Synthesis and Characterization of a New Ligand 2-(4, 5-Dihydro-2-thiazolyl)-6-methoxylbenzothiazole and Its Dinuclear Co(II) Complex

A new ligand 2-(4,5-dihydro-2-thiazolyl)-6-methoxyl benzothiazole and its new dinuclear Co(II) coordination complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 (1) have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co(II) salt with 2-(4,5-dihydro- 2-thiazolyl)-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C–H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288(12), b = 10.5273(15), c = 10.822(2), α = 93.416(3), β = 90.864(3), γ = 94.890(3)o, V = 943.60(2)3, Z = 2, Dc = 1.758 g/cm3, F(000) = 498 and μ = 1.840 mm-1. The final complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co(II) ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.

Energy transfer, anticounterfeiting, white light emission and sensing in fine-regulating series of lanthanide metal-organic frameworks

Three lanthanide ions and a rigid(1,1'-biphenyl)-2,4,6-tricarboxylic acid(H_(3)bptc) ligand led to the isostructural lanthanide metal-organic frameworks(Ln-MOFs) {[Ln(bptc)(H_(2)O)_(3)]·3H_(2)O}_n(Lnbptc, Ln = Eu,Tb, Gd, Eu_(x)Tb_(1—x), Eu_(x)Gd_(1-x), Tb_(x)Gd_(1-x), and Eu_(0.12)Tb_(0.52)Gd_(0.36)). The density functional theory(DFT) and time-dependent DFT calculation were expanded on H_3bptc, which point to the occurrence of “antenna effect”. The minor diameter samples of Eubptc, Tbbptc, and Gdbptc can also be attained via the microwave synthesis and employed for handwriting anticounterfeiting. Interestingly, the typical red emission of Eu^(3+) and green emission of Tb~(3+) could be fine-tuned by Gd^(3+) via chemical mixing to be full-color emissions bimetallic doped Eu_(x)Tb_(1-x)bptc, Eu_(x)Gd_(1-x)bptc, and Tb_(x)Gd_(1-x)bptc. The above synthetic bimetallic MOFs can be fixed in positioning boxes of quick response(QR) codes with diverse emission for anticounterfeiting. The message can be decoded under the irradiation of 365 nm ultraviolet lamp while invisible in the daylight. Notably, the trimetallic doped Eu_(0.12)Tb_(0.52)Gd_(0.36)bptc emits white light with the CIE color coordinate(0.34, 0.34). Furthermore, Tbbptc is demonstrated to be a sensitive probe toward nitrobenzene and acetone with multiple mechanisms.

Designing Tough,Printable,and Adaptable Eutectogels with Multinetworks via Synergy of Rapid Orthogonal Photopolymerizations and Solvent Effect in Seconds

Achieving a straightforward design of tough,printable,and adaptable polymeric eutectogels is still challenging in related fields due to the uncontrollable polymerization and solvent-exchanging processes,and inherent contrasting multiple networks.Here,we report a one-step synergistic strategy based on ruthenium chemistry-catalyzed photopolymerization and solvent effect for preparing high-performance eutectogels.This orthogonal ruthenium photochemistry helps multinetworks formation via phenol-coupling of gelatin and copolymerization of acrylamide(AAm)and[2-(methacryloyloxy)ethyl]trimethylammonium tetrafluoroborate(META)monomers in seconds.The obvious difference in the supramolecular interactions of free AAm monomers and polymerized units in P(AAm-co-META)with deep eutectic solvents(DESs)significantly promotes the microphase-separation behavior in eutectogels.Consequently,the in situ polymerization and microphase-separation behavior enable the as-prepared eutectogel materials to have excellent mechanical properties(stress of∼1.2 MPa),toughness(∼4.0 MJ m^(−3)),elasticity,adaptivity,and conductivity(∼0.5 S m^(−1)at room temperature).Also,the critical strength of the resultant eutectogels can be modulated by varying the DES constituents.This rapid and well-controlled synergistic approach is compatible with extrusion printing techniques to make flexible sensors with high sensitivities and response times to detect pressure in a range of 0–500 kPa.Such a general and simple strategy has application potential in biological,engineering,and material sciences.

Dramatic Impact of Auxiliary Ligands on the Dynamic Magnetic Relaxation in Tetranuclear Dy^(III)_(2)Zn^(II)_(2) Single Molecule Magnets

Better understanding the determining factors of dynamic magnetic relaxation in polynuclear lanthanide based single-molecule magnets(SMMs)remains a challenge due to the complexity of such architectures involving interactions between the magnetic centers.To address this issue,two structurally related heterometal Dy^(III)_(2)Zn^(II)_(2) SMMs,[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)(CH_(3)OH)]·CH_(3)OH·2H_(2)O(1)and[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)_(2)]·4CH_(3)CN(2)(H_(2)L=(E)-2-((2-hydroxy-3-methoxybenzylidene)amino)-4-methyphenol,DMF=N,N-dimethylformamide),are introduced and investigated.Through modifying the auxiliary ligands on one Dy^(III) site while retaining that on the other Dy^(III),the intramolecular magnetic interactions and relaxation dynamics in these two heterometallic-Dy^(III)_(2)Zn^(II)_(2) SMMs can be tuned,demonstrating a dramatic change in the magnet relaxation behavior with energy barrier changing from a negligible value for 1 to 305 K for 2.Ab initio calculations reveal that changing the coordination geometries on the Dy^(III) sites can significantly affect the magnetic interactions as well as single-ion anisotropy.

One New 3D Pillared-layer Ag(Ⅰ)-Coordination Framework Based on a Unique 1D Ag2O2 Ribbon： Synthesis,Crystal Structure and Luminescent Properties

A new 3D Ag(I) coordination polymer {[Ag(AZDB)_(0.5)(bpe)_(0.5)]·H_2O}_n(1) has been papared by azobenzene-3,3?-dicarboxylicate(H_2AZDB), 1,2-bis(4-pyridyl)ethylene(bpe) and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag_2O_2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal(4, 6)-connected fsc net with a(44·610·8)(44·62) topology.Moreover, the photoluminescent properties have also been discussed.

Efficient C_(2) Hydrocarbons and CO_(2) Adsorption and Separation in a Multi-site Functionalized MOF

A multi-site functionalized microporous metal-organic framework(MOF),H[Zn2(BDP)0.5(ATZ)3]·0.5 H_(2)O·0.5DMF(1),was synthesized through mixed ligands strategy.The pore surface of complex 1 was modified by uncoordinated carboxylate O atoms,phenyl and pyridyl rings as well as-NH_(2) groups,which strengthen interactions with C2H6,C_(2)H_(4) and CO_(2) molecules and lead to efficiently selective C2H6,C_(2)H_(4) and CO_(2) uptake over CH_(4).The selective adsorption mechanism was discussed deeply based on Grand Canonical Monte Carlo(GCMC)simulations.It is expected that this study will provide a new perspective for the rational design and synthesis of MOFs with efficient gas adsorption and separation performance.

The synthesis and study of the fluorescent probe for sensing Cu^(2+) based on a novel coumarin Schiff-base

A novel, fluorescent probe was synthesized from 2,4-dihydroxybenzaldehyde and 8-hydroxyquinoline for sensing Cu2+by the naked eye. The structure was confirmed by IR, MS,1H NMR,13 C NMR and the spectral properties of the probe were investigated. It exhibited strong fluorescence responses toward Cu2+and high selectivity over other metal ions. The binding constant between the probe and Cu2+was calculated using Benesi–Hildebrand equation.

Crystal Structure and Theoretical Calculation of 1,4-Bis- （1-ferrocenesulfonyl-2-benzimidazolyl） Butane

N， N-bisferrocenesulfonyl bisbenzimidazole 混合物 1,4 二度(1-ferrocenesulfonyl-2-benzimidazolyl ) 钢瓶煤气被准备。它的水晶结构是坚定的。水晶属于与空间组 P-1 和 a=0.87241 (13 ) 三斜晶系 nm， b=0.97553 (15 ) nm， c=1.4120 (2 ) nm，和 =83.041 (2 ) 呼搠 ? 湡 ??

Synthesis, structure and electrocatalytic H2-evoluting activity of a dinickel model complex related to the active site of [NiFe]-hydrogenases

Structural and functional biomimicking of the active site of [NiFe]-hydrogenases can provide helpful hints for designing bioinspired catalysts to replace the expensive noble metal catalysts for H2 generation and uptake.Treatment of dianion [Ni(phma)]2-[H4 phma=N,N’-1,2-phenylenebis(2-mercaptoacetamide)] with [NiCl2(dppp)](dppp=bis(diphenylphosphino)propane) yielded a dinickel product[Ni(phma)(μ-S,S’)Ni(dppp)](1) as the model complex relevant to the active site of [NiFe]-H2 ases.The structure of complex 1 has been characterized by single-crystal X-ray analysis.From cyclic voltammetry and controlled potential electrolysis studies,complex 1 was found to be a moderate electrocatalyst for the H2-evoluting reaction using ClCH2COOH as the proton source.

Modular Synthesis of Tetraurea and Octaurea Macrocycles Encoded with Specific Monomer Sequences

Intermolecular hydrogen bonding among urea units grants prominent mechanical strength to polyurea elastomer materials.However,such interactions can cause significant solubility problems when synthesizing oligourea macrocycles with a large number of urea units,and it remains unknown for macrocycles containing more than six urea units.Here,we demonstrate a two-step,modular strategy for making a new class of tetraurea and octaurea macrocycles using commercially available building blocks.Intramolecular hydrogen bonding within the fundamental o-phenylene bis(urea)unit is the key to overcoming intermolecular hydrogen bonding to form favorable conformations for ring-closure reactions.The size and monomer sequences can be controlled by varying the flexibility of the spacers.Rigid diphenyl methylene and diphenyl ether linkers selectively afford tetraurea macrocycles,whereas the flexible hexylene linker produces octaurea macrocycles.Macrocycles encoded with two different spacers were also made.All these macrocycles are confirmed by X-ray diffraction structural analysis of the complexed forms with sulfate anions.Interestingly,a unique“figure-eight”structure is observed for the complex of MUH octaurea macrocycle with two encapsulated sulfate anions.Our study shows a paradigm of making large oligourea macrocycles with designer properties in a programable manner with tunable monomer sequences.

Magnetoresponsive nanozyme:magnetic stimulation on the nanozyme activity of iron oxide nanoparticles

The iron oxide nanoparticles(IONPs)that combine the nanozyme activity and magnetothermal properties have attracted significant interest for various biomedical applications.However,the effect of magnetic stimulation in fine-tuning the nanozyme activities remains unclear.Here,we have constructed a series of IONPs with different magneto-thermal conversion abilities,and systematically study the effect of magnetic field stimulation on the peroxidase(POD)activity of IONPs.The results show that POD activity is effectively amplified via an in situ alternating magnetic field(AMF)stimulation with no solution temperature rise,and the degree of activity enhancement is closely related to the magnetic heating ability of the IONPs,confirming the origin of activity enhancement arises from the local magnetothermal effect.As the first report to prove magnetothermal regulation on nanozyme activity and to shed lights on the underlying correlation between activity enhancement and the intrinsic specific absorption rate(SAR),this work is expected to provide important support for future design of new magnetoresponsive nanozymes in various practical applications.

Pseudo[n,m]rotaxanes of Cucurbit[7/8]uril and Viologen‐Naphthalene Derivative: A Precise Definition of Rotaxane

Summary of main observation and conclusion Rotaxane is a kind of classic supramolecule, which is usually constructed from a number of macrocycles and one axis molecule. Herein, we have expanded the supramolecular structure of [n]rotaxane to offer a precise definition of (pseudo)[n,m]rotaxane for accurately describing the two kinds of (pseudo)rotaxanes structures, which are self‐assembled from cucurbit[7/8]uril (CB[7/8]) and viologen‐naphthalene derivative, respectively. Furthermore, these CB‐based pseudorotaxanes exhibit varied photophysical properties, stimuli‐responsive behavior triggered by competitive guest, and self‐sorting behavior.

Novel thioxanthone host material with thermally activated delayed fluorescence for reduced efficiency roll-off of phosphorescent OLEDs

2,7-Di(9,9-dimethyl-9 H-fluoren-1-yl)-9 H-thioxanthen-9-one(DMBFTX) with thermally activated delayed fluorescence(TADF) was well designed and synthesized. The phosphorescent organic lightemitting device(PHOLED) based on this novel TADF host material displays a stable red phosphorescence region, a peak external quantum efficiency(EQE) value of 12.9% and a low EQE roll-off of 38.8% at a luminance of 10000 cd/m^2, which is benefited from the reverse intersystem crossing(RISC) of TADF host and less populated triplet exitons. Notably, the red device based on the TADF host DMBFTX exhibits superior electroluminescence performance and reduced efficiency roll-off compared with the one hosted by commercially available host 1,3-bis(9-carbazolyl)benzene(mCP), illustrating the high potential of employing the TADF host material with small energy gap to reduce efficiency roll-off in PHOLED.

Modulating conductivity type of cuprous oxide（Cu2O） films on copper foil in aqueous solution by comproportionation

Cuprous oxide(Cu2O)is an attractive material for photoelectrochemical(PEC)hydrogen production or photovoltaic application,because of its appropriate band gap,low material cost and non-toxic.In this paper,Cu2O films were obtained by comproportionation in acid cupric sulfate solutions with varying concentrations of potassium nitrate.Photoelectrochemical and electrochemical experiments,such as zero-bias photocurrent responses,voltammograms,and Mott-Schottky measurements,show that the Cu2O films grown in low(≤0.75 mol dm^–3)and high(≥1.00 mol dm^–3)nitrate ion concentrations presented n-type and p-type conductivity,respectively.Open circuit potential and polarization behavior were monitored to investigate the mechanism of modulating conductivity type.Nitrate ions consume protons in the plating solution during comproportionation with different concentrations of nitrate ions creating different pH at the Cu2O/solution interface.This gradient leads to the transformation of Cu2Ofilms conductivity changing from n-type to p-type with increasing the concentration of nitrate ions in the plating solution.This method could be used to fabricate homojunction electrode on metal substrate for PEC hydrogen production or photoelectric application.

Supramolecular polymer network constructed by a functionalized polyimidazolium salt derived from metal-carbene template approach

In this study,we present a supramolecular templating approach for constructing polyimidazolium salt containing crown ether and cyclobutane moieties.This strategy involves the formation of metal-carbene templates,photochemical cycloaddition,and subsequent demetallation of metal ions.Driven by the host-guest chemistry between crown ether units and ammonium salts,we successfully fabricated a supramolecular polymer SPN1,which features imidazolium receptors and cyclobutane units.The obtained SPN1 demonstrates outstanding reversible stimulus-response,antibacterial behavior and conductivity.

A general strategy for selective detection of hypochlorous acid based on triazolopyridine formation

Triazolopyridines are an important kind of fused-ring compounds.A HOCl-promoted triazolopyridine formation strategy is reported here for the first time in which hypochlorous acid(HOCl)mildly and efficiently promotes the formation of 1,2,4-triazolo[4,3-a]pyridines NT1-NT6 from various 2-pyridylhydrazones N1-N6.N6,a rhodol-pyridylhydrazone hybrid,was developed into a fluorescent probe for the selective detection of HOCl,and successfully applied to probe endogenous HOCl in living cells and zebrafish in situ and in real time.The present intramolecular cyclization reaction is selective and atom-economical,thereby not only providing an important approach for the convenient synthesis of triazolopyridines,but also offering a general strategy for sensitive,selective and biocompatible detection of endogenous HOCl in complex biosystems.

Magnetic nanoparticles based cancer therapy: current status and applications

Nanotechnology holds a promising potential for developing biomedical nanoplatforms in cancer therapy. The magnetic nanoparticles, which integrate uniquely appealing features of magnetic manipulation, nanoscale heat generator, localized magnetic field and enzyme-mimics, prompt the development and application of magnetic nanoparticles-based cancer medicine. Considerable success has been achieved in improving the magnetic resonance imaging(MRI) sensitivity, and the therapeutic function of the magnetic nanoparticles should be given adequate attention. This work reviews the current status and applications of magnetic nanoparticles based cancer therapy. The advantages of magnetic nanoparticles that may contribute to improved therapeutics efficacy of clinic cancer treatment are highlighted here.

Reprogramming the tumor immune microenvironment via nanomaterial-mediated dynamic therapy

Our improved knowledge of tumor immunology laid a solid foundation for the clinical use of tumor immunotherapies such as immune checkpoint blockers,and the efficacy of these drugs increased our confidence that immunomodulation was a viable way of treating cancer.The basis of immunotherapy is to break the immune escape of the tumor and resolve the immune suppressive microenvironment of tumors.Nanomaterial-mediated dynamic therapy(NDT)is an emerging immuno-regulatable type for tumor therapy,whose effects are mediated by increased cellular levels of reactive oxygen species(ROS).ROS is a potent trigger of immunogenic cell death,and this process initiates antitumor immunity.Nanomaterials for use in NDT can be engineered to interact with almost all cell types in the tumor microenvironment to remodel this environment.In this review,we systematically examined the effects of NDT on four major cell types in the tumor microenvironment,namely tumor cells,lymphocytes,myeloid cells,and tumor stromal cells.We believe that this review will improve researchers’understanding of the anti-tumor immunity triggered by NDT,and provide ideas and inspiration for how optimally designed NDT schemes can be used to target the cells in the tumor microenvironment.

A Novel Dual Channel Fluorescent Probe for Ca^2＋ and Zn^2＋ Based on a Coumarin Schiff Base

一个新奇香豆素 Schiff 库荧光灯探查乙醇 7-hydroxycoumarin-3-carboxylate-8-formaldehyde benzoyl hydrazone ( EBH )被设计了并且综合它显示出溶剂依赖者双察觉到， viz ，在 DMF-H 22+的识别> O ( 91 ， V/V )解决方案基于 C = N 异构化， photoinduced 电子转移(宠物)抑制和 提高chelation 的荧光(厨师)在 H 22+的机制以及察觉> O-CH 3哦( 91 ， V/V )由 exc 的答案探查 EBH 的结构被单个水晶的 X 光检查衍射分析证实了。同时，探查也习惯于图象在有好表演的 MCF-7 房间的细胞内部的 Zn 2+ 离子。

Optically actuating ultra-stable radicals in a large π-conjugated ligand constructed photochromic complex

Producing ultra-stabilized radicals via light irradiation has raised considerable concern but remains a tremendous challenge in functional materials. Herein, optically actuating ultra-stable radicals are discovered in a sterically encumbered and large π-conjugated tri(4-pyridyl)-1,3,5-triazine(TPT) ligands constructed photochromic compound Cu_(3)(H-HEDP)_(2)TPT_(2)·2H_(2)O(QDU-12;HEDP=hydroxyethylidene diphosphonate). The photogeneration of TPT· radicals is the photoactive behavior of electron transfer from HEDP motifs to TPT units. The ultra-long-lived radicals are contributed from strong interchain π-π interactions between the large π-conjugated TPT components, with the radical lifetime maintained for about 18 months under ambient conditions. Moreover, the antiferromagnetic couplings between TPT· radicals and Cu^(2+)ions plummeted the demagnetization to 35% of its original state after light irradiation, showing the largest room temperature photodemagnetization in the current radicalbased photochromic materials.