Ultralow-Energy-Barrier H_(2)O_(2)Dissociation on Coordinatively Unsaturated Metal Centers in Binary Ce-Fe Prussian Blue Analogue for Efficient and Stable Photo-Fenton Catalysis

The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.

Syntheses,Crystal Structures and Thermal Stabilities of Two New Mixed Ligated Coordination Polymers with Rigid Dicarboxylate and Flexile N-donor Ligands

Two new coordination polymers,[Co（BIPA）（bpp）]（1） and [Zn（BIPA）（bpp）（H2O）]（2）（H2BIPA = 5-bromoisophthalic acid,bpp = 1,3-di（4-pyridyl）propane） have been synthesized via hydrothermal reactions.The two compounds were characterized by elemental analysis,IR spectra,TG analysis and single-crystal X-ray determination.Compound 1 crystallizes in triclinic,space group P1 with a = 9.0316（13）,b = 10.1179（14）,c = 11.8884（17） ,α = 68.022（2）,β = 84.749（2）,γ = 77.791（2）°,V = 984.5（2） 3,Z = 2,C21H17BrN2O4Co,Mr = 500.21,Dc = 1.687 g.cm-3,μ = 2.932 mm-1,S = 0.981,F（000） = 502,R = 0.0440 and wR = 0.1357 for 3773 observed reflections with I 2σ（I）.Compound 2 crystallizes in the monoclinic system,space group P21/c with a = 7.8466（10）,b = 27.483（4）,c = 9.6583（13） ,β = 96.663（3）°,V = 2068.8（5） 3,Z = 4,C21H19BrN2O5Zn,Mr = 524.66,Dc = 1.685 g.cm-3,μ = 3.155 mm-1,S = 0.969,F（000） = 1056,R = 0.0441 and wR = 0.0517 for 4058 observed reflections with I 2σ（I）.The two compounds are constructed from the BIPA2-and bpp ligands but they exhibit different kinds of one-dimensional chain structures.In 1,the chains are composed of the Co（Ⅱ） ions and BIPA2-ligands,and the chains are further extended into a 2D framework structure by π...π interactions of the benzene rings from the BIPA2-ligands between the adjacent chains.In 2,the chains are made up of Zn（Ⅱ） ions and BIPA2-ligands through another fashion,and the chains are further linked via hydrogen bonding interactions to yield a two-dimensional supramolecular layer structure.Furthermore,the bpp ligand features two kinds of different coordination modes in the two compounds.

9-Anthracenecarboxaldehyde Functionalized Second Generation Poly(amidoamine) Dendrimers: Synthesis and Metal Absorption

In this paper we report the peripheral functionalization of amine-terminated second generation poly（amidoamine） （PAMAM） with 9-anthracenecarboxalehyde and the preparation of dendrimer-encapsulated metal salts. The interesting different behaviors of these hybrid materials were observed by fluorescence and UV-Vis spectra.

SYNTHESIS AND PROPERTIES OF METAL COMPLEXES OF β-DIKETONE BASED SIDE CHAIN LIQUID CRYSTAL POLYSILOXANE

A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions with DKLCP greatly increases the phase transition temperature T_k from crystalline state to liquid crystalline state and T_(cl) from LC to isotropic state and makes the range of phase transition ΔT (ΔT=T_(cl)-T_k) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.

AROMATIC BOND INCLUDING METALLIC ATOM IN COORDINATE COMPOUNDS AND SOME OF ITS PROPERTIES

Aromatic bond including metallic atom (Ni) is investigated by EHMO calculation.The NMR spectra and the mechanism for hydrolysis are discussed on the ground of results of computation.

功能晶体材料CMTD生长动力学和结晶习性的研究

Process of crystal growth can be controlled by both surface kinetics and by volume transport as well.Although the complicated relation between the surface kinetics and volume transport exsits,generally,they are studied seprately.Due to the mathematical complexity of heat and mass transport equations,the in depth studies of heat and mass transport process become difficult.Most of the studies on the transport were performed for the growth from melt.Most of the work on Surface kinetics has been done for crystal growth from aqueous solution because the in situ observation of crystal growth is easily carried out.In recent years,the surface kinetics studies on the nanometer scale,even atomic scale,are demonstrated by using AFM.

Assembly of a highly stable luminescent Zn5 cluster and application to bio-imaging

OBJECTIVE To explore a novel pH-sensitive fluorescent probe for in vivo tumor imaging.METHODS Zn5 were obtained in 140℃ after mixed with Me OH,water,Zn(NO_3)2·6 H_2O,H4L and trimethylamine.The fluorescence spectra of Zn5 with the same concentration in different pH aqueous solutions were detected.And the stability of Zn5 was investigated by time dependent fluorescence emission spectra of Zn5 in BSA aqueous solution and 5.0% serum solution.Then,the cytotoxicity of Zn5 was detected by MTT assays.To clarify whether a similar fluorescence response occurs in biological organisms,He La cells were pretreated with probe Zn5(0.5 μmol·L^(-1)) and fluorescence imaging were collected for targeting lysosomes in living cells because of lysosomes′ acidic microenvironment.The A375 tumor-bearing mice were used to assess the imaging ability of Zn5 in vivo.Mouse tumor xenografts were established by injection of A375 cells with 2×10~6 cells per flank.Probe(1 μg·g^(-1)) was administered to mice by injection.Images were obtained using IVIS Spectrum CT Imaging System.RESULTS There is a 11-fold intensity increasing as the pH values changing from 8 to 2.The almost unchanged emission intensities suggest Zn5 is stable in both BSA and serum.Zn5 has negligible cytotoxicity for He La,293 T and CHO-K1 cells.Zn5 can selectively display lysosomes in living cells.Both the 2D and 3D images in vivo distinguish the tumor from other tissues with good fluorescence contrast.CONCLUSION The high chemical stability,emission in the Vis/NIR range,pH sensitivity,a pKa located in the tumor pH range,and low toxicity make Zn5 is suitable for application as a pH-sensitive fluorescent probe for bio-imaging.

Synthesis and Crystal Structure of Poly{diaqua[N-(2-hydroxybenzyl)- D,L- aspartate]cadmium(II)}

The title compound, [Cd(C11H11NO5)(H2O)2]n, crystallizes in orthorhombic, space group Pbca with a = 8.521(3), b = 10.154(3), c = 28.804(8) ?, V = 2492.2(13) ?3, Z = 8, C11H15NO7Cd, Mr = 385.64, Dc = 2.056 g/cm3, F(000) = 1536, μ(MoKα) = 1.786 mm-1, the final R = 0.0424 and wR = 0.0859 for 2026 observed reflections with I > 2σ(I). It has a one-dimensional zig-zag chain structure along the a axis driven by Cd–O coordination bonds. Three kinds of hydrogen bonds connect the chains along the b axis into a two-dimensional structure.

Hierarchical metal-peptide assemblies with chirality-encoded spiral architecture and catalytic activity

We report the coordination assembly of the ferrocene-diphenylalanine(Fc-FF)with divalent copper ions(Cu^(2+))into metalpeptide assemblies(MPAs)with hierarchical spiral architectures.The MPA particles are composed of helically organized nanofibers which can be correlated to the logarithmic spirals.The MPAs are hierarchically porous with abundant Fc and Cu2+active sites and show much higher catalytic activity than natural laccase toward the decolorization reaction.Moreover,a series of hierarchical structures of the MPAs can be synthesized by controlling the temperature and enantiomeric excess(ee).The peptide enantiomers with higher ee values will self-assemble into highly complex and ordered structures,which show higher surface area and porosity and thus enhanced catalytic activity compared with those assembled by peptides with lower ee values.The results provide new insights into the vital role of chirality in directing the self-assembly of biomolecules into highly ordered complex functional structures.

SYNTHESIS AND CHARACTERIZATION OF PALLADIUM COORDINATING IMINE SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANES

New thermotropic chloro-bridged dinuclear palladium coordinating imine side chain liquid crystalline polysiloxanes have been synthesized. Their mesomorphic properties have been investigated by DSC, X-ray diffraction and polarizing microscopy. The polymeric complexes show nematicdiscotic (Nd) mesophase. It is found that the temperature range of liquid crystalline state of chloro- bridged polymeric complexes is much wider than that of acetato- bridged ones and imine side chain polysiloxane. This indicates that the disc-like chloro-bridged palladium complexing units play a role as mesogen in mesophase.

In Situ Control of Multicolor Luminescence over the Entire Visible Spectral Region in a Single Chromophore by Sol–Gel Transformation and Dynamic Metal–Ligand Coordination

Controlling multicolor luminescence in a single chromophore is of fundamental significance but remains a great challenge.In this study,a carbazole group was incorporated into terpyridine through acylamide to produce a novel chromophore(N-{4-[(2,2′:6′,2″-terpyridine)-4′-yl]benzyl}-9-hexyl-9H-carbazole-3-carboxamide,TBCC)for achieving programmable luminescence switches.Significantly different emission states,such as nonemissive,blue,green,yellow,red,and white,were achieved in situ by controlling sol–gel transformation with sonication/heat and the reversible metal–ligand coordination between TBCC and various metal salts.

Regulating FUS Liquid-Liquid Phase Separation via Specific Metal Recognition

Liquid-liquid phase separation(LLPS)or biomolecular condensation that leads to formation of membraneless organelles plays a critical role in many biochemical processes.Mechanism study of regulating LLPS is therefore central to the understanding of protein aggregation and disease-relevant process.We report a fused in sarcoma protein(FUS)-derived low complexity(LC)sequence that undergoes LLPS in the presence of metal ions.The LC protein was constructed by fusing a hexhistidine-tag to the N-terminal low complexity domain(the residues 1–165 in QGSY-rich segment)of FUS.Spontaneous condensation of the intrinsic disordered protein into coacervate droplets was observed in the presence of metal ions that chelate oligohistidine moieties to form protein matrix.We demonstrate the key role of metal ion-histidine coordination in governing LLPS behaviours and the fluidity of biomolecular condensates.By taking advantage of competitive binding using chelators,we show the possibility of regulating dynamic behaviors of disease-relevant protein droplets,and developing a potential approach towards controllable biological encapsulation/release.

Preparation and properties of chitosan–metal complex：Some factors influencing the adsorption capacity for dyes in aqueous solution

Chitosan–metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan–metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan–Fe（ Ⅲ） complex prepared by sulfate salts exhibited the best adsorption efficiency（100%） for various dyes in very short time duration（10 min）, and its maximum adsorption capacity achieved 349.22 mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan–metal complex. SO4^（2-） ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process.Additionally, the p H sensitivity and the sensitivity of ionic environment for chitosan–metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan–metal complex can help not only in optimizing its use but also in designing new chitosan–metal based complexes.

Coordination polymers： Challenges and future scenarios for capture and degradation of volatile organic compounds

Over the past few decades, coordination polymers/metal organic frameworks （CPs/MOFs） have drawn a great deal of attention for diverse applications due to their advantages of intrinsically ttLnable chemical structure, flexible architecture, high pore volume, high surface area, multifunctional properties, etc. To date, numerous CPs/MOFs have been developed and employed for the treatment and control of gaseous pollutants, such as volatile organic compounds （VOCs）, through capture, sorptive removal, and catalytic degradation. Nevertheless, there are also some key drawbacks and challenges for the practical application of these systems （e.g., poor selectivity, high energy （and fiscal） cost, high synthesis cost, low capacity, and difficulties in regeneration and recycling）. In this review, recent developments in CPs/MOFs research are described with their associated mechanisms for capture, sorptive removal, and catalytic degradation of VOCs. To this end, we discuss the key variables and challenges for afforded abatement of VOCs through CPs/MOFs technologies. Hopefully, this review will help the scientific community set future directions for the advancement of CPs/MOFs techniques for the effective management of diverse environmental issues.

金属离子调控的高粘附弹性体用于组装多层弹性电路板

多层弹性印刷电路板被认为是在弹性基底上系统地集成各种电子元件的一种先进构造.然而在实际应用中,多层弹性基板之间的粘合界面很容易出现裂纹和分层,这是层间粘附力较弱导致的.在这里,我们通过调节不同金属离子与侧链为乙二胺基团的聚二甲基硅氧烷之间的配位键,得到了一种具有高粘附表皮和机械强韧内核的超分子复合夹层弹性体.这种夹层弹性体可以实现层间的强粘附(粘附强度0.80 MPa),同时兼具机械强度(断裂强度达0.81 MPa,杨氏模量为0.48 MPa,最大应变>500%).通过分层组装策略,此夹层弹性体可快速且牢固地组装具有多层结构的弹性电路板.这项研究为简单高效地制备机械稳定的多层柔性器件提供了新的思路,无需额外引入粘合层或者复杂的结构设计.

The homogenous growth of Co-based coordination compound on graphene nanosheet for high-performance K-organic battery and its reaction mechanism

Metal coordination compounds(MCCs)are gaining popularity for potassium-ion batteries(PIBs)owing to their tuneable structure,multiple reaction sites,low cost and unique morphology.However,they are generally subjected to intrinsic features of the sluggish ionic diffusion coefficient,low electronic conductivity and slow kinetics.Herein,a new MCC material of cobalt-1,3,5-trioxy-2,4,6-triamino-benzo(Co-TB)coordination compound was synthesized and homogenously grown on the surface of graphene nanosheets(GNS),forming a Co-TB@GNS composite with enhanced electronic conductivity and flexible capability.Benefiting from the overall enhanced conductivity,high surface area and abundant activated K-storage sites,Co-TB@GNS electrodes have exhibited superior cycling performance with high reversible capacities(312 mAh·g^(-1)after 100 cycles at 100 mA·g^(-1),224 mAh·g^(-1)after 500 cycles at 1 A·g^(-1))and better rate performances compared with the pure Co-TB compound when served as PIB's anodes.Furthermore,multiple in-situ measurement techniques have jointly confirmed that the organic functional groups(C=O,C=N and C=C of benzene rings)and Co^(2+)in Co-TB are the main reversible K-storage sites,including in-situ Fourier transform infrared spectroscopy(FTIR)and X-ray diffraction(XRD),and partial capacity contribution is originated from GNS by the apparent K-storage behavior in the in-situ XRD pattern,proving the possibility of K-storage for metal-organic materials.

Dynamic Oxime-Urethane Bonds, a Versatile Unit of High Performance Self-healing Polymers for Diverse Applications

Oxime-urethane bond featuring with high reversibility even at room temperature and multiple reactivity is an emerging dynamic covalent bond,and has shown great potential for self-healing polymers,which are one of the most attractive development directions for next generation of polymeric materials.In this review,recent progresses on the oxime-urethane-based self-healing polymers,including their designs and applications in diverse fields such as biomedicine,flexible electronics,soft robots,3D printing,protective materials,and adhesives,are summarized,and outlooks on the future development of this field are discussed.