(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Harnessing bacteria for superoxide production in bioremediation holds immense promise,yet its practical application is hindered by slow production rates and the relatively weak redox potential of superoxide.This study...Harnessing bacteria for superoxide production in bioremediation holds immense promise,yet its practical application is hindered by slow production rates and the relatively weak redox potential of superoxide.This study delves into a cost-effective approach to amplify superoxide production using an Arthrobacter strain,a prevalent soil bacterial genus.Our research reveals that introducing a carbon source along with specific iron-binding ligands,including deferoxamine(DFO),diethylenetriamine pentaacetate(DTPA),citrate,and oxalate,robustly augments microbial superoxide generation.Moreover,our findings suggest that these iron-binding ligands play a pivotal role in converting superoxide into hydroxyl radicals by modulating the electron transfer rate between Fe(Ⅲ)/Fe(Ⅱ)and superoxide.Remarkably,among the tested ligands,only DTPA emerges as a potent promoter of this conversion process when complexed with Fe(Ⅲ).We identify an optimal Fe(Ⅲ)to DTPA ratio of approximately 1:1 for enhancing hydroxyl radical production within the Arthrobacter culture.This research underscores the efficacy of simultaneously introducing carbon sources and DTPA in facilitating superoxide production and its subsequent conversion to hydroxyl radicals,significantly elevating bioremediation performance.Furthermore,our study reveals that DTPA augments superoxide production in cultures of diverse soils,with various soil microorganisms beyond Arthrobacter identified as contributors to superoxide generation.This emphasizes the universal applicability of DTPA across multiple bacterial genera.In conclusion,our study introduces a promising methodology for enhancing microbial superoxide production and its conversion into hydroxyl radicals.These findings hold substantial implications for the deployment of microbial reactive oxygen species in bioremediation,offering innovative solutions for addressing environmental contamination challenges.展开更多
Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-d...Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as vip molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.展开更多
The naturally fermented Inner Mongolian cheese’s flavor and nutritional value make it a popular choice among customers.In this work,to create multi-functional peptides that have taste and biological activity,peptidom...The naturally fermented Inner Mongolian cheese’s flavor and nutritional value make it a popular choice among customers.In this work,to create multi-functional peptides that have taste and biological activity,peptidomics and bioinformatics were used to screen flavor peptides from Inner Mongolian cheese and further assess their antioxidant and angiotensin I-converting enzyme(ACE)inhibitory properties.According to sensory data,YH8 and IL7 had detectable bitter tastes with low thresholds of 0.03 and 0.06 mmol/L,respectively.With an umami threshold range of 0.24‒0.81 mmol/L,VQ6,FK13,HP13 and QT14 exhibited a range of flavors dominated by umami,including sweet,bitter,salty,sour and kokumi.Antioxidant activity wise,YH8,VQ6,HP13 and QT14 were well represented.The above-mentioned peptides all had some ACE inhibitory effect.The bitter peptide IL7(IC_(50)=0.08 mmol/L)had the highest level of ACE inhibitory activity,followed by YH8(IC_(50)=0.33 mmol/L).These multi-functional peptides,which have been assessed for bioactive and taste features in Inner Mongolian cheese,may have positive impacts on health and harmonize the cheese’s overall flavor.These results suggest that some flavor peptides produced in fermented foods might be with bioactivities while providing a basis for the exploration and application of multi-functional peptides.展开更多
Figure 6(a)in the paper[Chin.Phys.B 33074203(2024)]was incorrect due to editorial oversight.The correct figure is provided.This modification does not affect the result presented in the paper.
Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a...Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.展开更多
Perovskite solar cells(PSCs)are promising in the field of photovoltaics but are hindered by surface defects and stability.However,the energetic losses occurring at the interfaces between the perovskite and the charge ...Perovskite solar cells(PSCs)are promising in the field of photovoltaics but are hindered by surface defects and stability.However,the energetic losses occurring at the interfaces between the perovskite and the charge transport layers often lead to reduced power conversion efficiency(PCE).Surface treatment is an effective strategy but the passivating ligands usually bind with a single active site.The resulted dense packing of resistive passivators perpendicular to the surface is detrimental to charge transport.Here,we present a passivator that can bind to two neighboring lead(Ⅱ)ion(Pb^(2+))defect sites simultaneously with an aligned parallel mode to the perovskite surface,effectively suppressing the surface trap density and preventing the aggregation.The target device fulfills a PCE of 25.1%and maintains over 85% of the initial efficiency after 800 h of exposure to a relative humidity(RH)of 65%±5%.展开更多
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination ...Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.展开更多
The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model clust...The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model cluster has been extensively investigated in various fields,including structural modulation,catalysis,and self-assembly under laboratory conditions,with the aim of gaining an in-depth understanding of their roles in biological functions.Herein,we revisited three well-known[Fe_(4)S_(4)(SR)_(4)]^(2–)molecules,namely[Me_(4)N]_(2)[Fe_(4)S_(4)(SR)_(4)](R=o-MBT,m-MBT,p-MBT),and successfully established their single crystal structures that remain unknown prior to this work.Interestingly,it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the[4Fe–4S]core,which further influences their overall packing patterns in single crystals.In addition,this work unveils two new structure transformation behaviors for the[Fe_(4)S_(4)(SR)_(4)]^(2–)system:i)the monomeric[Fe(SR)_(4)]^(2–)and tetrameric[Fe_(4)S_(4)(SR)_(4)]^(2–)can be interconverted,and ii)[Fe_(4)S_(4)(SR)_(4)]^(2–)can be transferred into an intriguing iron-oxide complex Na_(2)Fe_(6)O(OMe)_(18)·6MeOH in a well-controlled oxidizing environment.展开更多
Lead-halide perovskite nanocrystals(PNCs)exhibit exceptional optical properties with size-and dimensiontunable optical bandgaps,making them promising for diverse optoelectronic applications.The dimensionality of PNCs ...Lead-halide perovskite nanocrystals(PNCs)exhibit exceptional optical properties with size-and dimensiontunable optical bandgaps,making them promising for diverse optoelectronic applications.The dimensionality of PNCs has been controlled by tuning the oleic acid(OA)/oleylamine(OLA)feed ratio in conventional injection-based synthesis.Although the emerging bimolecular nucleophilic substitution(S_(N)2)-based heatup synthesis enables the production of high-quality and monodisperse PNCs,achieving dimensional tunability by altering the OA/OLA feed ratio remains challenging in this approach.Herein,we present an integrated strategy for controlling the dimensionality and surface properties of CsPbI_(3)-PNCs based on the S_(N)2-based heat-up method.Our approach focuses on the regulation of OLA protonation and oleylammonium(OAM^(+))latticeforming behavior.Using chemical analysis,we identify the protonation routes of OLA in S_(N)2 reactions and demonstrate that adjusting the acid–base and S_(N)2 reactions involving OA and OLA can reduce OLA protonation and the subsequent formation of OAM^(+).Furthermore,by enhancing the competitive lattice-forming behavior of Cs^(+)over OAM+,we suppress excessive surface termination by OAM^(+).These approaches achieve dimensional tunability between two-dimensional(2D)nanoplatelets and three-dimensional(3D)nanocubes in the S_(N)2-based heat-up synthesis,along with subsequent spectral control of optical features.To independently optimize their surface passivation,we employ a post-synthetic passivation(PSP)strategy using OAM^(+)–I−pairs,which increases the photoluminescence quantum yield of PNCs from 71.9%to 81.7%by reducing surface defects.展开更多
An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthrolin...An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.展开更多
Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly acti...Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly active ORR electrocatalysts with superior kinetics hinders progress in this field.Herein,we report the Fe/Ni dual single-atomic sites anchored by commercial carbon black(Fe/Ni-N/CB)using rigid ligand confined and high-temperature shock(HTS)strategy in less than 0.5 s.Theoretical calculation reveals that singleatomic Fe is the real active site.Single-atomic Fe and Ni species in Fe/Ni-N/CB synergistically accelerate the kinetics of ORR by reducing the energy barrier of the rate-determining step.A large half-wave potential(E_(1/2))of 0.907 V is achieved in 0.1 M KOH aqueous solution.The assembled aqueous Zn-air battery(A-ZAB)with Fe/Ni-N/CB cathode presents remarkable charge-discharge cycling stability for over 650 h without voltage gap degradation.The quasi-solid-state Zn-air battery(QSS-ZAB)exhibits excellent reversibility over a 150-h operation at 0.5 mA·cm^(-2) with negligible energy conversion efficiency recession.Impressively,Fe/Ni-N/CB||RuO_(2)chloralkali flow cell exhibits a low cell voltage of 1.60 V at a large current density of 300 mA·cm^(-2) at 80℃,and demonstrates exceptional durability with 7% current density decay over 150 h of continuous operation at 100 mA·cm^(-2).Fe/Ni-N/CB||RuO_(2)achieves near-ideal caustic current efficiency(~97.2%)at the current density of 300 mA·cm^(-2).This work provides a rapid and economical synthesis technique for the synthesis of catalysts at the atomic scale while demonstrating significant potential for application in energy-saving chlor-alkali electrolyzer.展开更多
We introduced bipyridine ligands into a series of two‐dimensional （2D） covalent organic frame‐works （COFs） using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde （2,2’‐BPyDCA） as a component in the mixed building bl...We introduced bipyridine ligands into a series of two‐dimensional （2D） covalent organic frame‐works （COFs） using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde （2,2’‐BPyDCA） as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium（II） acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd（II） ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd（II）‐loaded COFs exhibited good catalytic activity for the Heck reaction.展开更多
Multi-functional Al-matrix composites with high volume fraction （55%-57%） of SiC particles are produced with the new pressureless infiltration fabrication technology. X-ray detection and microscopic observation disp...Multi-functional Al-matrix composites with high volume fraction （55%-57%） of SiC particles are produced with the new pressureless infiltration fabrication technology. X-ray detection and microscopic observation display the composites which are macroscopically homogeneous without porosity. The investigation further reveals that the SiC/Al composites possess low density （2.94 g/cm^3）, high elastic modulus （220 GPa）, prominent thermal management function as a result of low coefficient of thermal expansion （8 × 10^4 K^-1） and high thermal conductivity （235 W/（m.K）） as well as unique preventability of resonance vibration. By adopting a series of developed techniques, the multi-functional SiC/Al composites have managed to be made into near-net-shape parts. Many kinds of precision components of space-based optomechanical structures and airborne optoelectronic platform have been turned out. Of them, several typical products are being under test in practices.展开更多
A series of glucose-cholesterol derivatives 8a-8e as ligands for brain targeting liposomes were synthesized. The preparation of compound 6 involved temporary protection of glucose with chlorotrimethylsilicane and hexa...A series of glucose-cholesterol derivatives 8a-8e as ligands for brain targeting liposomes were synthesized. The preparation of compound 6 involved temporary protection of glucose with chlorotrimethylsilicane and hexamethyldisilazane followed by selectively hydrolyzed. The known cholesteryl tosylate 1 were coupled to ethylene glycols to afford alcohol 2a-2e. Substitution and deprotection of alcohol 2a-2e furnished the acids 4a-4e, which was condensed with compound 6 to get compounds 7a-7e, and then was deprotected in tetrahydrofuran with TFA to obtain the title compounds. As a model drug, tegafur was entrapped by liposomes coupled with 8b, and preliminary in vivo evaluation shown 8b could enhance the ability of liposomes delivering tegafur across the blood brain barrier.展开更多
Three new lanthanide-organic compounds, namely, [Ln_2(OH)_2(oba)(2-pc)_2]n(Ln =Er(1), Ho(2), and Dy(3))(oba = 4,4?-oxybis(benzoate), 2-pc = 2-pyrazinecarboxylic acid) have been obtained under hydrothermal conditions. ...Three new lanthanide-organic compounds, namely, [Ln_2(OH)_2(oba)(2-pc)_2]n(Ln =Er(1), Ho(2), and Dy(3))(oba = 4,4?-oxybis(benzoate), 2-pc = 2-pyrazinecarboxylic acid) have been obtained under hydrothermal conditions. These compounds are isostructural and exhibit 2 D layered structures by incorporating [Ln_4(μ_3-OH)_4]^(8+) clusters and the mixed linkers of oba and 2-pc. It is interesting that decarboxylation occurred in the ortho position and 2,3-pyrazinedicarboxylic acid was partially transformed into 2-pc under hydrothermal conditions. Compound 3 emits a typical Dy^(3+) emission spectrum. Furthermore, the PXRD, TGA and IR spectra were also studied.展开更多
Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures ...Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.展开更多
The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of ...The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ) , respectively , the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ) , and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.展开更多
Citrate, oxalate, tartrate and malate were added into soils during the growthperiod of ryegrass to study the effect of different organic ligands on the release of variousinorganic P (Pi) fractions in a yellow-brown so...Citrate, oxalate, tartrate and malate were added into soils during the growthperiod of ryegrass to study the effect of different organic ligands on the release of variousinorganic P (Pi) fractions in a yellow-brown soil and a paddy soil. The results showed that oxalatewas most effective in promoting the release of total Pi in the yellow-brown soil and tartrate in thepaddy soil. The dominant Pi fractions released from the yellow-brown soil were calcium phosphate(Ca-P) and aluminum phosphate (Al-P) and those from the paddy soil were iron phosphate (Fe-P) andreductant soluble phosphate (O-P) mobilized by tartrate. Phosphorous-mobilizing capability oforganic acids in the yellow-brown soil revealed the following order: oxalate > citrate > malate >tartrate. In the paddy soil, the order was tartrate > citrate ≈ oxalate > malate. It wasdemonstrated that organic ligands were different in their capabilities of mobilizing Pi and the sameorganic ligand showed also a discrepancy in mobilizing P in different soils. Although the additionof organic ligands into soils could increase the amount of P taken up by ryegrass, the more uptakeof P, however, was not only due to the more release of Pi, but also partly from organic P. In manycases, organic ligands promoted the release of the total Pi, while different fractions showeddifferent trends: some increased and others decreased.展开更多
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
基金supported by the National Natural Science Foundation of China(Nos.52170156,52250056,and 52293443)the Shenzhen Science and Technology Program(No.KQTD20190929172630447).
文摘Harnessing bacteria for superoxide production in bioremediation holds immense promise,yet its practical application is hindered by slow production rates and the relatively weak redox potential of superoxide.This study delves into a cost-effective approach to amplify superoxide production using an Arthrobacter strain,a prevalent soil bacterial genus.Our research reveals that introducing a carbon source along with specific iron-binding ligands,including deferoxamine(DFO),diethylenetriamine pentaacetate(DTPA),citrate,and oxalate,robustly augments microbial superoxide generation.Moreover,our findings suggest that these iron-binding ligands play a pivotal role in converting superoxide into hydroxyl radicals by modulating the electron transfer rate between Fe(Ⅲ)/Fe(Ⅱ)and superoxide.Remarkably,among the tested ligands,only DTPA emerges as a potent promoter of this conversion process when complexed with Fe(Ⅲ).We identify an optimal Fe(Ⅲ)to DTPA ratio of approximately 1:1 for enhancing hydroxyl radical production within the Arthrobacter culture.This research underscores the efficacy of simultaneously introducing carbon sources and DTPA in facilitating superoxide production and its subsequent conversion to hydroxyl radicals,significantly elevating bioremediation performance.Furthermore,our study reveals that DTPA augments superoxide production in cultures of diverse soils,with various soil microorganisms beyond Arthrobacter identified as contributors to superoxide generation.This emphasizes the universal applicability of DTPA across multiple bacterial genera.In conclusion,our study introduces a promising methodology for enhancing microbial superoxide production and its conversion into hydroxyl radicals.These findings hold substantial implications for the deployment of microbial reactive oxygen species in bioremediation,offering innovative solutions for addressing environmental contamination challenges.
文摘Five cadmium naphthalene-diphosphonates,formulated as[Cd_(1.5)(1,4-ndpaH_(2))2(4,4'-bpyH)(4,4'-bpy)0.5(H_(2)O)_(2)]2(1),[Cd(1,4-ndpaH_(2))(1,4-bib)0.5(H_(2)O)](2),[Cd(1,4-ndpaH3)2(1,2-dpe)(H_(2)O)]·(1,2-dpe)·7H_(2)O(3),(1,2-bixH)[Cd3(1,4-ndpaH)(1,4-ndpaH_(2))2(H_(2)O)_(2)](4),and[Cd(1,4-ndpaH_(2))(H_(2)O)]·H_(2)O(5),have been synthesized from the selfassembly reactions of 1,4-naphthalenediphosphonic acid(1,4-ndpaH4)with Cd(NO3)2·4H_(2)O by introducing auxiliary ligands with variation of rigidity,such as 4,4'-bipyridine(4,4'-bpy),1,4-bis(1-imidazolyl)benzene(1,4-bib),1,2-di(4-pyridyl)ethylene(1,2-dpe),1,3-di(4-pyridyl)propane(1,3-dpp),and bis(imidazol-1-ylmethyl)benzene(1,2-bix),respectively.Structure resolution by single-crystal X-ray diffraction reveals that compound 1 possesses a layered framework,in which the{Cd3(PO2)2}trimers made up of corner-sharing two{CdO4N2}and one{CdO6}octahedra are connected by phosphonate groups,forming a ribbon,which are cross-linked by 4,4'-bipy ligands,forming a 2D layer.Compound 2 shows a 3D open-framework structure,where chains of corner-sharing{CdO4N}trigonal bipyramids and{PO3C}tetrahedra are cross-linked by 1,4-bib and/or phosphonate groups.A 1D ladder-like chain structure is found in compound 3,where the ladder-like chains made up of corner-sharing{CdO5N}octahedra and{PO3C}tetra hedra are connected by 1,4-ndpaH_(2)^(2-).Both compounds 4 and 5 obtained by the introduction of flexible ligands during the synthesis show a 2D layered structure,which is formed by ligand crosslinking double metal chains.Interestingly,In 4,flexible 1,2-bix was singly protonated,as vip molecules,filled between layer and layer,while flexible ligand 1,3-dpp is absent in 5.Photophysical measurements indicate that compounds 1-5 show ligand-centered emissions.
基金supported by the central government and guides local funds for science and technology development(2022ZY0109).
文摘The naturally fermented Inner Mongolian cheese’s flavor and nutritional value make it a popular choice among customers.In this work,to create multi-functional peptides that have taste and biological activity,peptidomics and bioinformatics were used to screen flavor peptides from Inner Mongolian cheese and further assess their antioxidant and angiotensin I-converting enzyme(ACE)inhibitory properties.According to sensory data,YH8 and IL7 had detectable bitter tastes with low thresholds of 0.03 and 0.06 mmol/L,respectively.With an umami threshold range of 0.24‒0.81 mmol/L,VQ6,FK13,HP13 and QT14 exhibited a range of flavors dominated by umami,including sweet,bitter,salty,sour and kokumi.Antioxidant activity wise,YH8,VQ6,HP13 and QT14 were well represented.The above-mentioned peptides all had some ACE inhibitory effect.The bitter peptide IL7(IC_(50)=0.08 mmol/L)had the highest level of ACE inhibitory activity,followed by YH8(IC_(50)=0.33 mmol/L).These multi-functional peptides,which have been assessed for bioactive and taste features in Inner Mongolian cheese,may have positive impacts on health and harmonize the cheese’s overall flavor.These results suggest that some flavor peptides produced in fermented foods might be with bioactivities while providing a basis for the exploration and application of multi-functional peptides.
文摘Figure 6(a)in the paper[Chin.Phys.B 33074203(2024)]was incorrect due to editorial oversight.The correct figure is provided.This modification does not affect the result presented in the paper.
基金supported by the National Natural Science Foundation of China(Nos.52300120 and 52070144)the Fundamental Research Funds for the Central Universities(No.22120240465).
文摘Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.
基金supported by the National Key R&D Program of China(2022YFB4200500)the Key Research and Development Plan Project of Anhui Province(2022h11020014)+3 种基金Collaborative Innovation Program of Hefei Science Center,CAS(2022HSCCIP006)the CASHIPS Director’s Fund(YZJJ201902 and YZJJZX202018)the Anhui Provincial Natural Science Foundation(2408085MB029)the Natural Science Foundation of Hebei Province of China(B2024402018)。
文摘Perovskite solar cells(PSCs)are promising in the field of photovoltaics but are hindered by surface defects and stability.However,the energetic losses occurring at the interfaces between the perovskite and the charge transport layers often lead to reduced power conversion efficiency(PCE).Surface treatment is an effective strategy but the passivating ligands usually bind with a single active site.The resulted dense packing of resistive passivators perpendicular to the surface is detrimental to charge transport.Here,we present a passivator that can bind to two neighboring lead(Ⅱ)ion(Pb^(2+))defect sites simultaneously with an aligned parallel mode to the perovskite surface,effectively suppressing the surface trap density and preventing the aggregation.The target device fulfills a PCE of 25.1%and maintains over 85% of the initial efficiency after 800 h of exposure to a relative humidity(RH)of 65%±5%.
基金the National Key R&D Program of China(2023YFA1507601)the National Natural Science Foundation of China(22522108,52373213,22301176).
文摘Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medi-cine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
基金supported by the Fundamental Research Funds for the Central Universities(22120240204 and 22120240039)the National Natural Science Foundation of China(22301219,Z.Z.,22101205,H.H.)。
文摘The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model cluster has been extensively investigated in various fields,including structural modulation,catalysis,and self-assembly under laboratory conditions,with the aim of gaining an in-depth understanding of their roles in biological functions.Herein,we revisited three well-known[Fe_(4)S_(4)(SR)_(4)]^(2–)molecules,namely[Me_(4)N]_(2)[Fe_(4)S_(4)(SR)_(4)](R=o-MBT,m-MBT,p-MBT),and successfully established their single crystal structures that remain unknown prior to this work.Interestingly,it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the[4Fe–4S]core,which further influences their overall packing patterns in single crystals.In addition,this work unveils two new structure transformation behaviors for the[Fe_(4)S_(4)(SR)_(4)]^(2–)system:i)the monomeric[Fe(SR)_(4)]^(2–)and tetrameric[Fe_(4)S_(4)(SR)_(4)]^(2–)can be interconverted,and ii)[Fe_(4)S_(4)(SR)_(4)]^(2–)can be transferred into an intriguing iron-oxide complex Na_(2)Fe_(6)O(OMe)_(18)·6MeOH in a well-controlled oxidizing environment.
基金supported by the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(Nos.RS-2023-00207907 and RS-2024-00444458).
文摘Lead-halide perovskite nanocrystals(PNCs)exhibit exceptional optical properties with size-and dimensiontunable optical bandgaps,making them promising for diverse optoelectronic applications.The dimensionality of PNCs has been controlled by tuning the oleic acid(OA)/oleylamine(OLA)feed ratio in conventional injection-based synthesis.Although the emerging bimolecular nucleophilic substitution(S_(N)2)-based heatup synthesis enables the production of high-quality and monodisperse PNCs,achieving dimensional tunability by altering the OA/OLA feed ratio remains challenging in this approach.Herein,we present an integrated strategy for controlling the dimensionality and surface properties of CsPbI_(3)-PNCs based on the S_(N)2-based heat-up method.Our approach focuses on the regulation of OLA protonation and oleylammonium(OAM^(+))latticeforming behavior.Using chemical analysis,we identify the protonation routes of OLA in S_(N)2 reactions and demonstrate that adjusting the acid–base and S_(N)2 reactions involving OA and OLA can reduce OLA protonation and the subsequent formation of OAM^(+).Furthermore,by enhancing the competitive lattice-forming behavior of Cs^(+)over OAM+,we suppress excessive surface termination by OAM^(+).These approaches achieve dimensional tunability between two-dimensional(2D)nanoplatelets and three-dimensional(3D)nanocubes in the S_(N)2-based heat-up synthesis,along with subsequent spectral control of optical features.To independently optimize their surface passivation,we employ a post-synthetic passivation(PSP)strategy using OAM^(+)–I−pairs,which increases the photoluminescence quantum yield of PNCs from 71.9%to 81.7%by reducing surface defects.
文摘An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol(FA)to aryl furans(AFs),a versatile monomer of photoelectric materials,in the presence of UiO-67-Pd(F)with phenanthroline/bipyridine,and poly-F substituted phenyl ligands as the mixture linkers.The results of control experiments and theoretical calculations reveal that the–F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr_(6) clusters bridges,which favors the adsorption and activation of the furan ring.Furthermore,the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation,respectively.As a result,the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects.Under the optimized conditions,72.2%FA conversion and 74.8%mono aryl furan(MAF)selectivity are shown in the Heck-type insertion.Meanwhile,85.3%of MAF is converted,affording 74.8%selectivity of final product(AFs)in the subsequent electrophilic palladation reaction.This process efficiency is remarkably higher than that with homogeneous catalysts.In addition,furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F)show significantly better properties than that from conventional Suzuki coupling method.Therefore,the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金supported financially by the National Natural Science Foundation of China(No.52172208)Taishan Scholar Young Talent Program(No.tsqn202306216)Shandong Excellent Young Scientists Fund Program(Overseas,2023HWYQ‑091).
文摘Oxygen reduction reaction(ORR)is crucial for Znair batteries,while also serves as a core electrochemical process in oxygen depolarized cathodes(ODCs)for chlor-alkali electrolysis.The lack of cost-effective,highly active ORR electrocatalysts with superior kinetics hinders progress in this field.Herein,we report the Fe/Ni dual single-atomic sites anchored by commercial carbon black(Fe/Ni-N/CB)using rigid ligand confined and high-temperature shock(HTS)strategy in less than 0.5 s.Theoretical calculation reveals that singleatomic Fe is the real active site.Single-atomic Fe and Ni species in Fe/Ni-N/CB synergistically accelerate the kinetics of ORR by reducing the energy barrier of the rate-determining step.A large half-wave potential(E_(1/2))of 0.907 V is achieved in 0.1 M KOH aqueous solution.The assembled aqueous Zn-air battery(A-ZAB)with Fe/Ni-N/CB cathode presents remarkable charge-discharge cycling stability for over 650 h without voltage gap degradation.The quasi-solid-state Zn-air battery(QSS-ZAB)exhibits excellent reversibility over a 150-h operation at 0.5 mA·cm^(-2) with negligible energy conversion efficiency recession.Impressively,Fe/Ni-N/CB||RuO_(2)chloralkali flow cell exhibits a low cell voltage of 1.60 V at a large current density of 300 mA·cm^(-2) at 80℃,and demonstrates exceptional durability with 7% current density decay over 150 h of continuous operation at 100 mA·cm^(-2).Fe/Ni-N/CB||RuO_(2)achieves near-ideal caustic current efficiency(~97.2%)at the current density of 300 mA·cm^(-2).This work provides a rapid and economical synthesis technique for the synthesis of catalysts at the atomic scale while demonstrating significant potential for application in energy-saving chlor-alkali electrolyzer.
基金supported by the National Natural Science Foundation of China(21473196,21403214)the 100‐Talents Program of Chinese Academy of SciencesState Key Laboratory of Fine Chemicals,Dalian University of Technology(KF1415)~~
文摘We introduced bipyridine ligands into a series of two‐dimensional （2D） covalent organic frame‐works （COFs） using 2,2’‐bipyridine‐5,5’‐dicarbaldehyde （2,2’‐BPyDCA） as a component in the mixed building blocks. The framework of the COFs was formed by the linkage of imine groups. The ligand content in the COFs was synthetically tuned by the content of 2,2’‐BPyDCA, and thus the amount of metal, palladium（II） acetate, bonded to the nitrogen ligands could be manipulated. Both the bipyri‐dine ligands and imine groups can coordinate with Pd（II） ions, but the loading position can be var‐ied, with one ligand favoring binding in the space between adjacent COFs’ layers and the other lig‐and favoring binding within the pores of the COFs. The Pd（II）‐loaded COFs exhibited good catalytic activity for the Heck reaction.
基金Foundation items： High-technology Research and Development Programme of China （2007AA03Z544） Aeronautical Science Foundation of China （20075221001）
文摘Multi-functional Al-matrix composites with high volume fraction （55%-57%） of SiC particles are produced with the new pressureless infiltration fabrication technology. X-ray detection and microscopic observation display the composites which are macroscopically homogeneous without porosity. The investigation further reveals that the SiC/Al composites possess low density （2.94 g/cm^3）, high elastic modulus （220 GPa）, prominent thermal management function as a result of low coefficient of thermal expansion （8 × 10^4 K^-1） and high thermal conductivity （235 W/（m.K）） as well as unique preventability of resonance vibration. By adopting a series of developed techniques, the multi-functional SiC/Al composites have managed to be made into near-net-shape parts. Many kinds of precision components of space-based optomechanical structures and airborne optoelectronic platform have been turned out. Of them, several typical products are being under test in practices.
基金supported by the National Natural Science Foundation of China(No.81072532)
文摘A series of glucose-cholesterol derivatives 8a-8e as ligands for brain targeting liposomes were synthesized. The preparation of compound 6 involved temporary protection of glucose with chlorotrimethylsilicane and hexamethyldisilazane followed by selectively hydrolyzed. The known cholesteryl tosylate 1 were coupled to ethylene glycols to afford alcohol 2a-2e. Substitution and deprotection of alcohol 2a-2e furnished the acids 4a-4e, which was condensed with compound 6 to get compounds 7a-7e, and then was deprotected in tetrahydrofuran with TFA to obtain the title compounds. As a model drug, tegafur was entrapped by liposomes coupled with 8b, and preliminary in vivo evaluation shown 8b could enhance the ability of liposomes delivering tegafur across the blood brain barrier.
文摘Three new lanthanide-organic compounds, namely, [Ln_2(OH)_2(oba)(2-pc)_2]n(Ln =Er(1), Ho(2), and Dy(3))(oba = 4,4?-oxybis(benzoate), 2-pc = 2-pyrazinecarboxylic acid) have been obtained under hydrothermal conditions. These compounds are isostructural and exhibit 2 D layered structures by incorporating [Ln_4(μ_3-OH)_4]^(8+) clusters and the mixed linkers of oba and 2-pc. It is interesting that decarboxylation occurred in the ortho position and 2,3-pyrazinedicarboxylic acid was partially transformed into 2-pc under hydrothermal conditions. Compound 3 emits a typical Dy^(3+) emission spectrum. Furthermore, the PXRD, TGA and IR spectra were also studied.
基金the National Natural Science Foundation of China(Nos20423002 and 20703034)Natural Science Foundation of Fujian Province of China(No2008J0235) for the financial support of this work
文摘Novel chiral PN_4-type multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and various chiral amino-sulfonamides.Their structures were fully characterized by IR,EI-MS and NMR.The catalytic systems,prepared in situ from the multidentate ligands and iridium（I） complexes,showed high activity in asymmetric transfer hydrogenation of propiophenone in 2-propanol solution,leading to corresponding optical alcohol with up to 75%ee.
文摘The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ) , respectively , the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ) , and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.
基金Project supported by the National Key Basic Research Support Foundation (NKBRSF) of China (No.G1999011806).
文摘Citrate, oxalate, tartrate and malate were added into soils during the growthperiod of ryegrass to study the effect of different organic ligands on the release of variousinorganic P (Pi) fractions in a yellow-brown soil and a paddy soil. The results showed that oxalatewas most effective in promoting the release of total Pi in the yellow-brown soil and tartrate in thepaddy soil. The dominant Pi fractions released from the yellow-brown soil were calcium phosphate(Ca-P) and aluminum phosphate (Al-P) and those from the paddy soil were iron phosphate (Fe-P) andreductant soluble phosphate (O-P) mobilized by tartrate. Phosphorous-mobilizing capability oforganic acids in the yellow-brown soil revealed the following order: oxalate > citrate > malate >tartrate. In the paddy soil, the order was tartrate > citrate ≈ oxalate > malate. It wasdemonstrated that organic ligands were different in their capabilities of mobilizing Pi and the sameorganic ligand showed also a discrepancy in mobilizing P in different soils. Although the additionof organic ligands into soils could increase the amount of P taken up by ryegrass, the more uptakeof P, however, was not only due to the more release of Pi, but also partly from organic P. In manycases, organic ligands promoted the release of the total Pi, while different fractions showeddifferent trends: some increased and others decreased.
