the unique luminescent and magnetic properties of lanthanide ions,the potential applications of lanthanide-organic cages in biological imaging applications are promising,but only a few corresponding explorations have been reported.He rein,we introduced a series of lanthanide tetrahedral cages,(Eu_(n)Gd_(4-n)L_(4))(sol)_8(n=0,1,2,3 and 4,where L=(4,4',4"-tris(4,4,4-trifluoro-1,3-dioxobutyl)-triphenylamine,and sol=dimethyl sulfoxide and methanol),with potential applications in biological imaging.Given the good luminescent and magnetic properties of Eu^(3+) and Gd^(3+) ions,Eu_(4)L_(4) and Gd_(4)L_(4) complexes show a high luminescence quantum yield of 29% in DMSO and large longitudinal relaxivity(r_(1)) of 11.4(mmol/L)^(-1)/s at 0.5 T in water containing 1 vol% DMSO,respectively.The heterobimetallic Eu-Gd complexes achieve a dual imaging mode by combining luminescent and magnetic centers in one cage.When the Gd:Eu ratio increases from 1:3 to 3:1,the r_(1) values increases from 5.33 to 8.64(mmoI/L)^(-1)/s,higher than that of commercial contrast agent Gd-DOTA(3.23(mmol/L)^(-1)/s).Owing to their low toxicity and good cell imaging ability toward ECA 109 cells,the selfassembled Eu-Gd heterobimetallic tetrahedral cages could be potential candidates for the multimodal imaging contrast agent.
基金financial support by the Summer Graduate School Fellowship from University of Colorado Boulder。
文摘Shape-persistent arylene ethynylene molecular cages have been investigated as transmembrane channels for ions and small molecules.The molecular cages were obtained starting from tetrayne monomers through alkyne metathesis cyclooligomerization.We found these porphyrin-based rigid molecular cages can insert into the lipid bilayer and efficiently transport ions and small molecules(e.g.,calcein).Our study reveals longer hydrophobic alkyl chains on the cage molecule promote the channeling efficiency,while shorter and/or more polar side chains impair such activity.Kinetic analysis shows linear correlation between the rate of proton transport and the concentration of the cage,suggesting the active species is likely a monomeric cage.We found that C_(70)-encapsulated cages are nearly inactive for transmembrane ion transportation,indicating that ions are likely transported through the internal cavity of the cage.Discrete shape-persistent organic cages represent highly stable synthetic ion channels or pores,which could have interesting applications in biomimetic signaling and drug delivery.
基金supported by the NKRD Program of China(No.2021YFA1500401)the National Natural Science Foundation of China(Nos.21821003,21890380)the LIRTP of Guangdong Pearl River Talents Program(No.2017BT01C161)。
文摘The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The vip encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.
基金Supported by Science and Technology Project of Shanxi Province(20140311021-2)Key Research Project of Shanxi Academy of Agricultural Sciences(YGG1609)Special Fund of China Agricultural Industry Research System(CARS-42)
文摘[Objective]The study was to monitor the indoor environmental parameters of broiler house with three-overlap cages and analyze the differences in winter and autumn. [Method] In the process of feeding,the same broiler house in the same farm was chosen to determine indoor ambient temperature,humidity and air quality at 3-6 weeks age of broilers in different seasons. The measure points were distributed in four different positions in the house. [Result] There was no significant difference in ambient temperature between autumn and winter( P > 0. 05). The ambient temperature in the house in winter was slightly higher than that in autumn. The humidity in autumn was significantly higher than that in winter( P < 0. 05). The temperature and humidity in two seasons could meet the requirements of broiler growth. There was no significant difference( P > 0. 05) in ammonia concentration between autumn and winter,while ammonia concentration in winter was slightly higher than that in autumn. The carbon dioxide concentration of broiler house in winter was significantly higher than that in autumn( P < 0. 05).The total number of airborne bacteria in winter was significantly higher than that in autumn( P < 0. 05). [Conclusion]The indoor temperature kept constant in autumn and winter seasons in closed poultry house. In winter,the humidity was reduced,the carbon dioxide concentration was increased,and the total number of bacteria in the air was increased. The ventilation in winter should be increased in case of heat preservation.
基金financially supported by the Ministry of Science and Technology of China(No.2012CB933200)the National Natural Science Foundation of China(Nos.51233007 and 51173191)
文摘pH responsive composite Janus cages of PS-silica-PEO are prepared using silica nanoparticles to crosslink two PAA contained di-block copolymers at an emulsion interface sequentially. Transverse channels are in situ created across the shell, which facilitates mass transfer. Shell is pH responsive owing to the presence of residual PAA chains tethered onto the silica nanoparticles. The Janus cages are capable to preferentially capture oil from their aqueous surroundings. The saturation absorption capacity is determined by pH and oil property. Other composite Janus cages are expected by extension the method using other copolymers and functional nanoparticles.
文摘Density functional theory calculations within the G03W package, with B3LYP exchange functional and applying basis set 6 - 31 G (d,p) are performed. The surface reactivity and electronic properties of endo-hydrogenation and exo-hydrogenation fullerene cages are studied. It is found that the surface reactivity of mono-hydrogenation fullerene cages is larger than the surface reactivity of un-hydrogenation fullerene cages and the later is larger than the fully hydrogenation fullerene cages. In addition, the calculations show that the endo-hydrogenation fullerene cages possess the same band gaps as the un-hydrogenation fullerene cages, however, the exo-hydrogenation is reduced the band gaps of the un-hydrogenated fullerene cages form ~7 eV to ~5 eV.
基金Supported by National Key Technology Research and Development Program of China during the 11th Five-Year Plan Period (No. JPPT-115-189)National Natural Science Foundation of China (No. 50975033)
文摘To investigate the cage stability of high-speed oil-lubricated angular contact ball bearings, a dynamic model of cages is developed on the basis of Gupta’s and Meeks’ work. The model can simulate the cage motion under oil lubrication with all six degrees of freedom. Particularly, the model introduces oil-film damping and hysteresis damping, and deals with the collision contact as imperfect elastic contact. In addition, the effects of inner ring rotational speed, the ratio of pocket clearance to guiding clearance and applied load on the cage stability are investigated by simulating the cage motion with the model. The results can provide a theoretical basis for the design of ball bearing parameters.
基金Supported by the National Natural Science Foundation of China(51706248,51876222)National Key R&D Program of China(2017YFC0307304)
文摘Study on the microscopic structure of clathrate hydrate has made significant progress in the past decades.This review aims to summarize the state of the art of the experimental characterization of vip molecular occupancy in clathrate hydrate cages,which is an important area of the microscopic structures.The characterizing method and features of different vip molecular,such as hydrocarbon,carbon dioxide,hydrogen and inhibitor/promoter,in different hydrate cages have been extensively reviewed.A comprehensive use of advanced technologies such as X-ray diffraction,Raman spectroscopy and nuclear magnetic resonance may provide better understanding on the compositions and microscopic mechanisms of clathrate hydrate.
基金supported by Primary Research&Development Plan of Shandong Province(2016GGF01068)the National Natural Science Foundation of China(Nos.31302193,41676147)+3 种基金Environment and Aquaculture Governance(CHN-2152,13/0033)Public Funds of Key Laboratory of East China Sea&Oceanic Fishery Resources Exploitation and Utilization,Ministry of Agriculture,P.R.China(2013K06)the Special Scientific Research Funds for Central Non-profit Institutes,Yellow Sea Fisheries Research Institutes(20603022015017)National Natural Science Foundation of China 41306117)
文摘The present study investigated the applicability of integrated polychaete-fish culture for fish waste removal to offset negative impact induced by organic benthic enrichment.A field study demonstrated that deposition rate was significantly higher underneath the fish farm than that in control area.The material settling under the farm was characterized by a high amount of fish feces(45%) and uneaten feed(27%).Both feeding rate(FR) and apparent digestibility rate(ADR) increased with decreasing body weight,as was indicated by significantly a higher rate observed for the groups containing smaller individuals in a lab study.The nutrient in fresh deposited material(De) was higher than that in sediments collected under the farm(Se),resulting in lower feces production but higher apparent digestibility rate for the De group as feeding rate was similar.Consequently,higher nutrient removal efficiency was observed in the De group.A mass balance approach indicated that approximately 400–500 individuals m^(-2) is required for removing all waste materials deposited underneath the fish farm,whereas abundance can be lower(about 300–350 individuals m^(-2)) when only the fish waste needs to be removed.The results showed that a significant amount of waste had been accumulated in the fish cages in Sanggou Bay.The integration of fish with P.aibuhitensis seems promising for preventing organic pollution in the sediment and therefore is an effective strategy for mitigating negative effect of fish farms.Thus such integration can become a new IMTA(integrated multi-trophic aquaculture) model in Sanggou Bay.
文摘The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as MOC-Py-M(M=H,Cu,and Zn),are designed for PMDs by combining metalloporphyrin-based ligands with catalytically active Pd^(2+)centers.These metal-organic cages(MOCs)are first successfully hybridized with graphitic carbon nitride(g-C_(3)N_(4))to form direct Z-scheme heterogeneous MOC-Py-M/g-C_(3)N_(4)(M=H,Cu,and Zn)photocatalysts via π-πinteractions.Benefiting from its better light absorption ability,the MOC-Py-Zn/g-C_(3)N_(4) catalyst exhibits high H_(2) production activity under visible light(10348μmol g^(-1) h^(-1)),far superior to MOC-Py-H/g-C_(3)N_(4) and MOC-Py-Cu/g-C_(3)N_(4).Moreover,the MOC-Py-Zn/g-C_(3)N_(4) system obtains an enhanced turn over number(TON)value of 32616 within 100 h,outperforming the homogenous MOC-Py-Zn(TON of 507 within 100 h),which is one of the highest photochemical hybrid systems based on MOC for visible-light-driven hydrogen generation.This confirms the direct Z-scheme heterostructure can promote effective charge transfer,expand the visible light absorption region,and protect the cages from decomposition in MOC-Py-Zn/g-C_(3)N_(4).This work presents a creative example that direct Z-scheme PMD-based systems for effective and persistent hydrogen generation from water under visible light are obtained by heterogenization approach using homogeneous porphyrin-based MOCs and g-C_(3)N_(4) semiconductors.
基金the financial support from Chengdu University of Technology (No. 10912-SJGG2021-06843)
文摘Luminescent metal organic cages(MOCs)have attracted great interest as a unique class of sensing substrates.In this work,intrinsically fluorescent Zr-MOCs were successfully used as fluorescent probes for the sensitive and selective detection of phosphate anions in water and real samples.When the ligand and Zr ion clusters form a cage,the intrinsic fluorescence of the ligand was tuned from high to weak emission due to the ligand-to-metal charge transfer(LMCT)effect,and this weakened fluorescence can be restored by the addition of phosphate.The degree of fluorescence enhancement is positively correlated with the added phosphate concentration,and the efficacy of this strategy is demonstrated by a linear phosphate detection range of 5–500µmol/L and a detection limit of 1.06µmol/L.We discuss the interaction between phosphate and Zr in scattering spectrum and MS,respectively.In comparison to phosphate adsorption on Zr-metal organic frameworks(MOFs),where phosphate connects different numbers of cages,both blocking the LMCT effect and causing the cages to aggregate.We also found that the phosphate displaces the ligand from the cage when the phosphate concentration is further expanded,resulting in the formation of new derivatives.This derivative was shown to be useful as a Lewis acid catalyst and as a rare earth ion adsorbent.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51239002 and 51221961)Cultivation Plan for Youth Agricultural Science and Technology Innovative Talents of Liaoning Province(Grant No.2014008)
文摘The goal of this paper is to provide a comparative analysis of two commonly used approaches to discretize offshore fish cages： the lumped-mass approach and the finite element technique. Two case studies are chosen to compare predictions of the LMA（lumped-mass approach） and FEA（finite element analysis） based numerical modeling techniques. In both case studies, we consider several loading conditions consisting of different uniform currents and monochromatic waves. We investigate motion of the cage, its deformation, and the resultant tension in the mooring lines. Both model predictions are sufficient close to the experimental data, but for the first experiment, the DUT-Flex Sim predictions are slightly more accurate than the ones provided by Aqua-FETM. According to the comparisons, both models can be successfully utilized to the design and analysis of the offshore fish cages provided that an appropriate safety factor is chosen.
基金the National Natural Science Foundation of China(Nos.22101267,21672192,21803059,U2004191,U1904212,21801063)for financial support。
文摘Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.
文摘Background: cervical spondylotic myelopathy is a common health problem that neurosurgeons face in Egypt. The aim of this study is to evaluate the efficacy of PEEK cage only in 4 levels anterior cervical discectomy as one of surgical option other than anterior cervical corpectomy, fixation by plat or posterior approach for cervical laminectomy, and assessment of post spinal surgery pain. Methods: this prospective study on 28 patients with cervical spondylotic myelopathy (CSM) over a period of 3 years (between April 2012 and April 2015) with mean period of follow up 30 months. We have done anterior cervical discectomy with fixation by cage only for all cases with perioperative assessment and scoring clinically and radiologically (Japanese Orthopaedic Association [JOA] scores, Visual Analogue Scale [VAS] scores for assessment of neck and arm pain, perioperative parameters (hospital stay, blood loss, operative time), the European Myelopathy Scoring (EMS) and Odom’s criteria, and the incidence of complication,post spinal surgery pain assessment). Results: clinical outcome was excellent (28.55), good (50%) and fair (21.5) according to Odom criteria. The European Myelopathy Scoring (EMS), improved from 10 to 16. The mean JOA score improved from 10.1 ± 2.1 to 14.2 ± 2.3. Fusion failure had been seen in 4 patients in one level for each secondary to anterior displacement of the cage with no other major complications. Conclusion: 4 levels anterior cervical discectomy with PEEK cage only is an effective, save and less costly with less post operative complication and hospital stay and less post spinal surgery pain.
文摘The synthesis of T_8, T_ 10 and T_ 12 silsesquioxane cages from a range of starting materials: phenyl-cis-tetrol, 1,3-divinyltetraethoxydisiloxane and cyclopentyl T resins by using tetra n-butylammonium fluoride(TBAF) as the catalyst is described in this paper. The reaction yields obtained viathe current route are better compared to those viathe literature routes. Some of the cage compounds have been characterized by X-ray crystallography.
基金National Natural Science Foundation of China(Nos.21971268,22171295)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07C069)+1 种基金Pearl River Talent Program(No.2017GC010623)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)for financial support.
文摘A pair of selenanthrene-bridged molecular cages have been constructed through a one-step cyclization reaction of a tetrakis(iodo) crown ether with selenium powder. The tubular belt-shaped cage has an intrinsic cavity which can adaptively transform to accommodate electron-deficient vips forming [2]pseudorotaxane complexes. The other product was determined to be an isomeric cage featuring a Mobius strip structure, which exhibits slower twist-migration dynamics than its thianthrene counterpart. The success of using selenanthrene as joints enables an alternative way to structural design and property regulation of molecular cages.
