Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their s...Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.展开更多
Low-cost thermal insulation porous ceramics with uniform pore diameter and low bulk density were prepared with soda-ash dregs and felsic tailings.We investigated the effect of temperature,foaming agent,fluxing agent,A...Low-cost thermal insulation porous ceramics with uniform pore diameter and low bulk density were prepared with soda-ash dregs and felsic tailings.We investigated the effect of temperature,foaming agent,fluxing agent,Al_(2)O_(3)and CaO content on the pore structure and crystal phase of porous ceramics.The effect of Ca^(2+)in soda-ash dregs on the preparation of quartz-feldspar based porous ceramics was studied.The results showed that the contribution of Ca^(2+)to the preparation of porous ceramics in this system was mainly to accelerate the Si-O bond fracture and reduce the sintering temperature at the initial stage of sintering,which destroyed the needle-like feldspar in the high temperature melt and reduced the melt viscosity,thus reduced the foaming resistance and promoted the porous products with uniform pore size distribution.The Ca^(2+)content on the high side can participate in the formation of crystals in sintering.The generated needle-like diopside and augite,which have small length-diameter ratio,will negligibly change in the viscosity of melt at high temperatures,and their inhibition effect on pores is not as good as that of feldspar with large length-diameter ratio,resulting in the merger and collapse of pores.But the increase of diopside and augite can improve the compressive strength of porous products to some extent.Porous ceramic products containing needle-like feldspar phase can be prepared by using two kinds of solid waste,which can improve the compressive strength of the products and reduce the raw material cost and energy consumption while comprehensively utilizing the double solid waste.The optimal product has a bulk density of 0.45 g/cm^(3),a compressive strength of 3.17 MPa,and a thermal conductivity of 0.11 W/(m·K).展开更多
Quantum chemical calculations on some possible equilibrium geometries of C24O2 isomers derived from C24 （D6） and C24O have been performed using density functional theory （DFT） method. The geometric and electronic ...Quantum chemical calculations on some possible equilibrium geometries of C24O2 isomers derived from C24 （D6） and C24O have been performed using density functional theory （DFT） method. The geometric and electronic structures as well as the relative energies and thermal stabilities of various C24O2 isomers at the ground state have been calculated at the B3LYP/6-31G（d） level of theory. And the 1,4,2,5-C24O2 isomer was found to be the most stable geometry where two oxygen atoms were added to the longest carbon-carbon bonds in the same pentagon from a thermodynamic point of view. Based on the optimized neutral geometries, the vertical ionization potential and vertical electron affinity have been obtained. Meanwhile, the vibrational frequencies, IR spectrum, and 13C chemical shifts of various C24O2 isomers have been calculated and analyzed.展开更多
Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structu...Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.展开更多
Two coordination polymers, namely {[Ni（cpna）（H2biim）（H2O）]·H2O}n （1） and {[Mn（cpna）（H2biim）]·H2O}n （2） （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, H2biim = 2,2＇- biimidazole）,have been ...Two coordination polymers, namely {[Ni（cpna）（H2biim）（H2O）]·H2O}n （1） and {[Mn（cpna）（H2biim）]·H2O}n （2） （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, H2biim = 2,2＇- biimidazole）,have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional （1D） step-like chain structure, which further builds a three-dimensional （3D） supramolecular architecture via O–HAAAO and N–HAAAO hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional （1D） double chain structure, which is further assembled into a 3D supramolecular framework by N–HAAAO hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni（II） centers, with g = 2.11 and J = –1.87 cm^-1.展开更多
In order to synthesize the targeting drug carrier system,magnetic chitosan-5-fluorouracil nano-particles were prepared by using 5-fluorouracil(5-Fu)as model drug,Fe3O4 nano-particles as kernel,chitosan as enveloping m...In order to synthesize the targeting drug carrier system,magnetic chitosan-5-fluorouracil nano-particles were prepared by using 5-fluorouracil(5-Fu)as model drug,Fe3O4 nano-particles as kernel,chitosan as enveloping material and glutaraldehyde as cross linking agent through ultrasonic technique.The morphology of the magnetic chitosan-5-Fu nano-particles was observed with a transmission electron microscope(TEM).The results showed that magnetic chitosan-5-Fu nano-particles were prepared in spherical structure with a size range of 50-60 nm.The delivering capacity and drug releasing properties of magnetic chitosan-5-Fu nano-particles were investigated by UV-vis spectrum analysis.The results showed that the loading capacity was 13.4%and the cumulative release percentage in the phosphate buffer(pH=7.2)solutions was 68%in 30 h.These data indicate that the wrapped drug of magnetic chitosan-5-Fu nano-particles was slowly-released.The magnetic response of magnetic chitosan-5-Fu nano-particles was studied by UV-vis spectrometer to detect the changes of solution absorbance.Without external magnetic field,the nano-particle deposition rate was slow.When being subjected to 8 mT magnetic field,the particle sedimentation rate was increased rapidly.The results showed that magnetic chitosan-5-Fu nano-particles have a magnetic stability and strong targeting characteristics.展开更多
Depigmenting agents were solvent-extracted and purified by preparative and analytical HPLC from three Chinese plants; Chrysanthemum morifolium Ramat（ Xizang Caijuhua）, Rhodiola sachalinensis, and Terminalia chebula ...Depigmenting agents were solvent-extracted and purified by preparative and analytical HPLC from three Chinese plants; Chrysanthemum morifolium Ramat（ Xizang Caijuhua）, Rhodiola sachalinensis, and Terminalia chebula Retzius. Four fractions obtained from the ethyl ether layer of C. m. Rama and two fractions from the ethyl acetate layer of Rhodiola salientness show depigmenting effects. At 8 200, the ethyl acetate layers of Chrysanthemum morifolium Ramat, Rhodiola sachalinensis and the methanol extract of Terminalia chebula Retzius, can inhibit the melanin production of mouse B16 melanoma cells by 92%, 60% and 90%, respectively, whereas 46% inhibition was observed by commercially available depigmenting agents（arbutin）. These results show the potential of these three Chinese plants as a novel resource for depigmenting agents in the cosmetic industry.展开更多
AIM: To investigate the performance of Gadofluorine P-enhanced magnetic resonance imaging(MRI) on the diagnosis of diabetes in a streptozotocin(STZ)-induced diabetic rat model.METHODS: Fischer 344 rats were treated wi...AIM: To investigate the performance of Gadofluorine P-enhanced magnetic resonance imaging(MRI) on the diagnosis of diabetes in a streptozotocin(STZ)-induced diabetic rat model.METHODS: Fischer 344 rats were treated with STZ.Rats not treated with STZ served as controls. T1-weighted MRI was performed using a 3T scanner before and after the injection of Gd-DOTA or Gadofluorine P(6 diabetic rats, 5 controls). The normalized signal intensity(SI) and the enhancement ratio(ER) of the pancreas were measured at each time point, and the values were compared between the normal and diabetic rats using the Mann-Whitney test. In addition,the values were correlated with the mean islet number.Optimal cut-off values were calculated using a positive test based on receiver operating characteristics.Intrapancreatic Gd concentration after the injection of each contrast media was measured using laser ablation-inductively coupled plasma-mass spectrometry in a separate set of rats(4 diabetic rats, 4 controls for Gadofluorine P; 2, 2 for Gd-DOTA).RESULTS: The normalized SI and ER of the pancreas using Gd-DOTA were not significantly different between diabetic rats and controls. With Gadofluorine P, the values were significantly higher in the diabetic rats than in the control rats 30 min after injection(P < 0.05). The area under the receiver operating characteristic curve that differentiated diabetic rats from the control group was greater for Gadofluorine P than for Gd-DOTA(0.967 vs 0.667, P = 0.085). An increase in normalized SI 30 min after Gadofluorine P was correlated with a decrease in the mean number of islets(r 2 = 0.510, P = 0.014). Intra-pancreatic Gd was higher in rats with Gadofluorine P injection than Gd-DOTA injection(Gadofluorine P vs Gd-DOTA, 7.37 vs 0.00, P < 0.01). A significant difference in the concentration of intrapancreatic Gd was observed between the control and diabetic animals that were sacrificed 30 min after Gadofluorine P injection(control vs diabetic, 3.25 ng/g vs 10.55 ng/g, P < 0.05)CONCLUSION: In this STZ-induced diabetes rat model,Gadofluorine P-enhanced MRI of the pancreas showed high accuracy in the diagnosis of diabetes.展开更多
Supercritical water oxidation （SCWO） has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An impor...Supercritical water oxidation （SCWO） has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate（DMMP）, which is similar to the nerve agent VX and GB（Sarin） in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon （TOC） on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.展开更多
Gas chromatography-mass spectrometry(GC-MS) and the chemometric resolution method(alternative moving window factor analysis,AMWFA) were used for comparative analysis of volatile constituents in herbal pair(HP) flos lo...Gas chromatography-mass spectrometry(GC-MS) and the chemometric resolution method(alternative moving window factor analysis,AMWFA) were used for comparative analysis of volatile constituents in herbal pair(HP) flos lonicerae-caulis lonicerae(FL-CL) and its single herbs.The temperature-programmed retention index(PTRI) was also employed for the identification of compounds.In total,44,39,and 50 volatile chemical components in volatile oil of FL,CL and HP FL-CL were separately determined qualitatively and quantitatively,accounting for 87.22%,94.54% and 90.08% total contents of volatile oil of FL,CL and HP FL-CL,respectively.The results show that there are 32 common volatile constituents between HP FL-CL and single herb FL,33 common volatile constituents between HP FL-CL and single herb CL,and 10 new constituents in the volatile oil of HP FL-CL.展开更多
Two coordination polymers, namely [Pb（Hbtc）（phen）]n（1） and {[Cd3（btc）2（H2O）4]·2H2O}n（2, H3btc = biphenyl-2,5,3＇-tricarboxylic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray d...Two coordination polymers, namely [Pb（Hbtc）（phen）]n（1） and {[Cd3（btc）2（H2O）4]·2H2O}n（2, H3btc = biphenyl-2,5,3＇-tricarboxylic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium（II） subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of（44·62）3（46·69）2. Thermal stability and luminescent properties of both compounds were studied and discussed.展开更多
A new Schiff base compound, 2-hydroxybenzoic acid [1-（3,5-dibromo-2-hydroxyphenyl） methylidene]hydrazide methanol （C14H10Br2N2O3·CH3OH）, has been synthesized by the condensation of equimolar 3,5-dibromosalicy...A new Schiff base compound, 2-hydroxybenzoic acid [1-（3,5-dibromo-2-hydroxyphenyl） methylidene]hydrazide methanol （C14H10Br2N2O3·CH3OH）, has been synthesized by the condensation of equimolar 3,5-dibromosalicylaldehyde and 2-hydroxybenzoic acid hydrazide in a methanol solution. The compound was characterized by elemental analysis, IR spectra, and singlecrystal X-ray diffraction. The compound consists of a Schiff base moiety 2-hydroxybenzoic acid [1-（3,5-dibromo-2-hydroxyphenyl）methylidene]hydrazide and a lattice methanol molecule. The crystal belongs to the monoclinic system, space group P21/n with a = 7.183（1）, b = 15.673（2）, c = 15.001（2） A, β = 98.345（2）°, Z = 4, V = 1670.9（4） A^3, Dc = 1.773 g/cm^3, Mr = 446.10, λ（MoKα） = 0.71073 , μ = 4.872 mm^-1, F（000） = 880, R = 0.0458 and wR = 0.0963. A total of 3445 unique reflections were collected, of which 2236 with I 〉 2σ（Ⅰ） were observed. As expected, the molecule adopts a trans configuration about the C=N double bond. The two benzene rings are nearly coplanar （mean deviation from the combined plane is 0.061（4） ）, with the dihedral angle of 7.9（3）°. The preliminary biological tests show that the compound has moderate antibacterial activities.展开更多
A Schiff base(a compound containing a C=N bond)induced anodic Ca−P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl_(2) and KH_(2)PO_(4) at 60℃ in the presence of glucose and L-cysteine.The microstru...A Schiff base(a compound containing a C=N bond)induced anodic Ca−P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl_(2) and KH_(2)PO_(4) at 60℃ in the presence of glucose and L-cysteine.The microstructure and chemical composition of the coatings were characterized using FE-SEM,FT-IR,XRD,and XPS.The in vitro degradation resistance of the coated samples was evaluated via potentiodynamic polarization(PDP),electrochemical impedance spectroscopy(EIS),and hydrogen evolution test.The experimental results show that the Ca−PSchiff base coating is composed of CaHPO_(4)(DCPA)and hydroxyapatite(HA),whereas HA is not present in the Ca−P coating.The Ca−P_(Schiff base) coating thickness is about 2 times that of Ca−P coating(Ca−P coating:(9.13±4.20)μm and Ca−P_(Schiff base):(18.13±5.78)μm).The corrosion current density of the Ca−P_(Schiff base) coating is two orders of magnitude lower than that of the Ca−P coating.The formation mechanism of the Ca−P_(Schiff base) is proposed.展开更多
Two coordination polymers, namely [Co（5-Clnic）2（H2biim）]n 1 and {[Ni（5-Clnic）（Hbiim）]·H2O}n 2（5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole）, were assembled. Single-crystal X-ray diffrac...Two coordination polymers, namely [Co（5-Clnic）2（H2biim）]n 1 and {[Ni（5-Clnic）（Hbiim）]·H2O}n 2（5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N–H…O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N–H…O and O–H…O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.展开更多
One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxili...One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxiliary ligands（H2bpdc = 2,2＇-bipyridine-5,5＇-dicarboxylic acid and py =pyridine）.The product 1 was characterized by IR spectroscopy,elemental,thermogravimetric,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction studies show that compound 1 possesses an intricate 3D metal-organic framework based on tetracobalt（Ⅱ） units.Magnetic susceptibility measurement indicates that compound 1 shows an antiferromagnetic coupling between the Co（Ⅱ） ions.展开更多
Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray d...Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.展开更多
A coordination polymer, [Cd（cpna）（py）]n （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, py -- pyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectr...A coordination polymer, [Cd（cpna）（py）]n （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, py -- pyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectra and single-crystal X-ray diffraction. Colorless crystals crystallize in the monoclinic system, space group P21/c with a = 8.589（2）, b = 13.047（3）, c = 14.940（4） A, fl = 96.001（2）°, V = 1664.9（7） A3, C18H12CdN204, Mr = 432.70, Dc = 1.726 g/cm3, F（000） = 856, Z = 4, p（MoKa） = 1.337 mm^-1, the final R = 0.0396 and wR = 0.0891 for 2422 observed reflections （1 〉 2a（I））. Complex I exhibits a two-dimensional （2D） sheet structure, which further builds a three-dimensional （3D） supramolecular architecture via C-H...O hydrogen-bonding interactions.展开更多
Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and charact...Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.展开更多
Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their a...Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.展开更多
文摘Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.
基金Supported by the National Natural Science Foundation of China(No.51674161)Major Basic Research Projects of Shandong Province Natural Science Foundation(No.ZR2017ZC0735)+1 种基金Open Topic of Key Laboratory of Gold Mineralization Processes and Resource Utilization Subordinated to the Ministry of Land and Resources and Key Laboratory of Metallogenic Geological Process and Resources Utilization in Shandong Province(No.Kfkt201812)Research on Precious Metal Mineral Achievement Integration and Tailings Comprehensive Utilization in Shandong Province(Shandong Geological Exploration Document:[2018]No.10)。
文摘Low-cost thermal insulation porous ceramics with uniform pore diameter and low bulk density were prepared with soda-ash dregs and felsic tailings.We investigated the effect of temperature,foaming agent,fluxing agent,Al_(2)O_(3)and CaO content on the pore structure and crystal phase of porous ceramics.The effect of Ca^(2+)in soda-ash dregs on the preparation of quartz-feldspar based porous ceramics was studied.The results showed that the contribution of Ca^(2+)to the preparation of porous ceramics in this system was mainly to accelerate the Si-O bond fracture and reduce the sintering temperature at the initial stage of sintering,which destroyed the needle-like feldspar in the high temperature melt and reduced the melt viscosity,thus reduced the foaming resistance and promoted the porous products with uniform pore size distribution.The Ca^(2+)content on the high side can participate in the formation of crystals in sintering.The generated needle-like diopside and augite,which have small length-diameter ratio,will negligibly change in the viscosity of melt at high temperatures,and their inhibition effect on pores is not as good as that of feldspar with large length-diameter ratio,resulting in the merger and collapse of pores.But the increase of diopside and augite can improve the compressive strength of porous products to some extent.Porous ceramic products containing needle-like feldspar phase can be prepared by using two kinds of solid waste,which can improve the compressive strength of the products and reduce the raw material cost and energy consumption while comprehensively utilizing the double solid waste.The optimal product has a bulk density of 0.45 g/cm^(3),a compressive strength of 3.17 MPa,and a thermal conductivity of 0.11 W/(m·K).
文摘Quantum chemical calculations on some possible equilibrium geometries of C24O2 isomers derived from C24 （D6） and C24O have been performed using density functional theory （DFT） method. The geometric and electronic structures as well as the relative energies and thermal stabilities of various C24O2 isomers at the ground state have been calculated at the B3LYP/6-31G（d） level of theory. And the 1,4,2,5-C24O2 isomer was found to be the most stable geometry where two oxygen atoms were added to the longest carbon-carbon bonds in the same pentagon from a thermodynamic point of view. Based on the optimized neutral geometries, the vertical ionization potential and vertical electron affinity have been obtained. Meanwhile, the vibrational frequencies, IR spectrum, and 13C chemical shifts of various C24O2 isomers have been calculated and analyzed.
文摘Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.
基金Funded by the National Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination polymers, namely {[Ni（cpna）（H2biim）（H2O）]·H2O}n （1） and {[Mn（cpna）（H2biim）]·H2O}n （2） （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, H2biim = 2,2＇- biimidazole）,have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional （1D） step-like chain structure, which further builds a three-dimensional （3D） supramolecular architecture via O–HAAAO and N–HAAAO hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional （1D） double chain structure, which is further assembled into a 3D supramolecular framework by N–HAAAO hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni（II） centers, with g = 2.11 and J = –1.87 cm^-1.
基金Projects(30572455,30670990)supported by the National Natural Science Foundation of ChinaProject(20060390891)supported by Postdoctor Foundation of China+1 种基金Project(NCET-06-0685)supported by the Program of New Century Excellent Talent in University of Ministry of Education of ChinaProject(2006FJ4243)supported by Science and Technology of Hunan Province,China
文摘In order to synthesize the targeting drug carrier system,magnetic chitosan-5-fluorouracil nano-particles were prepared by using 5-fluorouracil(5-Fu)as model drug,Fe3O4 nano-particles as kernel,chitosan as enveloping material and glutaraldehyde as cross linking agent through ultrasonic technique.The morphology of the magnetic chitosan-5-Fu nano-particles was observed with a transmission electron microscope(TEM).The results showed that magnetic chitosan-5-Fu nano-particles were prepared in spherical structure with a size range of 50-60 nm.The delivering capacity and drug releasing properties of magnetic chitosan-5-Fu nano-particles were investigated by UV-vis spectrum analysis.The results showed that the loading capacity was 13.4%and the cumulative release percentage in the phosphate buffer(pH=7.2)solutions was 68%in 30 h.These data indicate that the wrapped drug of magnetic chitosan-5-Fu nano-particles was slowly-released.The magnetic response of magnetic chitosan-5-Fu nano-particles was studied by UV-vis spectrometer to detect the changes of solution absorbance.Without external magnetic field,the nano-particle deposition rate was slow.When being subjected to 8 mT magnetic field,the particle sedimentation rate was increased rapidly.The results showed that magnetic chitosan-5-Fu nano-particles have a magnetic stability and strong targeting characteristics.
文摘Depigmenting agents were solvent-extracted and purified by preparative and analytical HPLC from three Chinese plants; Chrysanthemum morifolium Ramat（ Xizang Caijuhua）, Rhodiola sachalinensis, and Terminalia chebula Retzius. Four fractions obtained from the ethyl ether layer of C. m. Rama and two fractions from the ethyl acetate layer of Rhodiola salientness show depigmenting effects. At 8 200, the ethyl acetate layers of Chrysanthemum morifolium Ramat, Rhodiola sachalinensis and the methanol extract of Terminalia chebula Retzius, can inhibit the melanin production of mouse B16 melanoma cells by 92%, 60% and 90%, respectively, whereas 46% inhibition was observed by commercially available depigmenting agents（arbutin）. These results show the potential of these three Chinese plants as a novel resource for depigmenting agents in the cosmetic industry.
基金Supported by Innovative Research Institute for Cell Therapy,Ministry for Health,Welfare and Family Affairs(A062260)in South Korea
文摘AIM: To investigate the performance of Gadofluorine P-enhanced magnetic resonance imaging(MRI) on the diagnosis of diabetes in a streptozotocin(STZ)-induced diabetic rat model.METHODS: Fischer 344 rats were treated with STZ.Rats not treated with STZ served as controls. T1-weighted MRI was performed using a 3T scanner before and after the injection of Gd-DOTA or Gadofluorine P(6 diabetic rats, 5 controls). The normalized signal intensity(SI) and the enhancement ratio(ER) of the pancreas were measured at each time point, and the values were compared between the normal and diabetic rats using the Mann-Whitney test. In addition,the values were correlated with the mean islet number.Optimal cut-off values were calculated using a positive test based on receiver operating characteristics.Intrapancreatic Gd concentration after the injection of each contrast media was measured using laser ablation-inductively coupled plasma-mass spectrometry in a separate set of rats(4 diabetic rats, 4 controls for Gadofluorine P; 2, 2 for Gd-DOTA).RESULTS: The normalized SI and ER of the pancreas using Gd-DOTA were not significantly different between diabetic rats and controls. With Gadofluorine P, the values were significantly higher in the diabetic rats than in the control rats 30 min after injection(P < 0.05). The area under the receiver operating characteristic curve that differentiated diabetic rats from the control group was greater for Gadofluorine P than for Gd-DOTA(0.967 vs 0.667, P = 0.085). An increase in normalized SI 30 min after Gadofluorine P was correlated with a decrease in the mean number of islets(r 2 = 0.510, P = 0.014). Intra-pancreatic Gd was higher in rats with Gadofluorine P injection than Gd-DOTA injection(Gadofluorine P vs Gd-DOTA, 7.37 vs 0.00, P < 0.01). A significant difference in the concentration of intrapancreatic Gd was observed between the control and diabetic animals that were sacrificed 30 min after Gadofluorine P injection(control vs diabetic, 3.25 ng/g vs 10.55 ng/g, P < 0.05)CONCLUSION: In this STZ-induced diabetes rat model,Gadofluorine P-enhanced MRI of the pancreas showed high accuracy in the diagnosis of diabetes.
文摘Supercritical water oxidation （SCWO） has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate（DMMP）, which is similar to the nerve agent VX and GB（Sarin） in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon （TOC） on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.
基金Project(20976017) supported by the National Natural Science Foundation of China
文摘Gas chromatography-mass spectrometry(GC-MS) and the chemometric resolution method(alternative moving window factor analysis,AMWFA) were used for comparative analysis of volatile constituents in herbal pair(HP) flos lonicerae-caulis lonicerae(FL-CL) and its single herbs.The temperature-programmed retention index(PTRI) was also employed for the identification of compounds.In total,44,39,and 50 volatile chemical components in volatile oil of FL,CL and HP FL-CL were separately determined qualitatively and quantitatively,accounting for 87.22%,94.54% and 90.08% total contents of volatile oil of FL,CL and HP FL-CL,respectively.The results show that there are 32 common volatile constituents between HP FL-CL and single herb FL,33 common volatile constituents between HP FL-CL and single herb CL,and 10 new constituents in the volatile oil of HP FL-CL.
基金Funded by the National Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination polymers, namely [Pb（Hbtc）（phen）]n（1） and {[Cd3（btc）2（H2O）4]·2H2O}n（2, H3btc = biphenyl-2,5,3＇-tricarboxylic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium（II） subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of（44·62）3（46·69）2. Thermal stability and luminescent properties of both compounds were studied and discussed.
基金This work was supported by the Natural Science Foundation of Gansu Province (No. 3ZS061-A25-026)‘Qing Lan’ Talent Engineering Funds by Lanzhou Jiaotong University
文摘A new Schiff base compound, 2-hydroxybenzoic acid [1-（3,5-dibromo-2-hydroxyphenyl） methylidene]hydrazide methanol （C14H10Br2N2O3·CH3OH）, has been synthesized by the condensation of equimolar 3,5-dibromosalicylaldehyde and 2-hydroxybenzoic acid hydrazide in a methanol solution. The compound was characterized by elemental analysis, IR spectra, and singlecrystal X-ray diffraction. The compound consists of a Schiff base moiety 2-hydroxybenzoic acid [1-（3,5-dibromo-2-hydroxyphenyl）methylidene]hydrazide and a lattice methanol molecule. The crystal belongs to the monoclinic system, space group P21/n with a = 7.183（1）, b = 15.673（2）, c = 15.001（2） A, β = 98.345（2）°, Z = 4, V = 1670.9（4） A^3, Dc = 1.773 g/cm^3, Mr = 446.10, λ（MoKα） = 0.71073 , μ = 4.872 mm^-1, F（000） = 880, R = 0.0458 and wR = 0.0963. A total of 3445 unique reflections were collected, of which 2236 with I 〉 2σ（Ⅰ） were observed. As expected, the molecule adopts a trans configuration about the C=N double bond. The two benzene rings are nearly coplanar （mean deviation from the combined plane is 0.061（4） ）, with the dihedral angle of 7.9（3）°. The preliminary biological tests show that the compound has moderate antibacterial activities.
基金supported by the National Natural Science Foundation of China(No.52071191)the Open Foundation of Hubei Key Laboratory of Advanced Technology for Automotive Components,China(No.XDQCKF2021006)。
文摘A Schiff base(a compound containing a C=N bond)induced anodic Ca−P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl_(2) and KH_(2)PO_(4) at 60℃ in the presence of glucose and L-cysteine.The microstructure and chemical composition of the coatings were characterized using FE-SEM,FT-IR,XRD,and XPS.The in vitro degradation resistance of the coated samples was evaluated via potentiodynamic polarization(PDP),electrochemical impedance spectroscopy(EIS),and hydrogen evolution test.The experimental results show that the Ca−PSchiff base coating is composed of CaHPO_(4)(DCPA)and hydroxyapatite(HA),whereas HA is not present in the Ca−P coating.The Ca−P_(Schiff base) coating thickness is about 2 times that of Ca−P coating(Ca−P coating:(9.13±4.20)μm and Ca−P_(Schiff base):(18.13±5.78)μm).The corrosion current density of the Ca−P_(Schiff base) coating is two orders of magnitude lower than that of the Ca−P coating.The formation mechanism of the Ca−P_(Schiff base) is proposed.
基金supported by the Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination polymers, namely [Co（5-Clnic）2（H2biim）]n 1 and {[Ni（5-Clnic）（Hbiim）]·H2O}n 2（5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N–H…O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N–H…O and O–H…O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.
基金supported by the Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘One new mixed-ligand coordination polymer,namely[Co2（btc）（bpdc）（0.5）（py）3]n（1）,was hydrothermally synthesized using biphenyl-2,4,4＇-tricarboxylic acid（H3btc） as a main building block,along with two auxiliary ligands（H2bpdc = 2,2＇-bipyridine-5,5＇-dicarboxylic acid and py =pyridine）.The product 1 was characterized by IR spectroscopy,elemental,thermogravimetric,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction studies show that compound 1 possesses an intricate 3D metal-organic framework based on tetracobalt（Ⅱ） units.Magnetic susceptibility measurement indicates that compound 1 shows an antiferromagnetic coupling between the Co（Ⅱ） ions.
基金supported by the Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.
基金Funded by the Subject team of Taiyuan University of Science and Technology
文摘A coordination polymer, [Cd（cpna）（py）]n （H2cpna = 5-（2＇-carboxylphenyl） nicotic acid, py -- pyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectra and single-crystal X-ray diffraction. Colorless crystals crystallize in the monoclinic system, space group P21/c with a = 8.589（2）, b = 13.047（3）, c = 14.940（4） A, fl = 96.001（2）°, V = 1664.9（7） A3, C18H12CdN204, Mr = 432.70, Dc = 1.726 g/cm3, F（000） = 856, Z = 4, p（MoKa） = 1.337 mm^-1, the final R = 0.0396 and wR = 0.0891 for 2422 observed reflections （1 〉 2a（I））. Complex I exhibits a two-dimensional （2D） sheet structure, which further builds a three-dimensional （3D） supramolecular architecture via C-H...O hydrogen-bonding interactions.
基金Funded by the National Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.
基金financial support from the National Natural Science Foundation of China(21878270,21878267,21922811,21978258 and 21961160742)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)+3 种基金the Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Fundamental Research Funds for the Central Universities(2020XZZX002-09)the Startup Foundation for Hundred-Talent Program of Zhejiang Universitythe Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10)。
文摘Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.
