Efficient and low-cost recycling of spent lithium iron phosphate(LiFePO_(4),LFP)batteries has become an inevitable trend.In this study,an integrated closed-loop recycling strategy including isomorphic substitution lea...Efficient and low-cost recycling of spent lithium iron phosphate(LiFePO_(4),LFP)batteries has become an inevitable trend.In this study,an integrated closed-loop recycling strategy including isomorphic substitution leaching and solvent extraction process for spent LFP was proposed.An inexpensive FeCl_(3)was used as leaching agent to directly substitute Fe^(2+)from LFP.99%of Li can be rapidly leached in just 30 min,accompanied by 98%of FePO_(4)precipitated in lixivium.The tri-n-butyl phosphate(TBP)-sulfonated kerosene(SK)system was applied to extract Li from lixivium through a twelve-stage countercurrent process containing synchronous extraction and stepwise stripping of Li^(+)and Fe^(3+).80.81%of Li can be selectively enriched in stripping liquor containing 3.059 mol·L^(-1)of Li^(+)under optimal conditions.And the Fe stripping liquor was recovered for LFP re-leaching,of which,Fe^(2+)was oxidized to Fe^(3+)by appropriate H_(2)O_(2).Raffinate and lixivium were concentrated and entered into extraction process to accomplished closeloop recycling process.Overall,the results suggest that more than 99%of Li was recovered.FeCl_(3)holding in solution was directly regenerated without any pollutant emission.The sustainable mothed would be an alternative candidate for total element recycling of spent LFP batteries with industrial potential.展开更多
Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and non...Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and noncontact atomic force microscopy(nc-AFM),we investigated the adsorption structure of DOATF molecules on Au(111)surface,which shows the four furanzan rings in the STM images and a bright protrusion off the center of the molecule in the nc-AFM images.Combined with density functional theory(DFT)calculations,we confirmed that the bright feature in the nc-AFM images is an N-O coordinate bond pointing upwards in one of the two azoxy groups;while the other N-O bond pointing towards the Au(111)surface.Our work contributes for a deeper understanding of the adsorption structure of macrocyclic compounds,which would promote the designing of DOATF-metal frameworks.展开更多
The past decade has seen a sharp increase in machine learning(ML)applications in scientific research.This review introduces the basic constituents of ML,including databases,features,and algorithms,and highlights a few...The past decade has seen a sharp increase in machine learning(ML)applications in scientific research.This review introduces the basic constituents of ML,including databases,features,and algorithms,and highlights a few important achievements in chemistry that have been aided by ML techniques.The described databases include some of the most popular chemical databases for molecules and materials obtained from either experiments or computational calculations.Important two-dimensional(2D)and three-dimensional(3D)features representing the chemical environment of molecules and solids are briefly introduced.Decision tree and deep learning neural network algorithms are overviewed to emphasize their frameworks and typical application scenarios.Three important fields of ML in chemistry are discussed:(1)retrosynthesis,in which ML predicts the likely routes of organic synthesis;(2)atomic simulations,which utilize the ML potential to accelerate potential energy surface sampling;and(3)heterogeneous catalysis,in which ML assists in various aspects of catalytic design,ranging from synthetic condition optimization to reaction mechanism exploration.Finally,a prospect on future ML applications is provided.展开更多
The solute carrier family 12(SLC12)of cation-chloride cotransporters(CCCs)comprises potassium chloride cotransporters(KCCs,e.g.KCC1,KCC2,KCC3,and KCC4)-mediated Cl^(-)extrusion,and sodium potassium chloride cotranspor...The solute carrier family 12(SLC12)of cation-chloride cotransporters(CCCs)comprises potassium chloride cotransporters(KCCs,e.g.KCC1,KCC2,KCC3,and KCC4)-mediated Cl^(-)extrusion,and sodium potassium chloride cotransporters(N[K]CCs,NKCC1,NKCC2,and NCC)-mediated Cl^(-)loading.The CCCs play vital roles in cell volume regulation and ion homeostasis.Gain-of-function or loss-of-function of these ion transporters can cause diseases in many tissues.In recent years,there have been considerable advances in our understanding of CCCs'control mechanisms in cell volume regulations,with many techniques developed in studying the functions and activities of CCCs.Classic approaches to directly measure CCC activity involve assays that measure the transport of potassium substitutes through the CCCs.These techniques include the ammonium pulse technique,radioactive or nonradioactive rubidium ion uptakeassay,and thallium ion-uptake assay.CCCs'activity can also be indirectly observed by measuring gaminobutyric acid(GABA)activity with patch-clamp electrophysiology and intracellular chloride concentration with sensitive microelectrodes,radiotracer^(36)Cl^(-),and fluorescent dyes.Other techniques include directly looking at kinase regulatory sites phosphorylation,flame photometry,22Nat uptake assay,structural biology,molecular modeling,and high-throughput drug screening.This review summarizes the role of CCCs in genetic disorders and cell volume regulation,current methods applied in studying CCCs biology,and compounds developed that directly or indirectly target the CCCs for disease treatments.展开更多
Molecular structure of organic semiconductor plays a critical role in determining the performance and functionality of organic electronic devices,by optimizing the electrical,optical and physicochemical properties.Sub...Molecular structure of organic semiconductor plays a critical role in determining the performance and functionality of organic electronic devices,by optimizing the electrical,optical and physicochemical properties.Substituted alkyl chains are fundamental units in tailering the solubility and assemblability,among which the asymmetric properties have been reported as key element for controlling the packing motifs and intrinsic charge transport.Here,we expanded the scope of molecular asymmetry dependent sensing features based on a new series of naphthalene diimides(NDI)-based derivatives substituted with a same branching alkyl chain but various linear-shaped alkyl chains(Cn-).A clear molecular stacking change,from head-to-head bilayer to head-to-tail monolayer packing model,is observed based on the features of anisotropic molecular interactions with the change in the chain length.Most importantly,a unique LUMO level shift of 0.17 eV is validated for NDI-PhC4,providing a record sensitivity up to 150%to 0.01 ppb ammonia,due to the desired molecular reactivity and device amplification properties.These results indicate that asymmetric side-chain engineering opens a route for breath healthcare.展开更多
Bis(azidoacetamino)furazan (DAZAF) was synthesized and characterized by elemental analysis, IR, 1H NMR and MS as an energetic compound. The crystal structure of the title compound was determined by single-crystal X-ra...Bis(azidoacetamino)furazan (DAZAF) was synthesized and characterized by elemental analysis, IR, 1H NMR and MS as an energetic compound. The crystal structure of the title compound was determined by single-crystal X-ray diffraction with the following data: C6H6N10O3, monoclinic, P21/n, Z = 4, a = 8.402(3), b = 15.146(3), c = 9.247(3) ? ?= 111.09(2)? V = 1098.0(6) 3, Mr = 266.18, Dc = 1.610 g/cm3, F(000) = 544, ?=1.34 cm-1, R = 0.037 and wR = 0.044 for 2136 observed reflections (I > 2(I)). Intra- and inter-molecular hydrogen bonds were identified between the O and H atoms of two intramolecular acetylamino groups and two intermolecular acetylamino groups, respectively.展开更多
Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of am...Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorum was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly, from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.展开更多
Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.
An integrated poly(dimethylsiloxane) (PDMS) microchip with two sharpened stretching has been presented. The sample was directly introduced into the separation channel through the stretching inlet tip without complicat...An integrated poly(dimethylsiloxane) (PDMS) microchip with two sharpened stretching has been presented. The sample was directly introduced into the separation channel through the stretching inlet tip without complicated power switching supplies and without injection cross-channel. Operations of running buffer refreshing or channel cleaning also becomes simple by vacuumed in one end and placed another tip into solution vial. The fabrication method can be easily applied in most analytical laboratories at low cost in the absence of soft lithography and plasma bonding equipments. Characteristics of the chips were tested and it can be used to separate fluorescence labeled molecules.展开更多
Methodsfor the synthesis of acidic phenyl-and substituted phenylphosphonates bearing a branched longchain ester alkyl group are described.These synthetic routes are incomparably superior to other methods in vari-ous a...Methodsfor the synthesis of acidic phenyl-and substituted phenylphosphonates bearing a branched longchain ester alkyl group are described.These synthetic routes are incomparably superior to other methods in vari-ous aspects including better reaction yield and higher purity of the product.The behaviour of themono(2-butyloctyl)esters and mono(2-methyldodecyl)esters of both phenyl-and o-methylphenylphosphonicacids thus obtained in extraction of lanthanum,praseodymium,neodymium and lutecium as representatives oflight and heavy rare earths,is investigated and discussed on the basis of their chemical structure.The dependenceof the extraction constants and separation factors accords with the Reactivity-Selectivity Principle in solvent ex-traction proposed by us.The composition and structure of the extracted species have been characterized byinfra-red and proton nuclear magnetic resonance spectroscopy in addition to elemental analyses.展开更多
A neutral homoleptic lanthanide amide Yb(NPh 2) 3(THF) 2 was obtained by reaction of anhydrous YbCl 3 with LiNPh 2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallograp...A neutral homoleptic lanthanide amide Yb(NPh 2) 3(THF) 2 was obtained by reaction of anhydrous YbCl 3 with LiNPh 2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P2 1/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm 3, Z=4, D c=1.417 g·cm -3, μ=24.67 cm -1 (Mo Kα), F(000)=1668, R=0.036, R w=0.039. The central metal ytterbium is coordinated by three terminal NPh 2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.展开更多
In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) dur...In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.展开更多
The reaction of anhydrous YbCl3 with LiNPri2 in 1:3 molar ratio gave the homo- leptic lanthanide amide ate complex Yb(C6H14N)4Li(C4H8O). The crystal structure was determined by X-ray diffraction and the following crys...The reaction of anhydrous YbCl3 with LiNPri2 in 1:3 molar ratio gave the homo- leptic lanthanide amide ate complex Yb(C6H14N)4Li(C4H8O). The crystal structure was determined by X-ray diffraction and the following crystallographic data were obtained: C28H64N4OYbLi, Mg = 652.82, monoclinic, P21/c (#14), a = 15.239(3), b = 21.502(6), c = 21.288(4) ? b = 93.18(2), V = 6964(2) 3, Z = 8, Dc = 1.245 g/cm3, F(000) = 2728 and m(MoKa) = 27.08 cm-1. The final R and Rw are 0.044 and 0.053 for 6765 observed reflections with I > 3.00s(I), respectively. The ytterbium atom is bonded to two terminal amide ligands with the normal YbN distances of 2.171(6) and 2.174(7) ? and two bridging amide ligands with the YbN bonds about 0.1 ?longer than those of the formers, forming a distorted tetrahedral geometry.展开更多
The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained i...The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.展开更多
A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazol...A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazoles with yields of 49%～93%. The reaction time was shortened to 3～6 min. However, the reaction of ethylenediamine with carboxylic acids did not give imidazoles but the N,N-diacyl ethylenediamines. The alphatic diamines lacked the activity to form imidazole ring. With adipic acid, intermolecular acylation took place to afford poly(ethylene adipamide).展开更多
A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the pres...A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the present protocol attractive.展开更多
Polyoxetanes bearing short fluorinated and/or bromomethyl pendant groups were prepared from 3,3-bis(2,2,2-trifluoroethoxymethyl)oxetane and/or 3,3-bisbromomethyloxetane by ring-opening polymerization.A series of novel...Polyoxetanes bearing short fluorinated and/or bromomethyl pendant groups were prepared from 3,3-bis(2,2,2-trifluoroethoxymethyl)oxetane and/or 3,3-bisbromomethyloxetane by ring-opening polymerization.A series of novel polyurethanes(PUs)containing polyoxetanes as soft blocks was synthesized by the reaction of polyoxetanes,isophorone diisocyanate(IPDI),and 1,4-butanediol(BD).The thermal properties and wetting behavior of these novel polymers were evaluated using TGA,DSC and contact angle analysis.The cotton fabrics treated with PU3 showed good hydrophobic property,and its contact angle for water was 133°.展开更多
Two novel fluorinated acrylate monomers 4a and 4b containing perfluorohexyl group were designed and synthesized starting from 4-allylanisole and perfluorohexyl iodide.The monomers 4a and 4b were then copolymerized wit...Two novel fluorinated acrylate monomers 4a and 4b containing perfluorohexyl group were designed and synthesized starting from 4-allylanisole and perfluorohexyl iodide.The monomers 4a and 4b were then copolymerized with octadecyl acrylate and 2-hydroxyethyl acrylate by emulsion polymerization to give copolymers PFA 1 and PFA 2 respectively.The co-polymers were characterized by FT-IR and their heat stability was measured by TGA.The surface properties of PFA 1 and PFA 2 were studied by applying on cotton fabrics.The treated cotton fabrics showed good water-repellent property,and the contact angles for water reached 142° for PFA 1 and 136° for PFA 2.展开更多
基金financially supported by the National Natural Science Foundation of China(U1707601)project of Youth Innovation Promotion Association,Chinese Academy of Sciences(2021430)+1 种基金project of Innovation Academy for Green Manufacture,Chinese Academy of Sciences(IAGM2020C26)project of Bureau of International Cooperation,Chinese Academy of Sciences(122363KYSB20190033)。
文摘Efficient and low-cost recycling of spent lithium iron phosphate(LiFePO_(4),LFP)batteries has become an inevitable trend.In this study,an integrated closed-loop recycling strategy including isomorphic substitution leaching and solvent extraction process for spent LFP was proposed.An inexpensive FeCl_(3)was used as leaching agent to directly substitute Fe^(2+)from LFP.99%of Li can be rapidly leached in just 30 min,accompanied by 98%of FePO_(4)precipitated in lixivium.The tri-n-butyl phosphate(TBP)-sulfonated kerosene(SK)system was applied to extract Li from lixivium through a twelve-stage countercurrent process containing synchronous extraction and stepwise stripping of Li^(+)and Fe^(3+).80.81%of Li can be selectively enriched in stripping liquor containing 3.059 mol·L^(-1)of Li^(+)under optimal conditions.And the Fe stripping liquor was recovered for LFP re-leaching,of which,Fe^(2+)was oxidized to Fe^(3+)by appropriate H_(2)O_(2).Raffinate and lixivium were concentrated and entered into extraction process to accomplished closeloop recycling process.Overall,the results suggest that more than 99%of Li was recovered.FeCl_(3)holding in solution was directly regenerated without any pollutant emission.The sustainable mothed would be an alternative candidate for total element recycling of spent LFP batteries with industrial potential.
基金the National Key Research and Development Projects of China(Grant No.2019YFA0308500)the National Natural Science Foundation of China(Grant No.61888102)the Funds from the Chinese Academy of Sciences(Grant Nos.XDB30000000 and YSBR-003)。
文摘Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and noncontact atomic force microscopy(nc-AFM),we investigated the adsorption structure of DOATF molecules on Au(111)surface,which shows the four furanzan rings in the STM images and a bright protrusion off the center of the molecule in the nc-AFM images.Combined with density functional theory(DFT)calculations,we confirmed that the bright feature in the nc-AFM images is an N-O coordinate bond pointing upwards in one of the two azoxy groups;while the other N-O bond pointing towards the Au(111)surface.Our work contributes for a deeper understanding of the adsorption structure of macrocyclic compounds,which would promote the designing of DOATF-metal frameworks.
基金financial support from the National Key Research and Development Program of China(2018YFA0208600)the National Natural Science Foundation of China(12188101,22033003,91945301,91745201,92145302,22122301,and 92061112)the Tencent Foundation for XPLORER PRIZE,and Fundamental Research Funds for the Central Universities(20720220011)。
文摘The past decade has seen a sharp increase in machine learning(ML)applications in scientific research.This review introduces the basic constituents of ML,including databases,features,and algorithms,and highlights a few important achievements in chemistry that have been aided by ML techniques.The described databases include some of the most popular chemical databases for molecules and materials obtained from either experiments or computational calculations.Important two-dimensional(2D)and three-dimensional(3D)features representing the chemical environment of molecules and solids are briefly introduced.Decision tree and deep learning neural network algorithms are overviewed to emphasize their frameworks and typical application scenarios.Three important fields of ML in chemistry are discussed:(1)retrosynthesis,in which ML predicts the likely routes of organic synthesis;(2)atomic simulations,which utilize the ML potential to accelerate potential energy surface sampling;and(3)heterogeneous catalysis,in which ML assists in various aspects of catalytic design,ranging from synthetic condition optimization to reaction mechanism exploration.Finally,a prospect on future ML applications is provided.
基金We are very grateful for the financial support from the National Natural Science Foundation of China(Grant Nos.:82170406,81970238,and 32111530119)Shanghai Municipal Science and Technology Major Project,China(Grant No.:2018SHZDZX01)+1 种基金The Royal Society UK(Grant No.:IEC\NSFC\201094)the Commonwealth Scholarship Commission UK(Grant No.:NGCA-2020-43).
文摘The solute carrier family 12(SLC12)of cation-chloride cotransporters(CCCs)comprises potassium chloride cotransporters(KCCs,e.g.KCC1,KCC2,KCC3,and KCC4)-mediated Cl^(-)extrusion,and sodium potassium chloride cotransporters(N[K]CCs,NKCC1,NKCC2,and NCC)-mediated Cl^(-)loading.The CCCs play vital roles in cell volume regulation and ion homeostasis.Gain-of-function or loss-of-function of these ion transporters can cause diseases in many tissues.In recent years,there have been considerable advances in our understanding of CCCs'control mechanisms in cell volume regulations,with many techniques developed in studying the functions and activities of CCCs.Classic approaches to directly measure CCC activity involve assays that measure the transport of potassium substitutes through the CCCs.These techniques include the ammonium pulse technique,radioactive or nonradioactive rubidium ion uptakeassay,and thallium ion-uptake assay.CCCs'activity can also be indirectly observed by measuring gaminobutyric acid(GABA)activity with patch-clamp electrophysiology and intracellular chloride concentration with sensitive microelectrodes,radiotracer^(36)Cl^(-),and fluorescent dyes.Other techniques include directly looking at kinase regulatory sites phosphorylation,flame photometry,22Nat uptake assay,structural biology,molecular modeling,and high-throughput drug screening.This review summarizes the role of CCCs in genetic disorders and cell volume regulation,current methods applied in studying CCCs biology,and compounds developed that directly or indirectly target the CCCs for disease treatments.
基金financially supported by the National Natural Science Foundation of China(Nos.6197396,21905276)Natural Science Foundation of Beijing(No.4202077)+1 种基金Chinese Academy of Scinece(No.ZDBS-LY-SLH034)the Fundamental Research Funds for the Central Universities(No.E2ET0309X2)。
文摘Molecular structure of organic semiconductor plays a critical role in determining the performance and functionality of organic electronic devices,by optimizing the electrical,optical and physicochemical properties.Substituted alkyl chains are fundamental units in tailering the solubility and assemblability,among which the asymmetric properties have been reported as key element for controlling the packing motifs and intrinsic charge transport.Here,we expanded the scope of molecular asymmetry dependent sensing features based on a new series of naphthalene diimides(NDI)-based derivatives substituted with a same branching alkyl chain but various linear-shaped alkyl chains(Cn-).A clear molecular stacking change,from head-to-head bilayer to head-to-tail monolayer packing model,is observed based on the features of anisotropic molecular interactions with the change in the chain length.Most importantly,a unique LUMO level shift of 0.17 eV is validated for NDI-PhC4,providing a record sensitivity up to 150%to 0.01 ppb ammonia,due to the desired molecular reactivity and device amplification properties.These results indicate that asymmetric side-chain engineering opens a route for breath healthcare.
文摘Bis(azidoacetamino)furazan (DAZAF) was synthesized and characterized by elemental analysis, IR, 1H NMR and MS as an energetic compound. The crystal structure of the title compound was determined by single-crystal X-ray diffraction with the following data: C6H6N10O3, monoclinic, P21/n, Z = 4, a = 8.402(3), b = 15.146(3), c = 9.247(3) ? ?= 111.09(2)? V = 1098.0(6) 3, Mr = 266.18, Dc = 1.610 g/cm3, F(000) = 544, ?=1.34 cm-1, R = 0.037 and wR = 0.044 for 2136 observed reflections (I > 2(I)). Intra- and inter-molecular hydrogen bonds were identified between the O and H atoms of two intramolecular acetylamino groups and two intermolecular acetylamino groups, respectively.
基金the National Natural Science Foundation of China （No.30371002）.
文摘Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorum was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly, from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.
基金the National Natural Science Foundation of China(Project No.20072033)Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.
文摘An integrated poly(dimethylsiloxane) (PDMS) microchip with two sharpened stretching has been presented. The sample was directly introduced into the separation channel through the stretching inlet tip without complicated power switching supplies and without injection cross-channel. Operations of running buffer refreshing or channel cleaning also becomes simple by vacuumed in one end and placed another tip into solution vial. The fabrication method can be easily applied in most analytical laboratories at low cost in the absence of soft lithography and plasma bonding equipments. Characteristics of the chips were tested and it can be used to separate fluorescence labeled molecules.
基金supported by the National Natural Science Foundation of China
文摘Methodsfor the synthesis of acidic phenyl-and substituted phenylphosphonates bearing a branched longchain ester alkyl group are described.These synthetic routes are incomparably superior to other methods in vari-ous aspects including better reaction yield and higher purity of the product.The behaviour of themono(2-butyloctyl)esters and mono(2-methyldodecyl)esters of both phenyl-and o-methylphenylphosphonicacids thus obtained in extraction of lanthanum,praseodymium,neodymium and lutecium as representatives oflight and heavy rare earths,is investigated and discussed on the basis of their chemical structure.The dependenceof the extraction constants and separation factors accords with the Reactivity-Selectivity Principle in solvent ex-traction proposed by us.The composition and structure of the extracted species have been characterized byinfra-red and proton nuclear magnetic resonance spectroscopy in addition to elemental analyses.
文摘A neutral homoleptic lanthanide amide Yb(NPh 2) 3(THF) 2 was obtained by reaction of anhydrous YbCl 3 with LiNPh 2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P2 1/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm 3, Z=4, D c=1.417 g·cm -3, μ=24.67 cm -1 (Mo Kα), F(000)=1668, R=0.036, R w=0.039. The central metal ytterbium is coordinated by three terminal NPh 2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.
基金National Key Research and Development Program of China(No.2018YFC0604800)National Natural Science Foundation of China(No.U1707601)+1 种基金Science and Technology Major Project of Qinghai Province(2019-GX-A5)West Light Talent Program of Chines Academy of Sciences(Doctor Project,2016)
文摘In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.
基金Supported by the National Natural Science Foundation of China (20072027) Department of Education of Jiangsu province and the Key Laboratory of Organic Synthesis of Jiangsu province
文摘The reaction of anhydrous YbCl3 with LiNPri2 in 1:3 molar ratio gave the homo- leptic lanthanide amide ate complex Yb(C6H14N)4Li(C4H8O). The crystal structure was determined by X-ray diffraction and the following crystallographic data were obtained: C28H64N4OYbLi, Mg = 652.82, monoclinic, P21/c (#14), a = 15.239(3), b = 21.502(6), c = 21.288(4) ? b = 93.18(2), V = 6964(2) 3, Z = 8, Dc = 1.245 g/cm3, F(000) = 2728 and m(MoKa) = 27.08 cm-1. The final R and Rw are 0.044 and 0.053 for 6765 observed reflections with I > 3.00s(I), respectively. The ytterbium atom is bonded to two terminal amide ligands with the normal YbN distances of 2.171(6) and 2.174(7) ? and two bridging amide ligands with the YbN bonds about 0.1 ?longer than those of the formers, forming a distorted tetrahedral geometry.
文摘The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n- butylammonium fluoride (TBAF) in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.
文摘A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazoles with yields of 49%～93%. The reaction time was shortened to 3～6 min. However, the reaction of ethylenediamine with carboxylic acids did not give imidazoles but the N,N-diacyl ethylenediamines. The alphatic diamines lacked the activity to form imidazole ring. With adipic acid, intermolecular acylation took place to afford poly(ethylene adipamide).
基金the National Natural Science Foundation of China （No. 20072033）Specialized Research Fund for the Doctoral Program of Higher Education of China.
文摘A convenient method has been developed toward the stereoselective synthesis of N-substituted benzotriazole derivatives under mild conditions. The good stereolectivity,high yields and the simple procedure make the present protocol attractive.
基金Program for Changjiang Scholars and Innovative Research Teamin University,China(No.IRT0526)Shanghai Municipal Scientific Committee,China(No.08JC1400400)
文摘Polyoxetanes bearing short fluorinated and/or bromomethyl pendant groups were prepared from 3,3-bis(2,2,2-trifluoroethoxymethyl)oxetane and/or 3,3-bisbromomethyloxetane by ring-opening polymerization.A series of novel polyurethanes(PUs)containing polyoxetanes as soft blocks was synthesized by the reaction of polyoxetanes,isophorone diisocyanate(IPDI),and 1,4-butanediol(BD).The thermal properties and wetting behavior of these novel polymers were evaluated using TGA,DSC and contact angle analysis.The cotton fabrics treated with PU3 showed good hydrophobic property,and its contact angle for water was 133°.
基金Programfor Changjiang Scholars and Innovative Research Teamin University,China(No.IRT0526)Shanghai Municipal Scientific Committee,China(No.08JC1400400)
文摘Two novel fluorinated acrylate monomers 4a and 4b containing perfluorohexyl group were designed and synthesized starting from 4-allylanisole and perfluorohexyl iodide.The monomers 4a and 4b were then copolymerized with octadecyl acrylate and 2-hydroxyethyl acrylate by emulsion polymerization to give copolymers PFA 1 and PFA 2 respectively.The co-polymers were characterized by FT-IR and their heat stability was measured by TGA.The surface properties of PFA 1 and PFA 2 were studied by applying on cotton fabrics.The treated cotton fabrics showed good water-repellent property,and the contact angles for water reached 142° for PFA 1 and 136° for PFA 2.
