Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff-Base Covalent Organic Frameworks

Covalent organic frameworks(COFs)after undergoing the superlithiation process promise high-capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox-active sites.Herein,integrating carbon nanotubes(CNTs)with imine-linked covalent organic frameworks(COFs)was rationally executed by in-situ Schiff-base condensation between 1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde and 1,4-diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites(CNT@COF).Accordingly,the redox-active shell of COF nanoparticles around one-dimensional conductive CNTs synergistically creates robust three-dimensional hybrid architectures with high specific surface area,thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode.Remarkably,upon the full activation with a superlithiation process,the as-fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g^(−1),which is the highest specific capacity among organic electrode materials reported so far.Meanwhile,the superior rate capability and excellent cycling stability are also obtained.The redox reaction mechanisms for the COF moiety were further revealed by Fourier-transform infrared spectroscopy in conjunction with X-ray photoelectron spectroscopy,involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.

Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Subtraction of liposome signals in cryo-EM structural determination of protein-liposome complexes

Reconstituting membrane proteins in liposomes and determining their structure is a common method for determining membrane protein structures using single-particle cryo-electron microscopy(cryo-EM).However,the strong signal of liposomes under cryo-EM imaging conditions often interferes with the structural determination of the embedded membrane proteins.Here,we propose a liposome signal subtraction method based on single-particle two-dimensional(2D)classification average images,aimed at enhancing the reconstruction resolution of membrane proteins.We analyzed the signal distribution characteristics of liposomes and proteins within the 2D classification average images of protein–liposome complexes in the frequency domain.Based on this analysis,we designed a method to subtract the liposome signals from the original particle images.After the subtraction,the accuracy of single-particle three-dimensional(3D)alignment was improved,enhancing the resolution of the final 3D reconstruction.We demonstrated this method using a PIEZO1-proteoliposome dataset by improving the resolution of the PIEZO1 protein.

Antioxidant activity of bovine serum albumin binding amino acid Schiff-bases metal complexes

Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.

SVNTHESES AND CHARACTERIZATION OF TWO HIGH VALENCE VANADIUM COMPLEXES (?) SCHIFF-BASE LIGAND WITH RICH PHENOLATE OXVGEN AND THEIR CONVERSION

Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.

n-Octyloxyallene homopolymerization and random copolymerization with styrene using catalyst system composed of lanthanide Schiff-base complexes and Al(i-Bu)_3

The catalyst system composed of lanthanide Schiff-base complexes with [3,5-tBu2-2-（O）C6H2CH=NC6Hs]3Ln（THF）（Ln（Salen）3, Ln = Sc, Y, La, Nd, Sm, Gd, Yb） and triisobutyl aluminum shows high activity for n-octyloxyallene （A） homopolymerization with narrow molecular weight distribution （MWD）. The influences of reaction conditions on polymerization behavior are in- vestigated, and poly（n-octyloxyallene） has a weight average molecular weight （Mw） of 20.6 ~ 103 with MWD of 1.39 and 100% yield is obtained under the optimum conditions： [A1]/[Y] = 50 mol/mol, [A]/[Y] = 100 mol/mol, with polymerization at 80 ~C for 16 h in bulk. The kinetic studies of n-octyloxyallene homopolymerization indicate that the polymerization rate is first-order with respect to the monomer concentration and shows some controlled polymerization characteristics. Random co- polymer of n-octyloxyallene with styrene is obtained by using the same binary catalyst system; the reactivity ratios of the comonomer determined by Kelen-Ttld/Ss method are rA = 1.20 and rst = 0.35, respectively, the ratio of each segment and Mw of the resulting copolymer could be controlled by varying the feed ratio of each monomer. Determined by differential scanning calorimetry, the copolymers obtained show only one glass transition temperature, which increases gradually with the increase of styrene content in the copolymer.

DFT Studies on Second-order Nonlinear Optical Properties of a Series of Axially Substituted Bis（salicylaldiminato） Zinc（II） Schiff-base Complexes

Coordination of an axial ligand to metal center to enhance the second-order nonlinear optical（NLO） re- sponse of a two-dimensional bis（salicylaldiminato） zinc（II） Schiff-base complex is an unprecedented model. The second-order NLO responses of a series of axially substituted bis（salicylaldiminato） zinc（II） Schiff-base complexes were explored according to the finite field（FF） method at CAM-B3LYP/6-31＋G（d） level（LANL2DZ basis set for metal atoms）. The results show that the second-order NLO properties can be effectively tuned by exchanging the do- nor and accepter of the axial ligand and extending the length of the conjugated bridge along the axial direction. A system involving the electron acceptor along the appropriate direction has a large three-dimensional second-order NLO response. Meanwhile, time dependent density functional theory（TD-DFT） method was employed to calculate the physical parameters of excited states. The results show that the Y- and Z-polarized transitions of the zinc（II） Schiff-base complex are the first and second excited states, respectively, and have a low-lying excited energy. Al- though the X-polarized transition has a high excited energy, the large oscillator strength indicates that it will signifi- cantly contribute to the second-order NLO response.

Synthesis, structure, optoelectronic properties of novel zinc Schiff-base complexes

Two novel zinc Schiff-base complexes, bis-(N-(2-hydroxybenzidene)-p-aminodimethylaniline)zinc(II) (2) and bis-(N-(2-hydroxy-1-naphthidene)-p-aminodimethylaniline)zinc(II) (4) were designed and synthesized. Both the complexes exhibit good solubility in organic solvents and excellent thermal stabilities. A single crystal of 2 was grown and its crystalline structure was determined from X-ray diffraction data. Analysis of the electronic structures of both the zinc complexes calculated by density functional theory reveals a localization of orbital. The UV-Vis absorption and photoluminescence profiles of 4 in thin film are similar to those of 2, but the emission for 4 is red-shifted compared to 2. Three-layered devices with a configuration of ITO/NPB/2/Alq 3 /LiF/Al and ITO/NPB/4/Alq 3 /LiF/Al show a yellow and red emission, respectively.

DNA-free genome editing in grapevine using CRISPR/Cas9 ribonucleoprotein complexes followed by protoplast regeneration

CRISPR/Cas9 genome editing technology can overcome many limitations of traditional breeding,offering enormous potential for crop improvement and food production.Although the direct delivery of Cas9-single guide RNA(sgRNA)ribonucleoprotein(RNP)complexes to grapevine(Vitis vinifera)protoplasts has been shown before,the regeneration of edited protoplasts into whole plants has not been reported.Here,we describe an efficient approach to obtain transgene-free edited grapevine plants by the transfection and subsequent regeneration of protoplasts isolated from embryogenic callus.As proof of concept,a single-copy green f luorescent protein reporter gene(GFP)in the grapevine cultivar Thompson Seedless was targeted and knocked out by the direct delivery of RNPs to protoplasts.CRISPR/Cas9 activity,guided by two independent sgRNAs,was confirmed by the loss of GFP f luorescence.The regeneration of GFP−protoplasts into whole plants was monitored throughout development,confirming that the edited grapevine plants were comparable in morphology and growth habit to wild-type controls.We report the first highly efficient protocol for DNA-free genome editing in grapevine by the direct delivery of preassembled Cas9-sgRNA RNP complexes into protoplasts,helping to address the regulatory concerns related to genetically modified plants.This technology could encourage the application of genome editing for the genetic improvement of grapevine and other woody crop plants.

Density Functional Theory Study on La Complex with Schiff-base as Building Block

Quantum density functional theory （DFT） results are reported for the building block [LaL^1（NO3）] of La complex [LaL^1（NO3）]NO3·5H2O （L^1 = （CH3）2CHCH2CH（NCHC4H3O）COO^-）. The structure was optimized and the calculation results show that the lanthanum ion is coordinated by one nitrogen atom and three oxygen atoms of L^1 and two oxygen atoms of nitrate ion. The bond length of La-N is 0.2637 nm and the average length of La-O is 0.2526 nm, which are consistent with the literatures. In addition, the stabilities, electronic structural characteristics and IR spectra of the complex have been analyzed, which describe the coordination of lanthanum ion with other atoms in detail.

Synergistic Optimization of Buried Interface by Multifunctional Organic-Inorganic Complexes for Highly Efficient Planar Perovskite Solar Cells

For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is challenging to effectively optimize this interface as it is buried beneath the perovskite film.Herein,we have designed and synthesized a series of multifunctional organic-inorganic(OI)complexes as buried interfacial material to promote electron extraction,as well as the crystal growth of the perovskite.The OI complex with BF4−group not only eliminates oxygen vacancies on the SnO_(2) surface but also balances energy level alignment between SnO_(2) and perovskite,providing a favorable environment for charge carrier extraction.Moreover,OI complex with amine(−NH_(2))functional group can regulate the crystallization of the perovskite film via interaction with PbI2,resulting in highly crystallized perovskite film with large grains and low defect density.Consequently,with rational molecular design,the PSCs with optimal OI complex buried interface layer which contains both BF4−and−NH_(2) functional groups yield a champion device efficiency of 23.69%.More importantly,the resulting unencapsulated device performs excellent ambient stability,maintaining over 90%of its initial efficiency after 2000 h storage,and excellent light stability of 91.5%remaining PCE in the maximum power point tracking measurement(under continuous 100 mW cm−2 light illumination in N2 atmosphere)after 500 h.

Schiff-base polymer derived FeCo-N-doped porous carbon flowers as bifunctional oxygen electrocatalyst for long-life rechargeable zinc-air batteries

Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.

Synthesis and Crystal Structure of a Novel Binuclear Cu(Ⅱ) Complex with Tetradentate Schiff-base Ligand

A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511（10）, b = 15.750（12）, c = 14.281 （12） A, β = 100.564（14）°, C22H31CIN4O9Cu2, Mr = 658.04, V = 2766（4） A^3, Z = 4, Dc = 1.580 g/cm^3,μ（MoKα = 1.689 mm^-1, F（000） = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound, and two Cu（Ⅱ） ions in the binuclear cation are in different coordination environments. The Cu（1） ion adopts a distorted square pyramidal geometry （x = 0.22） with four donor atoms （N2O2） of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position. The Cu（2） ion assumes the geometry of a distorted square plane with four donor atoms （N2O2） of the ligand. The Cu...Cu separation is 3.103 A,. In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.

Crystal Structure of Binuclear Manganese(Ⅲ) Complex with Schiff-base Ligand,〔Mn_2(C_(22)H_(22)N_2O_2)_2(EtOH)_2 (bipy)〕(ClO_4)_2

The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.

Synthesis, Crystal Structure and Characterization of a New Mononuclear Zn(Ⅱ) Complex from Schiff-base Ligand

A new mononuclear [Zn（H-1L）2] （L = 1H-indole-3-ethylene-salicylaldimine） was synthesized through the reaction of Zn（Ac）2, salicylaldehyde and tryptamine in hot ethanol solution and characterized by X-ray crystal structure analysis. The crystal belongs to monoclinic, space group P21/n with a = 15.014（2）, b = 10.857（1）, c = 17.489（1）A,β = 95.49（1）°, V = 2837.8（5） A^3, Z = 4, Dc = 1.386 g/cm^3, μ = 0.904 mm-1, F（000） = 1232, the final R = 0.0463 and wR = 0.0890 for 4990 independent reflections. In the complex, the Zn2＋ ion presents a distorted N2O2 tetrahedral coordination involving two H-1L ligands.

Encapsulation of Ru(II) Polypyridine Complexes for Tumor-Targeted Anticancer Therapy

Ru(II)polypyridine complexes have attracted much attention as anticancer agents because of their unique photophysical,photochemical,and biological properties.Despite their promising therapeutic profile,the vast majority of compounds are associated with poor water solubility and poor cancer selectivity.Among the different strategies employed to overcome these pharmacological limitations,many research efforts have been devoted to the physical or covalent encapsulation of the Ru(II)polypyridine complexes into nanoparticles.This article highlights recent developments in the design,preparation,and physicochemical properties of Ru(II)polypyridine complex-loaded nanoparticles for their potential application in anticancer therapy.

A Novel Copper(Ⅱ)Complex Based on 4-Amino-1,2,4-triazole Schiff-base:Synthesis,Crystal Structure,Spectral Characterization,and Hirshfeld Surface Analysis

A novel copper complex Cu2（L）4（1, HL = 2-ethoxy-6-（[1,2,4]triazol-4-yliminomethyl）-phenol） has been synthesized and characterized by IR, single-crystal X-ray diffraction, and elemental analysis（CHN）. The single crystal belongs to the triclinic system, space group P1 with a = 10.0991（10）, b = 10.5280（12）, c = 10.5777（11） A, α = 97.230（9）, β = 90.640（8）, γ = 92.412（9）°, Mr = 1052.05, V = 1114.6（2） A3, Z = 1, Dc = 1.567 g/cm3, F（000） = 542, μ = 1.029 mm–1, R = 0.0562 and w R = 0.1562. The fluorescence and electrochemiluminescence（ECL） of 1and HL ligand were studied. The luminescence properties of 1 can be attributed to the ligand-metal charge transfer.