Synthesis and cercaricidal activities of a serial of novel self-diffused cercaricides derived from niphensamide

A serial of novel cercaricides that can self-diffuse on the water surface were designed and synthesized according to the special habit of cercariae larvae.These compounds were derived from niphensamide.While the compounds were dropped on the surface of water,the liquor diffused along the air-water interface and formed thin membranes floating on the water surface immediately.The strong cercaricidal activities against the cereariae larvae of Schistosome japonicum of these compounds have been revealed by further experiments.

Asymmetric radical allylation of β-keto esters with vinyl cyclopropanes by dual photoredox/nickel catalysis

Radical-involved allylation reactions have emerged as a powerful platform for construction of carbon-carbon and carbonheteroatom bonds, facilitating the strategic incorporation of diverse allyl moieties. Nevertheless, this burgeoning field still faces ongoing challenges, including limitations of radical precursors and coupling partners, and difficulties in achieving enantiocontrol. Herein, we report for the first time a highly enantioselective radical allylation involving β-keto esters with vinyl cyclopropanes utilizing a synergistic dual photoredox/nickel catalysis under visible light irradiation. The mild and redox-neutral catalytic protocol demonstrates an extensive substrate compatibility and good functional tolerance, providing access to enantioenriched β-keto esters featuring quaternary α-stereocenter with good yields and high enantioselectivities. Preliminary mechanistic studies have uncovered that the success of the reaction hinges on the dual roles of nickel catalyst, including in situ formation of photoredox sensitive substrate/Ni complex and the ensuing asymmetric radical addition step.

Visible-Light-Driven Four-Component Radical Relay Aminocarbonylation of Unactivated Alkenes

Catalytic four-component radical carbonylation of unactivated alkenes has recently been recognized as a robust protocol for rapid construction of various structurally diverse carbonyl compounds.Given the significance of fluorine-containing groups,this reaction class has been extensively applied to assembly of a variety of perfluoroalkyl carboxylic acid derivatives by transition metal catalysis.Herein,we report a visible-light-driven radical relay 1,2-perfluoroalkylation aminocarbonylation of unactivated alkenes using CO gas as carbonyl source and 4CzIPN as organic photocatalyst.A wide range of alkenes and amines were well tolerated,providing the valuableβ-perfluoroalkylated amides with generally good yields and high chemoselectivity.

Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries:A DFT study

Nowadays,lithium-ion batteries(LIBs)play a crucial role in modern society in the aspect of portable electronic devices and large-scale smart grids.However,the current performance of lithium-ion batteries has been unable to meet the growing expectations of society and scientific community.Herein,we have synthetically investigated availability of 2D Ni-TABQ monolayer as anode based on DFT for LIBs applications.Our findings have demonstrated that 2D Ni-TABQ monolayer is a semiconductor with a small band gap of 0.2 eV,which suggest that the electronic property of 2D Ni-TABQ monolayer would take place an evident shift from semiconductor property to metallic property after Li adsorption.Furthermore,we checked the stability of 2D Ni-TABQ monolayer and investigated the viability of exfoliation from bulk multilayer Ni-TABQ to form 2D Ni-TABQ monolayer in the light of exfoliation energy and binding energy.We continuously studied electrochemical properties of 2D Ni-TABQ monolayer with respect of theoretical specific capacity,Li-ion diffusion barriers and open-circuit voltage.During the charging process,2D Ni-TABQ monolayer can achieve a high specific capacity of 722 m Ah/g with an open-circuit voltage range from 1.12 V to 0.22 V.These aforementioned results make the 2D Ni-TABQ monolayer a promising anode for LIBs.

Weakly-solvating electrolytes enable ultralow-temperature (-80°C) and high-power CF_(x)/Li primary batteries

Fluorinated carbons(CF_(x))/Li primary batteries with high theoretical energy density have been applied as indispensable energy storage devices with no need for rechargeability,yet plagued by poor rate capability and narrow temperature adaptability in actual scenarios.Herein,benefiting from precise solvation engineering for synergistic coordination of anions and low-affinity solvents,the optimized cyclic ether-based electrolyte is elaborated to significantly facilitate overall reaction dynamics closely correlated to lower desolvation barrier.As a result,the excellent rate(15 C,650 mAh g^(-1))at room-temperature and ultra-lowtemperature performance dropping to-80°C(495 mAh g^(-1)at average output voltage of 2.11 V)is delivered by the end of 1.5 V cut-off voltage,far superior to other organic liquid electrolytes.Furthermore,the CF_(x)/Li cell employing the high-loading electrode(18-22 mg cm^(-2))still yields 1,683 and 1,395 Wh kg^(-1)in the case of-40°C and-60°C,respectively.In short,the novel design strategy for cyclic ethers as basic solvents is proposed to enable the CF_(x)/Li battery with superb subzero performances,which shows great potential in practical application for extreme environments.

三功能多位点绣球状电催化剂用于高效的安培级全解水/尿素制氢

电解水是绿氢制备最有希望的路线之一,它的颈瓶是阳极析氧反应需要极高的过电位,导致电解水制氢整体能耗高.因此,迫切需要开发廉价、高活性、大电流稳定的非贵金属基多功能催化剂以期降低电解水的制氢能耗,如淡水或含尿素的水.鉴于此,我们合理设计并合成了绣球状的CoP/Ni3FeN异质结,用于碱性析氢、析氧和尿素电催化氧化反应.该催化剂呈现出优异的三功能催化活性和出色的大电流耐久性,在进行析氢、析氧和尿素电氧化反应时,分别需要-0.160、1.538和1.419 V的超低电位就能达到1000 mA cm^(-2)的高电流密度.此外,将该电催化剂作为正极和负极耦合全解水/尿素器件,仅需要1.577/1.668 V的电压就能驱动500 mA cm^(-2).此外,结合原位拉曼光谱、测试后的X射线光电子能谱分析与密度泛函理论计算,我们验证了CoP/Ni3FeN异质结催化剂可以极大地促进析氧和尿素氧化反应中的活性物种金属羟基氧化物的形成,同时降低析氢反应中的水吸附和活性氢中间体的吸附能垒,从而协同促进高效的析氢、析氧和尿素电催化氧化性能.这项工作为开发多功能电催化剂用于低电压电化学制氢提供了一条有效途径.

先进钠离子电池材料的前景与展望

According to the reports of"Top Ten Emerging Technologies in Chemistry 2022"released by the International Union of Pure and Applied Chemistry,sodium-ion battery(SIB)technology is identified as a crucial emerging technology,indicating its promising development for future energy-storage applications[1].In practical applications,commercialized lithium-ion batteries(LIBs)with lithium cobalt oxide and ternary oxide as cathode materials have assumed a dominant position[2].However,these cathode materials of LIBs are highly dependent on expensive cobalt and nickel,rendering them less sustainable for grid-scale energy storage.Conversely,cathode materials in SIBs appear more sustainable due to their lower dependence on cobalt.Furthermore,the strategic importance of reducing over-dependence on lithium resources cannot be overstated.Hence,SIB technology can serve as one of the potential solutions to mitigate this issue[3].

Synergistic regulation of intermolecular interactions to control chiral structures for chiral recognition

Understanding the regulatory mechanism of self-assembly processes is a necessity to modulate nanostructures and their properties. Herein, we have studied the mechanism of self-assembly in the C3 symmetric 1,3,5-benzentricarboxylic amino acid methyl ester enantiomers(TPE) in a mixed solvent system consisting of methanol and water. The resultant chiral structure was used for chiral recognition. The formation of chiral structures from the synergistic effect of multiple noncovalent interaction forces was confirmed by various techniques. Molecular dynamics simulations were used to characterize the time evolution of TPE structure and properties in solution. The theoretical results were consistent with the experimental results. Furthermore, the chiral structure assembled by the building blocks of TPE molecules was highly stereoselective for diamine compounds.

Porous coordination polymers based on three planar rigid ligands

During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chemical functions.This article provides a short review of recent advances in the design and constructions of porous coordination polymers based on three planar rigid ligands,including imidazole-4,5-dicarboxlate(H3IDC),1H-tetrazole(HTz),as well as 1H-tetrazole-5-carboxylate(H2Tzc).Their preparations,crystal structures,and desirable properties have been reviewed.

Tumor-homing peptide-based NIR-II probes for targeted spontaneous breast tumor imaging

Fluorescence imaging in the second near-infrared window(NIR-Ⅱ,1000-1700 nm)is a promising modality for real-time imaging of cancer and image-guided surgery with superior in vivo optical properties.So far,very few NIR-Ⅱfluorophores have been reported for in vivo biomedical imaging of chemically-induced spontaneous breast carcinoma.Herein,a NIR-Ⅱfluorescent probe CH1055-F3 with the nucleolin-targeted tumor-homing peptide F3 was demonstrated to prefe rentially accumulate in 4 T1 tumors.More importantly,CH1055-F3 exhibited specific NIR-Ⅱsignals with high spatial and temporal resolution,strong tumor uptake,and remarkable NIR-Ⅱimage-guided surgery in dimethylbenzanthracene(DMBA)-induced spontaneous breast tumor rats.This report presents the first tumor-homing peptide-based NIR-Ⅱprobe to diagnose transplantable and spontaneous breast tumors by the active targeting.

β-Cyclodextrin polymer networks stabilized gold nanoparticle with superior catalytic activities

Support materials play a significant role in heterogeneous nanocatalysis.In this work,β-cyclodextrin(β-CD)was used directly as a monomer to construct polymer networks for gold nanoparticles(Au NPs)immobilization.Using the simple nucleophilic substitution reaction,β-CD based polymer networks(β-CDP-N andβ-CDP-C)were successfully prepared.Compared toβ-CDP-C,the hydroxyl groups and N atoms inβ-CDP-N played a synergistic role in immobilizing smaller Au NPs,thus leading to high catalytic activities.Notably,the apparent rate constant(Kapp)value for Au@β-CDP-N in the reduction of 4-nitrophenol to 4-aminophenol is 14.15×10^(-2)s^(-1),which shows a significant improvement over all previously reported Au NPs with solid supports under similar conditions.Considering the negligible porosity of theβ-CDP-N support,we purposed a"capture-catalysis-release"model to explain the high catalytic activity of Au@β-CDP-N.This explanation is supported by the guest-responsive properties ofβ-CDP-N.Moreover,the Au@β-CDP-N is easily recycled and maintained its high catalytic efficiency after seven successful cycles.

Base mediated direct C–H amination for pyrimidines synthesis from amidines and cinnamaldehydes using oxygen as green oxidants

A direct metal-free C-H amination reaction of cinnamaldehydes and amidines to realize the synthesis of polysubstituted pyrimidines was developed in the presence of base. This greener synthetic methodology provides a straightforward approach to the synthesis of a variety of pyrimidine derivatives under mild reaction condition using oxygen as sole oxidants.

Formation of heterocaryotic and homonuclear bridged–dimeric complexes on surface

The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.

Hydrogen bonding networks controllable by the substitution position of tetrathiafulvalene on the pyridine ring

Tetrathiafulvalene(TTF), as a classical building unit, has attracted considerable attention, especially its functional derivatives. Hydrogen bonding(H-bonding) networks are a class of traditional and stable nanostructures, which play an important role in two-dimensional self-assembly and multi-component co-assembly. In this paper, we studied the regulation of H-bonding networks by functional groups in TTF derivatives. The results indicate that the position of pyridine on TTF not only affects their self-assembly structures in different solvents, but also controls the H-bonding networks through different mechanisms. Both para-TTF and meta-TTF molecules show different co-assembled structures with solvents depending on whether or not the presence of carboxylic acid group. On the pre-prepared H-bonding networks formed by famous 1,3,5-tris(10-carboxydecyloxy)-benzene(TCDB) molecule, both para-TTF and meta-TTF disturbed the original network structures with different degree of TCDB deformation. The formed new H-bonding networks with or without TTF derivatives participation are mainly attributed to the position of pyridine in TTF-based molecules. These results would be important for design of exceptional and functional nanostructures starting with the design of building block.

Efficient Copper（I）-Catalyzed S-Arylation of KSCN with Aryl Halides in PEG-400

A simple and efficient protocol for Cul-catalyzed C-S bond formation of aryl halides with KSCN to symmet- rical diaryl sulfides was reported in PEG-400 without any other additives. A variety of aryl halides were converted to the corresponding diaryl sulfides in good to excellent yields. The present procedure tolerated a variety of func- tional groups and the steric hindrance of ortho-substituents on aryl halides did not affect the outcome.

Single molecular insight into steric effect on C-terminal amino acids with various hydrogen bonding sites

Amino acids are basic units to construct a protein with the assistance of various interactions.During this building process,steric hindrance derived from amino acid side groups or side chains is a factor that could not be ignored.In this contribution,adsorption behaviors of C-terminal amino acid derivatives with amino acid residues fused in 3,4,9,10-perylenetetracarboxylic dianhydride were investigated by scanning tunneling microscopy(STM)and density functional theory(DFT)calculations at various liquid/solid interfaces.STM results at 1-phenyloctane/HOPG interface show that N,N'-3,4,9,10-perylenedicarboximide(GP)and N,N'-methyl-3,4,9,10-perylenedicarboximide(AP)formed linear and herringbone structures,respectively.The driving force could be attributed to different H-bonding sites induced by steric hindrance at side groups.N,N'-Benzyl-3,4,9,10-perylenedicarboximide(PP)generates both linear and herringbone structures because steric hindrance changes the H-bonding sites between PP molecules,whereas N,N'-isopropyl-3,4,9,10-perylenedicarboximide(LP)failed to be imaged because of strong steric hindrance coming from larger side group.To further investigate the impact of steric hindrance,we utilized octanoic acid(OA)as solvent to capture the adsorption details of LP and PP.We found that OA molecules drag PP and LP molecules in a different direction to generate linear structure,impeding the molecular rotation.The structure–solvent relationship shows that the steric hindrance is brought by the large side group,which makes it easier to recognize OA molecules at the interface.These results demonstrate that steric effect plays a significant role in altering interaction sites of the compounds during the adsorption process at the liquid/solid interface.

A novel small-molecule near-infrared II fluorescence probe for orthotopic osteosarcoma imaging

Osteosarcoma is the most common primary malignant tumor of bone,particularly among children and adolescents.Advances in imaging,surgical techniques,and implants have dramatically reduced the need for amputation in the past three decades.Recently,in vivo fluorescence imaging in the second near-infrared window(NIR-II,1,000–1,700 nm)shows impressive advantages of deeper tissue penetration and higher spatial resolution,which makes it a promising tool for the early diagnosis and post-operative observation of Osteosarcoma.To the best of our knowledge,this paper is the first time to develop a novel NIR-II fluorescence probe conjugated with an osteosarcoma targeted oligopeptide for molecular tumor imaging in a xenograft orthotopic osteosarcoma mouse model.

Design, synthesis and herbicidal activities of novel self-dispreading phenoxy carboxylic acid derivatives for the control of water hyacinth floating on the water surface

A series of novel self-dispreading phenoxy carboxylic acid derivatives were designed and synthesized by I2 catalyzed one-step reaction. Their structures were confirmed by IR, NMR, and HRMS. The derivatives can self-spread and float on the water surface. Preliminary bioassays showed that some compounds, 3i–3p, had excellent herbicidal activities against water hyacinth. This strategy provided a novel approach for the water hyacinth control.

Transition-metal-switchable divergent synthesis of nitrile-containing pyrazolo[1,5-a]pyridines and indolizines

Palladium-catalyzed oxidative formal [4 + 1] annulation of pyridine-substituted acrylonitriles toward divergent fused N-heterocycles synthesis is reported. The heterodifunctionalization reaction with Cu(OAc);and urea as the nitrogen source accesses to nitrile-substituted pyrazolo[1,5-a]pyridines in moderate to good yields, while the homodifunctionalization reaction with FeBr;leads to synthesis of nitrilesubstituted indolizines in excellent yields.

Highly-efficient photosensitizer based on AIEgen-decorated porphyrin for protein photocleaving

An AIEgen decorated porphyrin(TPETPyP)was easily obtained through a one-step reaction.The bulky TPE in TPETPyP greatly impeded the intermolecularπ-πstacking of the porphyrin core,which significantly suppressed aggregation-caused quenching(ACQ)effect of TPETPyP in aqueous solution.The four pyridinium salts formed in TPETPyP also render the whole molecule water solubility,which eliminated its aggregation.TPETPyP exhibited 1O2 quantum yield as high as 0.85 in PBS.Moreover,it also showed high binding affinity to proteins,the major biotarget of 1O2.The high 1O2 quantum yield plus the great binding ability of TPETPyP toward proteins makes it a highly-efficient protein photocleaving agent.Protein electrophoresis experiments demonstrated that TPETPyP can photocleave BSA upon visible light irradiation,indicating that TPETPyP can act as a promising photosensitizer(PS)in PDT.The work here will provide a facile strategy to utilize AIEgens modified traditional PSs for photodynamic therapy(PDT).