Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6...Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
The solidification behavior and intermetallic phase evolution during homogenization annealing of an Al-Zn-Mg-Cu alloy with 0.12 wt%Ce addition were examined.The residual Al_(2)CuMg phase is completely dissolved after ...The solidification behavior and intermetallic phase evolution during homogenization annealing of an Al-Zn-Mg-Cu alloy with 0.12 wt%Ce addition were examined.The residual Al_(2)CuMg phase is completely dissolved after homogenization and is replaced by a large number of dispersed micro/nanoscaled AlCuCe enrichment phases within Al matrix.This change occurs because of the formation of a large number of finer lamellar eutectic network structures which are more easily dissolved into Al matrix during the homogenization process.In addition,the trapping of Cu atoms in the stable AlCuCe phase also prevents the formation of Al_(2)CuMg phase,leading to the complete dissolution of Al_(2)CuMg phase in the Al-Zn-MgCu alloy.The grain refinement behavior in Al alloy with Ce addition is similar to that in alloys with the addition of Sc,because of the formation of primary Ce-enriched Al_(11)Ce_(3)phase as the nucleation agent ofα(Al)during solidification.展开更多
Three novel rhodamine-based Hg^2＋ fluorescent sensors were designed and synthesized. The sensors could work in semi-aqueous solutions with nearly neutral p H and showed high selectivity and sensitivity to Hg^2＋ with...Three novel rhodamine-based Hg^2＋ fluorescent sensors were designed and synthesized. The sensors could work in semi-aqueous solutions with nearly neutral p H and showed high selectivity and sensitivity to Hg^2＋ with remarkable fluorescence enhancement. For these three sensors, the linear working range broadened（0–80, 0–100 and 0–140 μmol/L, respectively） and the sensitivity increased（7.7, 15.5 and 17.6 folds of the fluorescence enhancement and 512, 66.2 and 37.6 ppb of the detection limit） with the rising of the thiourea-unit numbers. Furthermore the sensors exhibited excellent interference immunity to multiple environmentally and biologically relevant metal ions. Pond and tap water assay showed good practicability of the sensors. The number of the bound Hg^（2＋） equaling to that of the thiourea units and the irreversible recognition process implied a new interaction way between Hg^（2＋） and the sensor.展开更多
Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthe...Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.展开更多
Polygonatum cyrtonema Hua from five different areas was used as experimental material,total saponins and total flavonoids.Colorimetric analysis method was used to compare those contents.The results showed that the con...Polygonatum cyrtonema Hua from five different areas was used as experimental material,total saponins and total flavonoids.Colorimetric analysis method was used to compare those contents.The results showed that the contents of Polygonatum polysaccharides from different areas were in the range of 8.09%~11.78%,whereas the content of total saponins and total flavonoids was quite different,which were 2.73%~5.01%and 0.21%~0.71%,respectively.In general,these Polygonatum samples had higher polysaccharide content with obvious differences for the contents of total saponins and a low contents of flavones.展开更多
A 2D plane coordination compound [Ag_2（Dpya）_2.（NO_3）_2]n was synthesized and characterized by FT-IR,elemental analysis and TG analysis.The red crystal was obtained via solvent diffusion method at room temperature...A 2D plane coordination compound [Ag_2（Dpya）_2.（NO_3）_2]n was synthesized and characterized by FT-IR,elemental analysis and TG analysis.The red crystal was obtained via solvent diffusion method at room temperature and is slightly soluble in organic solvents.Its structure was determined by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group P1 with a = 10.7995（13）,b = 7.4748（8）,c = 18.364（2） A,β = 98.916（4）o,V = 1464.5（3） A^3,Z = 2,C_（26）H_（28）Ag_2N_（10）O_6,M_r = 792.32,Dc = 1.302 Mg/m^3,F（000） = 792,μ（Mo Ka） = 1.356 mm^-1,R = 0.0575 and w R = 0.0826.The compound [Ag_2（Dpya）_2.（NO_3）_2]_n is a two-dimensional structure and there are two kinds of coordination configurations about the Ag atoms in the compound.The Ag（1） center is tetrahedrally coordinated with two O atoms of NO_3^-and two N atoms from the ligand Dpya.Meanwhile,the Ag（2） is five-coordinated by five O atoms from three NO_3^-anions.The Ag centers（Ag（1） and Ag（2）） connect to themselves as well as with each other by the bridging NO_3^-anions.And the coordination compound shows photoluminescence with an emission peak at 530 nm（λex = 450 nm） as the ligand Dpya.展开更多
A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high ...A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.展开更多
AIM To examine the effects of Acanthopanax senticosus polysaccharides(ASPS) on intestinal tight junction(TJ) disruption and nuclear factor-kappa B(NF-κB)/myosin light chain kinase(MLCK) activation in endotoxemia.METH...AIM To examine the effects of Acanthopanax senticosus polysaccharides(ASPS) on intestinal tight junction(TJ) disruption and nuclear factor-kappa B(NF-κB)/myosin light chain kinase(MLCK) activation in endotoxemia.METHODS BALB/C mice(6-8-weeks-old) received continuous intragastric gavage of ASPS for 7 d before injection of lipopolysaccharide(LPS), or received ASPS once after LPS injection. Blood and intestinal mucosal samples were collected 6 h after LPS challenge. Clinical symptoms, histological injury, intestinal permeability,TJ ultrastructure, and TJ protein expression were determined.RESULTS Compared with mice in the LPS group, pretreatment with ASPS improved clinical and histological scores by 390.9%(P < 0.05) and 57.89%(P < 0.05), respectively, and gut permeability change in endotoxemic mice was shown by a 61.93% reduction in reduced leakage of fluorescein isothiocyanate-dextran 6 h after LPS injection(P < 0.05). ASPS pretreatment also prevented LPS-induced TJ ultrastructure breakdown supported by increased electron dense materials between adjoining cells, sustained redistribution and expression of occludin(0.597 ± 0.027 vs 0.103 ± 0.009, P < 0.05) and zonula occludens-1(0.507 ± 0.032 vs 0.125 ± 0.019, P < 0.05), and suppressed activation of the NF-κB/MLCK pathway indicated by reduced expression of NF-κB, phospho-inhibitor kappa B-alpha, MLCK and phospho-myosin light-chain-2 by 16.06%(P < 0.05), 54.31%(P < 0.05), 66.10%(P < 0.05) and 64.82%(P < 0.05), respectively. CONCLUSION ASPS pretreatment may be associated with inhibition of the NF-κB/MLCK pathway and concomitant amelioration of LPS-induced TJ dysfunction of intestinal epithelium in endotoxemia.展开更多
Plasma tungstening followed by carburization(W-C duplex treatment)was performed on the Ti2AlNb-based(O phase) alloy by using the double glow plasma process to enhance its wear resistance.The microstructure and high-te...Plasma tungstening followed by carburization(W-C duplex treatment)was performed on the Ti2AlNb-based(O phase) alloy by using the double glow plasma process to enhance its wear resistance.The microstructure and high-temperature tribological behaviors of the un-treated and W-C duplex-treated samples were investigated.The results show that the duplex-treated layer is mainly composed of W2C or W6C2.54 phases and the contents of W and C elements in the alloyed layer change gradually along the depth by surface plasma duplex treatment.The diffusion depth of W is about 12μm,while the carbon atoms most exist in the depth more than 12μm.High temperature tribometer tests indicate that the friction coefficient of the W-C duplex-treated layer is approximately 1/6 that of substrate.The wear rate of the duplex-treated layer is about 28%that of the untreated one.So,plasma surface W-C duplex treatment can obviously improve the high-temperature tribological resistance of Ti2AlNb-based alloy.The tribological mechanism of the duplex-treated layer is discussed by dividing the friction process of the duplex-treated layer into three fluctuate stages.The first stage is the formation of oxide film between W-C duplex-treated layer and counterface.The second stage is the detachment of oxide film,acting as "the third body" .The last stage is the period that the friction and wear occur between the compact particle layer and counterface.展开更多
The purpose of this paper is to investigate heat dissipation performance of porous copper with long cylindrical pores fabricated by a unidirectional solidification method. Three samples with porosity of 29.87%, 34.47%...The purpose of this paper is to investigate heat dissipation performance of porous copper with long cylindrical pores fabricated by a unidirectional solidification method. Three samples with porosity of 29.87%, 34.47% and 50.98% were chosen and cut into size of 60 mm （length） × 26 mm （width） × 2 mm （thickness） along the vertical direction of pore axis. Their heat dissipation performance was evaluated by a nonsteady method in air and compared to those of not only bulk copper but also bored coppers with porosity of 30.61% and 32.20%. It is found that the porous copper dissipated heat faster by a forced air convection than that by natural convection from 80 ℃ to room temperature and both porosity and pore size play an important role in the performance for the porous copper. Furthermore, the heat dissipation rate is higher when the forced air was circulated along the specimens than that perpendicular to the specimens for the porous copper. It is revealed that porous copper with bigger porosity and a proper pore size possesses a higher heat dissipation rate. It is concluded that the porous copper with elongated cylindrical pores has larger heat dissipation performance than both the bulk copper and the bored copper, which is attributed to its higher specific surface area. Application of the porous copper for heat dissipation is promising.展开更多
The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of ar...The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.展开更多
The occurrence of arc interference between the adjacent arcs becomes an important problem in triple-electrode high speed CO2 fillet welding. To clarify this problem, polarities effects on arc interference were investi...The occurrence of arc interference between the adjacent arcs becomes an important problem in triple-electrode high speed CO2 fillet welding. To clarify this problem, polarities effects on arc interference were investigated. The experimental results and theoretical analysis showed that the reverse magnetic field generated by the middle wire （ DCEN or DCEP ） decreased the arc deflection due to arc interference. The average arc voltage fluctuations induced by DCEP/DECN/DCEP and DCEN/DCEP/DCEN were smaller than those induced by the other polarities.展开更多
The stability of ultrathin polymer films plays a crucial role in their technological applications.Here,we systematically investigated the influence of interfacial adsorption in physical aging and the stability of thin...The stability of ultrathin polymer films plays a crucial role in their technological applications.Here,we systematically investigated the influence of interfacial adsorption in physical aging and the stability of thin polymer films in the solvent-induced process.We further identify the stability mechanism from the theory of thin film stability.Our results show that the aging temperature and film thickness can strongly influence the stability of thin PS films in acetone vapor.Physical aging can greatly improve the stability of thin polymer films when the aging temperature T_(aging1)>T_(g).A thinner PS film more quickly reaches a stable state via physical aging.At short aging time,the formation of the adsorbed layer can reduce the polar interaction;however,it slightly influences the stability of thin polymer films in the solvent-induced process.At later aging stage,the conformational rearrangement of the polymer chains induced by the interfacial effect at the aging temperature Taging1 plays an important role in stabilizing the thin polymer films.However,at T_(aging2)<T_(g),the process of physical aging slightly influences the stability of the thin polymer films.The formation of the adsorbed layer at Taging2 can reduce the short-range polar interaction of the thin film system and cannot suppress the instability of thin polymer films in the solvent-induced process.These results provide further insight into the stable mechanism of thin polymer films in the solvent-induced process.展开更多
A reexamination of the structural constraints on the amino acid-functionalized heteropolymolybdates has afforded four polyanions,namely the double-layer [(SeO_(3))_(2)Mo_(12)O_(36)(CH_(3)COO)_(3)]^(7-)(1),[(SeO_(3))_(...A reexamination of the structural constraints on the amino acid-functionalized heteropolymolybdates has afforded four polyanions,namely the double-layer [(SeO_(3))_(2)Mo_(12)O_(36)(CH_(3)COO)_(3)]^(7-)(1),[(SeO_(3))_(1.3)(HPO_(3))_(0.7)Mo_(12)O_(36)(NH_(3)CH_(2)COO)_(3)]^(4-)(2),[(SeO_(3))_(1.4)(HPO_(3))_(0.6)Mo_(12)O_(36)(LNH_(3)C_(2)H_(3)OHCOO)_(3)]^(4-)(3),and the mono-layer [(SeO_(3))-Mo_6O_(18)(L-NH_(3)C_(2)H_(3)OHCOO)_(3)]^(2-)(4),which were crystallized as the hydrated ammonium salts.展开更多
Radiotherapy(RT)is one of the most feasible and routinely used therapeutic modalities for treating malignant tumors.In particular,immune responses triggered by RT,known as radio-immunotherapy,can partially inhibit the...Radiotherapy(RT)is one of the most feasible and routinely used therapeutic modalities for treating malignant tumors.In particular,immune responses triggered by RT,known as radio-immunotherapy,can partially inhibit the growth of distantly spreading tumors and recurrent tumors.How-ever,the safety and efficacy of radio-immunotherapy is impeded by the radio-resistance and poor immu-nogenicity of tumor.Herein,we report oxaliplatin(IV)-iron bimetallic nanoparticles(OXA/Fe NPs)as cascade sensitizing amplifiers for low-dose and robust radio-immunotherapy.The OXA/Fe NPs exhibit tumor-specific accumulation and activation of OXA(I)and Fe^(2+)in response to the reductive and acidic microenvironment within tumor cells.The cascade reactions of the released metallic drugs can sensitize RT by inducing DNA damage,increasing ROS and O_(2) levels,and amplifying the immunogenic cell death(ICD)effect after RT to facilitate potent immune activation.As a result,OXA/Fe NPs-based low-dose RT triggered a robust immune response and inhibited the distant and metastatic tumors effectively by a strong abscopal effect.Moreover,a long-term immunological memory effect to protect mice from tumor rechal-lenging is observed.Overall,the bimetallic NPs-based cascade sensitizing amplifier system offers an effi-cient radio-immunotherapy regimen that addresses the key challenges.展开更多
An iron film percolation system is fabricated by vapour-phase deposition on fracture surfaces of α-Al2O3 ceramics. The zero-field-cooled （ZFC） and field-cooled （FC） magnetization measurement reveals that the magn...An iron film percolation system is fabricated by vapour-phase deposition on fracture surfaces of α-Al2O3 ceramics. The zero-field-cooled （ZFC） and field-cooled （FC） magnetization measurement reveals that the magnetic phase of the film samples evolve from a high-temperature ferromagnetic state to a low-temperature spin-glass-like state, which is also demonstrated by the temperature-dependent ac susceptibility of the iron films. The temperature dependence of the exchange bias field He of the iron film exhibits a minimum peak around the temperature T=5 K, which is independent of the magnitude of the cooling field Hcf. However, for T 〉 10K, （1） He is always negative when Hcf=2kOe and （2） for Hcf= 20 kOe （1Oe≈80 A/m）, He changes from negative to positive values as T increases. Our experimental results show that the anomalous hysteresis properties mainly result from the oxide surfaces of the films with spin-glass-like phase.展开更多
By metalloscopy,scanning electron microscope,X-ray diffraction,electron probe,salt water erosion and hot steam erosion,the microstructures and the aging resistance of zinc alloy ZA-27 with different contents of yttriu...By metalloscopy,scanning electron microscope,X-ray diffraction,electron probe,salt water erosion and hot steam erosion,the microstructures and the aging resistance of zinc alloy ZA-27 with different contents of yttrium were studied. The results show that with optimum addition of yttrium in the alloy ZA-27 the fine YAl_3 phase forms. The fine YAl_3 granules can act as the condensation nuclei of α phase and the number of the α phase′s nuclei increases greatly and the growth of the nuclei comes in for restrict during the crystallization and the alloy′s grains become fine and the segregation reduces. In addition,yttrium also combines with zinc and the fine dispersion Y-Zn phase forms which improves grain boundary conditions and the alloy′s aging resistance. But when the content of yttrium is overmuch some YAl_3 granules grow to be lumpy,so the fine and close texture of the alloy′s boundaries is damaged and the proportion of the interface among the phases increase which brings a decline in the alloy′s resistance to corrosion.展开更多
A series of lanthanide complexes [Ln(4-Cl-2-MOBA)3phen]2(Ln=Sm(1), Nd(2), Ho(3), Eu(4), Dy(5), and Tb(6); 4-Cl-2-MOBA=4-chloro-2-methoxybenzoate, phen=1,10-phenanthroline) were synthesized and characterized. The singl...A series of lanthanide complexes [Ln(4-Cl-2-MOBA)3phen]2(Ln=Sm(1), Nd(2), Ho(3), Eu(4), Dy(5), and Tb(6); 4-Cl-2-MOBA=4-chloro-2-methoxybenzoate, phen=1,10-phenanthroline) were synthesized and characterized. The single-crystal X-ray diffraction demonstrates that 1–3 are isomorphous, which present dimeric structures with four 4-Cl-2-MOBA anions function as bridging ligands. Complexes 1 and 4–6 display their characteristic luminescence emission bands of central Ln3?ions. The heat capacities, the thermodynamic functions and the thermogravimetry–Fourier transform infrared spectra of gaseous products of complexes 1–6 were investigated.Their non-isothermal kinetics of the second decomposition stage was studied by the integral isoconversional non-linear method and Stark method. Furthermore, 1–6 exhibited excellent antibacterial activity against Candida albicans,Escherichia coli and Staphylococcus aureu.展开更多
Five new binuclear lanthanide compounds [Ln(2,4-DClBA)3phen]2(Ln = Pr(1), Eu(2), Tb(3), Ho(4) and Er(5); 2,4-DClBA = 2,4-dichlorobenzoate; phen = 1,10-phenanthroline) have been synthesized and structurally characteriz...Five new binuclear lanthanide compounds [Ln(2,4-DClBA)3phen]2(Ln = Pr(1), Eu(2), Tb(3), Ho(4) and Er(5); 2,4-DClBA = 2,4-dichlorobenzoate; phen = 1,10-phenanthroline) have been synthesized and structurally characterized by X-ray crystallography. And all of them were carefully investigated by elemental analysis, molar conductance, IR, UV and TG/DSC-FTIR technology. Single-crystal X-ray diffraction studies revealed that compounds 1–5 were binuclear molecules with an inversion center and the Ln3+ ions contained two kinds of coordination environment that was a distorted monocapped square-antiprism in the compounds 1–2, and a distorted square-antiprism geometry in the compounds 3–5. The 3D surface graphs for the FTIR spectra of gaseous products for the compounds 1–5 were recorded using simultaneous TG/DSC-FTIR technique which is intended to further analysis of the thermal decomposition processes. Hence the gaseous products were identified by the solved single IR spectra obtained at different temperatures from the 3D surface graphs. Furthermore, the Eu(Ш) and Tb(Ш) ternary compounds exhibited intense luminescence under the radiation of UV light. And the results for antimicrobial test show that these compounds exhibit good bacteriostatic activity against Staphylococcus aureus, and better antimicrobial activity against Escherichia coli and Candida albicans.展开更多
文摘Two novel lanthanide complexes,[Sm_(2)(BA)_(6)(4-OH-terpy)_(2)]·2H_(2)O·2EtOH(1)and[Pr_(2)(BA)_(6)(4-OH-terpy)_(2)(H_(2)O)_(2)]·HBA·H_(2)O(2),where HBA=benzoic acid,4-OH-terpy=4-hydroxy-2,2'∶6',2″-terpyridine,were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4-OH-terpy.During the synthesis,4-OH-terpy was involved in the reaction as a neutral ligand,while HBA,in its deprotonated form(BA-),coordinated with the lanthanide ions as an acidic ligand.The crystal structures of these two complexes were precisely determined by single-crystal X-ray diffraction.Elemental analysis,infrared and Raman spectroscopy,and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes.The single-crystal X-ray diffraction data indicate that,despite their structural differences,both complexes belong to the triclinic crystal system P1 space group.The central lanthanide ions have the same coordination number but exhibit different coordination environments.To comprehensively evaluate the thermal stability of these two complexes,comprehensive tests including thermogravimetric analysis,differential thermogravimetric analysis,differential scanning calorimetry,Fourier transform infrared spectroscopy,and mass spectrometry were conducted.Meanwhile,an in-depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes.In addition,studies of the fluorescence properties of complex1 showed that it exhibited fluorescence emission matching the Sm^(3+)characteristic transition.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
基金the Natural Science Foundation of Shandong Province,China(Nos.ZR2017PEM005 and ZR2017MEM005)the Project of Scientific Research Development of Shandong Universities China(Nos.J17KA043 and J17KB076)+2 种基金the Key Research Program of Shandong Province,China(No.2015GGX102021)the Foundation for Applied Science and Technology Research and Development Program of Guangdong Province,China(No.2015B090926007)2015 Shandong Province Project of Outstanding Subject Talent Group。
文摘The solidification behavior and intermetallic phase evolution during homogenization annealing of an Al-Zn-Mg-Cu alloy with 0.12 wt%Ce addition were examined.The residual Al_(2)CuMg phase is completely dissolved after homogenization and is replaced by a large number of dispersed micro/nanoscaled AlCuCe enrichment phases within Al matrix.This change occurs because of the formation of a large number of finer lamellar eutectic network structures which are more easily dissolved into Al matrix during the homogenization process.In addition,the trapping of Cu atoms in the stable AlCuCe phase also prevents the formation of Al_(2)CuMg phase,leading to the complete dissolution of Al_(2)CuMg phase in the Al-Zn-MgCu alloy.The grain refinement behavior in Al alloy with Ce addition is similar to that in alloys with the addition of Sc,because of the formation of primary Ce-enriched Al_(11)Ce_(3)phase as the nucleation agent ofα(Al)during solidification.
基金supported by the National Natural Science Foundation of China (No. 21074085)the Priority Academic Program Development of Jiangsu Higher Education Institutions+1 种基金the Graduate Student Innovation Training Project of Jiangsu Province (No. KYLX_1241)the State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials
文摘Three novel rhodamine-based Hg^2＋ fluorescent sensors were designed and synthesized. The sensors could work in semi-aqueous solutions with nearly neutral p H and showed high selectivity and sensitivity to Hg^2＋ with remarkable fluorescence enhancement. For these three sensors, the linear working range broadened（0–80, 0–100 and 0–140 μmol/L, respectively） and the sensitivity increased（7.7, 15.5 and 17.6 folds of the fluorescence enhancement and 512, 66.2 and 37.6 ppb of the detection limit） with the rising of the thiourea-unit numbers. Furthermore the sensors exhibited excellent interference immunity to multiple environmentally and biologically relevant metal ions. Pond and tap water assay showed good practicability of the sensors. The number of the bound Hg^（2＋） equaling to that of the thiourea units and the irreversible recognition process implied a new interaction way between Hg^（2＋） and the sensor.
基金supported by the National Natural Science Foundation of China(21073053,21473049)the Natural Science Foundation of Hebei Province,China(B2016205207)
文摘Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.
文摘Polygonatum cyrtonema Hua from five different areas was used as experimental material,total saponins and total flavonoids.Colorimetric analysis method was used to compare those contents.The results showed that the contents of Polygonatum polysaccharides from different areas were in the range of 8.09%~11.78%,whereas the content of total saponins and total flavonoids was quite different,which were 2.73%~5.01%and 0.21%~0.71%,respectively.In general,these Polygonatum samples had higher polysaccharide content with obvious differences for the contents of total saponins and a low contents of flavones.
基金the sponsorship and financial support from the Key Laboratory of Organic Synthesis of Jiangsu Province
文摘A 2D plane coordination compound [Ag_2（Dpya）_2.（NO_3）_2]n was synthesized and characterized by FT-IR,elemental analysis and TG analysis.The red crystal was obtained via solvent diffusion method at room temperature and is slightly soluble in organic solvents.Its structure was determined by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group P1 with a = 10.7995（13）,b = 7.4748（8）,c = 18.364（2） A,β = 98.916（4）o,V = 1464.5（3） A^3,Z = 2,C_（26）H_（28）Ag_2N_（10）O_6,M_r = 792.32,Dc = 1.302 Mg/m^3,F（000） = 792,μ（Mo Ka） = 1.356 mm^-1,R = 0.0575 and w R = 0.0826.The compound [Ag_2（Dpya）_2.（NO_3）_2]_n is a two-dimensional structure and there are two kinds of coordination configurations about the Ag atoms in the compound.The Ag（1） center is tetrahedrally coordinated with two O atoms of NO_3^-and two N atoms from the ligand Dpya.Meanwhile,the Ag（2） is five-coordinated by five O atoms from three NO_3^-anions.The Ag centers（Ag（1） and Ag（2）） connect to themselves as well as with each other by the bridging NO_3^-anions.And the coordination compound shows photoluminescence with an emission peak at 530 nm（λex = 450 nm） as the ligand Dpya.
基金financially supported by the National Natural Science Foundation of China(No.22001066)the Natural Science Foundation of Hunan Province(Nos.2021JJ40049 and 2022JJ20007)+3 种基金the Science and Technology Innovation Program of Hunan Province(No.2022RC1115)J.Du acknowledges the Science and Technology Project of Hebei Education Department(No.QN2023049)Science Foundation of Hebei Normal University(No.L2023B51)TianHe-2(LvLiang,China)Cloud Computing Center for support。
文摘A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.
文摘AIM To examine the effects of Acanthopanax senticosus polysaccharides(ASPS) on intestinal tight junction(TJ) disruption and nuclear factor-kappa B(NF-κB)/myosin light chain kinase(MLCK) activation in endotoxemia.METHODS BALB/C mice(6-8-weeks-old) received continuous intragastric gavage of ASPS for 7 d before injection of lipopolysaccharide(LPS), or received ASPS once after LPS injection. Blood and intestinal mucosal samples were collected 6 h after LPS challenge. Clinical symptoms, histological injury, intestinal permeability,TJ ultrastructure, and TJ protein expression were determined.RESULTS Compared with mice in the LPS group, pretreatment with ASPS improved clinical and histological scores by 390.9%(P < 0.05) and 57.89%(P < 0.05), respectively, and gut permeability change in endotoxemic mice was shown by a 61.93% reduction in reduced leakage of fluorescein isothiocyanate-dextran 6 h after LPS injection(P < 0.05). ASPS pretreatment also prevented LPS-induced TJ ultrastructure breakdown supported by increased electron dense materials between adjoining cells, sustained redistribution and expression of occludin(0.597 ± 0.027 vs 0.103 ± 0.009, P < 0.05) and zonula occludens-1(0.507 ± 0.032 vs 0.125 ± 0.019, P < 0.05), and suppressed activation of the NF-κB/MLCK pathway indicated by reduced expression of NF-κB, phospho-inhibitor kappa B-alpha, MLCK and phospho-myosin light-chain-2 by 16.06%(P < 0.05), 54.31%(P < 0.05), 66.10%(P < 0.05) and 64.82%(P < 0.05), respectively. CONCLUSION ASPS pretreatment may be associated with inhibition of the NF-κB/MLCK pathway and concomitant amelioration of LPS-induced TJ dysfunction of intestinal epithelium in endotoxemia.
基金Project supported by the Scientific Research Foundation of Nanjing University of Information and Technology,China
文摘Plasma tungstening followed by carburization(W-C duplex treatment)was performed on the Ti2AlNb-based(O phase) alloy by using the double glow plasma process to enhance its wear resistance.The microstructure and high-temperature tribological behaviors of the un-treated and W-C duplex-treated samples were investigated.The results show that the duplex-treated layer is mainly composed of W2C or W6C2.54 phases and the contents of W and C elements in the alloyed layer change gradually along the depth by surface plasma duplex treatment.The diffusion depth of W is about 12μm,while the carbon atoms most exist in the depth more than 12μm.High temperature tribometer tests indicate that the friction coefficient of the W-C duplex-treated layer is approximately 1/6 that of substrate.The wear rate of the duplex-treated layer is about 28%that of the untreated one.So,plasma surface W-C duplex treatment can obviously improve the high-temperature tribological resistance of Ti2AlNb-based alloy.The tribological mechanism of the duplex-treated layer is discussed by dividing the friction process of the duplex-treated layer into three fluctuate stages.The first stage is the formation of oxide film between W-C duplex-treated layer and counterface.The second stage is the detachment of oxide film,acting as "the third body" .The last stage is the period that the friction and wear occur between the compact particle layer and counterface.
基金The financial supports of Cooperative Foundation between Industry,Colleges or Scientific Institutes and Relevant Issuesfrom Guangdong Province(00124720225267058)Natural Science of Foundation from Liaoning Province(No.201102222)Science and Technology Project(No.2010AZ2010)from Jiaxing City
文摘The purpose of this paper is to investigate heat dissipation performance of porous copper with long cylindrical pores fabricated by a unidirectional solidification method. Three samples with porosity of 29.87%, 34.47% and 50.98% were chosen and cut into size of 60 mm （length） × 26 mm （width） × 2 mm （thickness） along the vertical direction of pore axis. Their heat dissipation performance was evaluated by a nonsteady method in air and compared to those of not only bulk copper but also bored coppers with porosity of 30.61% and 32.20%. It is found that the porous copper dissipated heat faster by a forced air convection than that by natural convection from 80 ℃ to room temperature and both porosity and pore size play an important role in the performance for the porous copper. Furthermore, the heat dissipation rate is higher when the forced air was circulated along the specimens than that perpendicular to the specimens for the porous copper. It is revealed that porous copper with bigger porosity and a proper pore size possesses a higher heat dissipation rate. It is concluded that the porous copper with elongated cylindrical pores has larger heat dissipation performance than both the bulk copper and the bored copper, which is attributed to its higher specific surface area. Application of the porous copper for heat dissipation is promising.
文摘The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.
文摘The occurrence of arc interference between the adjacent arcs becomes an important problem in triple-electrode high speed CO2 fillet welding. To clarify this problem, polarities effects on arc interference were investigated. The experimental results and theoretical analysis showed that the reverse magnetic field generated by the middle wire （ DCEN or DCEP ） decreased the arc deflection due to arc interference. The average arc voltage fluctuations induced by DCEP/DECN/DCEP and DCEN/DCEP/DCEN were smaller than those induced by the other polarities.
基金supported by the Science Challenge Project(No.TZ2018004)the Fundamental Research Funds for the Central Universities(No.2232019D3-10)+1 种基金the National Natural Science Foundation of China(Nos.51473168,21674113,21334007,21790340)the Programs of Chinese Academy of Sciences(Nos.QYZDY-SSW-SLH027,YJKYYQ20190084).
文摘The stability of ultrathin polymer films plays a crucial role in their technological applications.Here,we systematically investigated the influence of interfacial adsorption in physical aging and the stability of thin polymer films in the solvent-induced process.We further identify the stability mechanism from the theory of thin film stability.Our results show that the aging temperature and film thickness can strongly influence the stability of thin PS films in acetone vapor.Physical aging can greatly improve the stability of thin polymer films when the aging temperature T_(aging1)>T_(g).A thinner PS film more quickly reaches a stable state via physical aging.At short aging time,the formation of the adsorbed layer can reduce the polar interaction;however,it slightly influences the stability of thin polymer films in the solvent-induced process.At later aging stage,the conformational rearrangement of the polymer chains induced by the interfacial effect at the aging temperature Taging1 plays an important role in stabilizing the thin polymer films.However,at T_(aging2)<T_(g),the process of physical aging slightly influences the stability of the thin polymer films.The formation of the adsorbed layer at Taging2 can reduce the short-range polar interaction of the thin film system and cannot suppress the instability of thin polymer films in the solvent-induced process.These results provide further insight into the stable mechanism of thin polymer films in the solvent-induced process.
基金financially supported by the National Natural Science Foundation of China (No. 22001066)the Natural Science Foundation of Hunan Province (Nos. 2021JJ40049 and 2022JJ20007)+1 种基金the Scientific Research Foundation of the Education Department of Hunan Province (No. 21B0028)the Science and Technology Innovation Program of Hunan Province (No. 2022RC1115)。
文摘A reexamination of the structural constraints on the amino acid-functionalized heteropolymolybdates has afforded four polyanions,namely the double-layer [(SeO_(3))_(2)Mo_(12)O_(36)(CH_(3)COO)_(3)]^(7-)(1),[(SeO_(3))_(1.3)(HPO_(3))_(0.7)Mo_(12)O_(36)(NH_(3)CH_(2)COO)_(3)]^(4-)(2),[(SeO_(3))_(1.4)(HPO_(3))_(0.6)Mo_(12)O_(36)(LNH_(3)C_(2)H_(3)OHCOO)_(3)]^(4-)(3),and the mono-layer [(SeO_(3))-Mo_6O_(18)(L-NH_(3)C_(2)H_(3)OHCOO)_(3)]^(2-)(4),which were crystallized as the hydrated ammonium salts.
基金This work is supported by grants from the National Natural Science Foundation of China(Nos.22275081,and 82372117)Guangdong Basic and Applied Basic Research Foundation(2021B1515120065,China)+2 种基金Guangzhou Science and Technology Bureau(202206010068)the Natural Science Foundation of Hebei Province(E2023205004,China)China Postdoctoral Science Foundation(2022M711532 and 2022T150302).
文摘Radiotherapy(RT)is one of the most feasible and routinely used therapeutic modalities for treating malignant tumors.In particular,immune responses triggered by RT,known as radio-immunotherapy,can partially inhibit the growth of distantly spreading tumors and recurrent tumors.How-ever,the safety and efficacy of radio-immunotherapy is impeded by the radio-resistance and poor immu-nogenicity of tumor.Herein,we report oxaliplatin(IV)-iron bimetallic nanoparticles(OXA/Fe NPs)as cascade sensitizing amplifiers for low-dose and robust radio-immunotherapy.The OXA/Fe NPs exhibit tumor-specific accumulation and activation of OXA(I)and Fe^(2+)in response to the reductive and acidic microenvironment within tumor cells.The cascade reactions of the released metallic drugs can sensitize RT by inducing DNA damage,increasing ROS and O_(2) levels,and amplifying the immunogenic cell death(ICD)effect after RT to facilitate potent immune activation.As a result,OXA/Fe NPs-based low-dose RT triggered a robust immune response and inhibited the distant and metastatic tumors effectively by a strong abscopal effect.Moreover,a long-term immunological memory effect to protect mice from tumor rechal-lenging is observed.Overall,the bimetallic NPs-based cascade sensitizing amplifier system offers an effi-cient radio-immunotherapy regimen that addresses the key challenges.
基金supported by the National Natural Science Foundation of China (Grant Nos 10574109 and 50701037)the Zhejiang Provincial Science and Technology Department of China (Grant No 2005C24008)
文摘An iron film percolation system is fabricated by vapour-phase deposition on fracture surfaces of α-Al2O3 ceramics. The zero-field-cooled （ZFC） and field-cooled （FC） magnetization measurement reveals that the magnetic phase of the film samples evolve from a high-temperature ferromagnetic state to a low-temperature spin-glass-like state, which is also demonstrated by the temperature-dependent ac susceptibility of the iron films. The temperature dependence of the exchange bias field He of the iron film exhibits a minimum peak around the temperature T=5 K, which is independent of the magnitude of the cooling field Hcf. However, for T 〉 10K, （1） He is always negative when Hcf=2kOe and （2） for Hcf= 20 kOe （1Oe≈80 A/m）, He changes from negative to positive values as T increases. Our experimental results show that the anomalous hysteresis properties mainly result from the oxide surfaces of the films with spin-glass-like phase.
文摘By metalloscopy,scanning electron microscope,X-ray diffraction,electron probe,salt water erosion and hot steam erosion,the microstructures and the aging resistance of zinc alloy ZA-27 with different contents of yttrium were studied. The results show that with optimum addition of yttrium in the alloy ZA-27 the fine YAl_3 phase forms. The fine YAl_3 granules can act as the condensation nuclei of α phase and the number of the α phase′s nuclei increases greatly and the growth of the nuclei comes in for restrict during the crystallization and the alloy′s grains become fine and the segregation reduces. In addition,yttrium also combines with zinc and the fine dispersion Y-Zn phase forms which improves grain boundary conditions and the alloy′s aging resistance. But when the content of yttrium is overmuch some YAl_3 granules grow to be lumpy,so the fine and close texture of the alloy′s boundaries is damaged and the proportion of the interface among the phases increase which brings a decline in the alloy′s resistance to corrosion.
基金supported by the National Natural Science Foundation of China (21073053, 21173067 and 20773034)the Natural Science Foundation of Hebei Province (B2012205022, B2011205037)
文摘A series of lanthanide complexes [Ln(4-Cl-2-MOBA)3phen]2(Ln=Sm(1), Nd(2), Ho(3), Eu(4), Dy(5), and Tb(6); 4-Cl-2-MOBA=4-chloro-2-methoxybenzoate, phen=1,10-phenanthroline) were synthesized and characterized. The single-crystal X-ray diffraction demonstrates that 1–3 are isomorphous, which present dimeric structures with four 4-Cl-2-MOBA anions function as bridging ligands. Complexes 1 and 4–6 display their characteristic luminescence emission bands of central Ln3?ions. The heat capacities, the thermodynamic functions and the thermogravimetry–Fourier transform infrared spectra of gaseous products of complexes 1–6 were investigated.Their non-isothermal kinetics of the second decomposition stage was studied by the integral isoconversional non-linear method and Stark method. Furthermore, 1–6 exhibited excellent antibacterial activity against Candida albicans,Escherichia coli and Staphylococcus aureu.
基金supported by the National Natural Science Foundation of China(21073053,21141002,20773034)the Natural Science Foundation of Hebei Province(B2012205022)
文摘Five new binuclear lanthanide compounds [Ln(2,4-DClBA)3phen]2(Ln = Pr(1), Eu(2), Tb(3), Ho(4) and Er(5); 2,4-DClBA = 2,4-dichlorobenzoate; phen = 1,10-phenanthroline) have been synthesized and structurally characterized by X-ray crystallography. And all of them were carefully investigated by elemental analysis, molar conductance, IR, UV and TG/DSC-FTIR technology. Single-crystal X-ray diffraction studies revealed that compounds 1–5 were binuclear molecules with an inversion center and the Ln3+ ions contained two kinds of coordination environment that was a distorted monocapped square-antiprism in the compounds 1–2, and a distorted square-antiprism geometry in the compounds 3–5. The 3D surface graphs for the FTIR spectra of gaseous products for the compounds 1–5 were recorded using simultaneous TG/DSC-FTIR technique which is intended to further analysis of the thermal decomposition processes. Hence the gaseous products were identified by the solved single IR spectra obtained at different temperatures from the 3D surface graphs. Furthermore, the Eu(Ш) and Tb(Ш) ternary compounds exhibited intense luminescence under the radiation of UV light. And the results for antimicrobial test show that these compounds exhibit good bacteriostatic activity against Staphylococcus aureus, and better antimicrobial activity against Escherichia coli and Candida albicans.
