All-solid-state batteries(ASSBs)with sulfide-type solid electrolytes(SEs)are gaining significant attention due to their potential for the enhanced safety and energy density.In the slurry-coating process for ASSBs,nitr...All-solid-state batteries(ASSBs)with sulfide-type solid electrolytes(SEs)are gaining significant attention due to their potential for the enhanced safety and energy density.In the slurry-coating process for ASSBs,nitrile rubber(NBR)is primarily used as a binder due to its moderate solubility in non-polar solvents,which exhibites minimal chemical reactivity with sulfide SEs.However,the NBR binder,composed of butadiene and acrylonitrile units with differing polarities,exhibits different chemical compatibility depending on the subtle differences in polarity of solvents.Herein,we systematically demonstrate how the chemical compatibility of solvents with the NBR binder influences the performance of ASSBs.Anisole is found to activate the acrylonitrile units,inducing an elongated polymer chain configuration in the binder solution,which gives an opportunity to strongly interact with the solid components of the electrode and the current collector.Consequently,selecting anisole as a solvent for the NBR binder enables the fabrication of a mechanically robust graphite-silicon anode,allowing ASSBs to operate at a lower stacking pressure of 16 MPa.This approach achieves an initial capacity of 480 mAh g^(-1),significantly higher than the 390 mAh g^(-1)achieved with the NBR/toluene binder that has less chemical compatibility.Furthermore,internal stress variations during battery operation are monitored,revealing that the enhanced mechanical properties,achieved through acrylonitrile activation,effectively mitigate internal stress in the graphite/silicon composite anode.展开更多
The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to re...The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to reveal the mechanism of the influence of rubber hardness on the static and dynamic behavior of seals.The optimized selections of rubber hardness are then investigated under different conditions.Results show that the low hardness seal is prone to stress concentration due to the extrusion effect under high pressure conditions;it is also more prone to leaking.A high hardness seal can better prevent leakage by reducing film thickness but it will cause large frictional power loss and increase the probability of wear failure.The choice of low hardness is recommended to reduce friction with the premise that leakage requirements are met.展开更多
A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium sa...A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium salts as the amidyl radical precursors,the reaction enables the formation of two new bonds,one C(sp^(3))-N bond and one C(sp^(2))-C(sp)bond,in a single reaction step.This reaction represents a mild,general route to the construction of theα-amido allenyl nitrile architectures,which characterizes a broad scope,a good functional group compatibility and an excellent selectivity.展开更多
The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presen...The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented.This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cy-cloadducts bearing one or two contiguous stereocenters in good yields(up to 97%yield)with high regioselectivities(100%)and enantioselectivities(up to 97.5%ee).Following that,chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process,additionally,toward five kinds of derivatization reac-tions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.展开更多
A series of novel poly（aryl ether nitrile）s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers （I） with 2,6-difluorobenzonitrile. The inherent vis...A series of novel poly（aryl ether nitrile）s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers （I） with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly（aryl ether nitrile）s including solubility and crystallinity were also studied.展开更多
A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochlor...A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide（ZnO） as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration（〈1 min）,high selectivity;and high yield（90-98%）.展开更多
A simple and convenient procedure for the synthesis of nitriles by dehydration of aldoxime using supported sulphuric acid on melamine-formaldehyde resin （MFR） under solvent-free condition has been developed. A varie...A simple and convenient procedure for the synthesis of nitriles by dehydration of aldoxime using supported sulphuric acid on melamine-formaldehyde resin （MFR） under solvent-free condition has been developed. A variety of aromatic and aliphatic aldoximes were converted to the corresponding nitriles. The resin was recovered and reused for subsequent reactions. ~ 2011 Ramin Rezaei. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination cros...By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination crosslinking. This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber. No other vulcanizing agent or additional additive is involved in this process. By analyzing the results of DMA, XPS and FT-IR, it is found that the crosslinking of CuSO4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups （-CN） and copper ions （Cu^2＋） from CuSO4. SEM and EDX results revealed the generation of a core （CuSO4 solid particle）- shell （adherent NBR） structure, which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover, poly（vinyl chloride） （PVC） and liquid acrylonitrile-butadiene rubber （LNBR） were used as mobilizer to improve the coordination crosslinking of CuSO4/NBR. The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization. In addition, crystal water in CuSO4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO4 and promoted the metal ionization.展开更多
With the expanding application of capacitors,thermal resistant dielectric materials are in high demand due to the increasing harsh environments where the capacitors are needed and the heat generated by the capacitors....With the expanding application of capacitors,thermal resistant dielectric materials are in high demand due to the increasing harsh environments where the capacitors are needed and the heat generated by the capacitors.Herein,we present polyarylene ether nitrile and titanium dioxide hybrids which can be used as thermal resistant dielectrics for these capacitors.Phthalonitrile modified titanium dioxide(TiO_(2)-CN)and phthalonitrile end-capped polyarylene ether nitrile(PEN-Ph)are firstly prepared.After being cast into TiO_(2)-CN/PEN nanocomposite films,these composites self-crosslink upon heating at 320℃for 4 h,forming the polyarylene ether nitrile and titanium dioxide hybrids(TiO_(2)-PEN).Improved dielectric constants which are stable from room temperature to 200℃of these hybrids are observed,indicating the potential application of the hybrids as thermal resistant dielectrics.展开更多
Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-ste...Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-steady state assumption.Effects of hydration temperature,product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics.The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions.When acrylamide concentration was higher than 250 g·L1,the deactivation of NHases became serious and the bi-steady state assumption was not applicable.When the hydration temperature was controlled at a relatively higher level such as 28°C,the total deactivation rate constant was about 2.8-fold of that at 20°C.展开更多
A simple and direct method has been developed for synthesis of nitriles based on one-pot reaction of aromatic aldehydes with three different kind of reagents： CeCl3.7H20/KI/H2O2, CeCl3.7H2O/KI/UHP and （NH4）2Ce（NO3...A simple and direct method has been developed for synthesis of nitriles based on one-pot reaction of aromatic aldehydes with three different kind of reagents： CeCl3.7H20/KI/H2O2, CeCl3.7H2O/KI/UHP and （NH4）2Ce（NO3）6/KI/H2O2 in aqueous ammonia.展开更多
N,N,N＇,N＇-Tetrabromobenzene-1,3-disulfonamide （TBBDA）/triphenylphosphine and N,N,N＇,N＇-tetra- chlorobenzene-1,3-disulfonamide （TCBDA）/triphenylphosphine have been introduced as highly efficient systems for the...N,N,N＇,N＇-Tetrabromobenzene-1,3-disulfonamide （TBBDA）/triphenylphosphine and N,N,N＇,N＇-tetra- chlorobenzene-1,3-disulfonamide （TCBDA）/triphenylphosphine have been introduced as highly efficient systems for the versatile conversion of aldoxime derivatives into nitriles. The process reported here is operationally simple and reactions have been mildly performed in dichloromethane at room temperature.展开更多
Challenges facing high-voltage/high-capacity cathodes,in addition to the longstanding problems pertinent to lithium(Li)-metal anodes,should be addressed to develop high-energy-density Li-metal batteries.This issue mos...Challenges facing high-voltage/high-capacity cathodes,in addition to the longstanding problems pertinent to lithium(Li)-metal anodes,should be addressed to develop high-energy-density Li-metal batteries.This issue mostly stems from interfacial instability between electrodes and electrolytes.Conventional carbonate-or ether-based liquid electrolytes suffer from not only volatility and flammability but also limited electrochemical stability window.Here,we report a nitrile electrolyte strategy based on concentrated nitrile electrolytes(CNEs)with co-additives.The CNE consists of high-concentration lithium bis(fluorosulfonyl)imide(LiFSI)in a solvent mixture of succinonitrile(SN)/acetonitrile(AN).The SN/AN solvent mixture is designed to ensure high oxidation stability along with thermal stability,which are prerequisites for high-voltage Li-metal cells.The CNE exhibits interfacial stability with Li metals due to the coordinated solvation structure.Lithium nitrate(LiNO_(3))and indium fluoride(InF_(3))are incorporated in the CNE as synergistic co-additives to further stabilize solid-electrolyte interphase(SEI)on Li metals.The resulting electrolyte(CNE+LiNO_(3)/InF_(3))enables stable cycling performance in Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)and 4.9 V-class Li||LiNi_(0.5)Mn_(1.5)O_(4)cells.Notably,the Li||LiNi_(0.5)Mn_(1.5)O_(4)cell maintains its electrochemical activity at high temperature(100℃)and even in flame without fire or explosion.展开更多
The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction co...The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction conditions. Herein, we report a new and efficient access to aryl nitriles by an electrochemical synthesis. Compared with the conventional synthetic methods, this electrochemical synthesis is more environmentally friendly and easier to handle.展开更多
The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2...The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni^0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni^2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni^0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.展开更多
Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over...Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. From these experimental data, the excess available volume, E a V , excess free volume, E f V , excess isothermal compressibility, E T β , excess thermal expansion coefficient, E α , and excess internal pressure, E i π , are calculated. The variation of these properties with composition and temperature are discussed in terms of molecular interactions between unlike molecules of the mixtures. It is found that the values of E a V , E f V , E T β and E α are positive and those of E i π are negative for all the mixtures at each temperature studied, indicating the presence of weak interactions between 2M2P and AN/PN/BN molecules. The variations of E a V , E f V , E T β , E α and E i π values with composition indicate that the interactions in these mixtures follow the order: AN<PN<BN, i.e., the 2M2P-nitrile interaction decreases with the increase of alkyl chain length in these nitrile molecules. In addition, the theoretical ultrasonic velocity is calculated using the scaled particle theory and compared with the experimental values.展开更多
A simple,efficient,and general method has been developed for the synthesis ofα-amino nitriles.Oxalic acid as a BrФnsted acid promotes the addition of TMSCN to various imines（generated in situ）.
Cross-linked enzyme aggregates(CLEAs) of nitrile hydratase(NHase) ES-NHT-118 from Escherichia coli were prepared by using ammonium sulfate as precipitating agent followed by cross-linking with dextran polyaldehyde for...Cross-linked enzyme aggregates(CLEAs) of nitrile hydratase(NHase) ES-NHT-118 from Escherichia coli were prepared by using ammonium sulfate as precipitating agent followed by cross-linking with dextran polyaldehyde for the first time. In this process, egg white was added as protein feeder for facilitating the formation of CLEAs. The optimal conditions of the immobilization process were determined. Michaelis constants(Km) of free NHase and NHase CLEAs were also determined. The NHase CLEAs exhibited increased stability at varied pH and temperature conditions compared to its free counterpart. When exposed to high concentrations of acrylamide, NHase CLEAs also exhibited effective catalytic activity.展开更多
Inducing expression and the reaction characteristic of nitrile hydratase （NHase） from Rhodococcus sp. SHZ-1 were investigated. The results showed that the expression of NHase was greatly enhanced with the cooperatio...Inducing expression and the reaction characteristic of nitrile hydratase （NHase） from Rhodococcus sp. SHZ-1 were investigated. The results showed that the expression of NHase was greatly enhanced with the cooperation of acrylonitrile and ammonium chloride as inducer in the medium and the specific activity of NHase was increased of 44%. Then the temperature, pH, concentration of acrylonitrile and acrylamide were evaluated, which affected the activity and reaction characteristic of NHase. It was found that the temperature and concentration of acrylarnide were the most important factors for the catalyzation of NHase. The optimal catalysis temperature of NHase from Rhodococcus sp. SHZ-1 was 30℃, and the activation energy of the hydration of NHase was 90.2kJ·mol^-1 in the temperature range from 5℃ to 30℃. Kmof NHase was 0.095mol·L^-1 using acrylonitrile（AN） as substrate, and NHase activity was inhibited seriously when acrylonitrile concentration was up to 40g·L^-1, the substrate inhibition constant Ki is 0.283mol·L^-1. Moreover, the NHase from Rhodococcus sp. SHZ-1 had very strong tolerance to acrylamide, in which the final concentration of acrylamide reached to 642g·L^-1 and the residual activity of NHase still maintained 8.6% of the initial enzyme activity.展开更多
A mixture of nine biphenyl nitrile compounds with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 min. The buffer system containe...A mixture of nine biphenyl nitrile compounds with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 min. The buffer system contained 100 mmol/L sodium dodecyl sulfate (SDS), 80 mmol/L sodium cholate (SC), 0.81% heptane, 7.5% n-butanol, 10% acetonitrile and 10 mmol/L borate. The addition of SC, organic modifiers, sample preparation and temperature all showed remarkable effect on the separation. Meanwhile, the MEEKC method was briefly compared with micellar electrokinetic chromatography (MEKC) method.展开更多
基金supported by the Technology Innovation Program(00404166,Development of thin-film coating current collector and aqueous binder to enhance the adhesion and conductivity properties on the silicon-rich anode)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea),the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(No.2710024139)the Institute of Civil Military Technology Cooperation funded by the Defense Acquisition Program Administration and Ministry of Trade,Industry and Energy of Korean government under grant No.22-CM-FC-20。
文摘All-solid-state batteries(ASSBs)with sulfide-type solid electrolytes(SEs)are gaining significant attention due to their potential for the enhanced safety and energy density.In the slurry-coating process for ASSBs,nitrile rubber(NBR)is primarily used as a binder due to its moderate solubility in non-polar solvents,which exhibites minimal chemical reactivity with sulfide SEs.However,the NBR binder,composed of butadiene and acrylonitrile units with differing polarities,exhibits different chemical compatibility depending on the subtle differences in polarity of solvents.Herein,we systematically demonstrate how the chemical compatibility of solvents with the NBR binder influences the performance of ASSBs.Anisole is found to activate the acrylonitrile units,inducing an elongated polymer chain configuration in the binder solution,which gives an opportunity to strongly interact with the solid components of the electrode and the current collector.Consequently,selecting anisole as a solvent for the NBR binder enables the fabrication of a mechanically robust graphite-silicon anode,allowing ASSBs to operate at a lower stacking pressure of 16 MPa.This approach achieves an initial capacity of 480 mAh g^(-1),significantly higher than the 390 mAh g^(-1)achieved with the NBR/toluene binder that has less chemical compatibility.Furthermore,internal stress variations during battery operation are monitored,revealing that the enhanced mechanical properties,achieved through acrylonitrile activation,effectively mitigate internal stress in the graphite/silicon composite anode.
基金supported by the National Natural Science Foundation of China(No.52005470)the Natural Science Foundation of Zhejiang Province(No.LQ21E050020)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.2021YW17),China.
文摘The nitrile butadiene rubber(NBR)hardness effect on the sealing characteristics of hydraulic O-ring rod seals is analyzed based on a mixed lubrication elastohydrodynamic model.Parameterized studies are conducted to reveal the mechanism of the influence of rubber hardness on the static and dynamic behavior of seals.The optimized selections of rubber hardness are then investigated under different conditions.Results show that the low hardness seal is prone to stress concentration due to the extrusion effect under high pressure conditions;it is also more prone to leaking.A high hardness seal can better prevent leakage by reducing film thickness but it will cause large frictional power loss and increase the probability of wear failure.The choice of low hardness is recommended to reduce friction with the premise that leakage requirements are met.
基金the National Natural Science Foundation of China(No.22271245)for the financial supportthe Yantai“Double Hundred Plan”the Talent Induction Program for Youth Innovation Teams in Colleges and Universities of Shan-dong Province。
文摘A new 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN using a copper and photoredox synergetic catalysis for producingα-amido allenyl nitriles is developed.Employing N-amidopyridin-1-ium salts as the amidyl radical precursors,the reaction enables the formation of two new bonds,one C(sp^(3))-N bond and one C(sp^(2))-C(sp)bond,in a single reaction step.This reaction represents a mild,general route to the construction of theα-amido allenyl nitrile architectures,which characterizes a broad scope,a good functional group compatibility and an excellent selectivity.
基金Project supported by the National Natural Science Foundation of China(Nos.22278098,21908034,22008045)the Natural Science Foundation of Heilongjiang Province(Nos.LH2021H001,LH2023B013)。
文摘The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented.This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cy-cloadducts bearing one or two contiguous stereocenters in good yields(up to 97%yield)with high regioselectivities(100%)and enantioselectivities(up to 97.5%ee).Following that,chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process,additionally,toward five kinds of derivatization reac-tions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.
文摘A series of novel poly（aryl ether nitrile）s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers （I） with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly（aryl ether nitrile）s including solubility and crystallinity were also studied.
文摘A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide（ZnO） as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration（〈1 min）,high selectivity;and high yield（90-98%）.
文摘A simple and convenient procedure for the synthesis of nitriles by dehydration of aldoxime using supported sulphuric acid on melamine-formaldehyde resin （MFR） under solvent-free condition has been developed. A variety of aromatic and aliphatic aldoximes were converted to the corresponding nitriles. The resin was recovered and reused for subsequent reactions. ~ 2011 Ramin Rezaei. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金This work was financially supported by the Program of National Natural Science Foundation of China(No.50473031).
文摘By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination crosslinking. This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber. No other vulcanizing agent or additional additive is involved in this process. By analyzing the results of DMA, XPS and FT-IR, it is found that the crosslinking of CuSO4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups （-CN） and copper ions （Cu^2＋） from CuSO4. SEM and EDX results revealed the generation of a core （CuSO4 solid particle）- shell （adherent NBR） structure, which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover, poly（vinyl chloride） （PVC） and liquid acrylonitrile-butadiene rubber （LNBR） were used as mobilizer to improve the coordination crosslinking of CuSO4/NBR. The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization. In addition, crystal water in CuSO4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO4 and promoted the metal ionization.
基金financially supported by the National Natural Science Foundation of China(No.51773028)。
文摘With the expanding application of capacitors,thermal resistant dielectric materials are in high demand due to the increasing harsh environments where the capacitors are needed and the heat generated by the capacitors.Herein,we present polyarylene ether nitrile and titanium dioxide hybrids which can be used as thermal resistant dielectrics for these capacitors.Phthalonitrile modified titanium dioxide(TiO_(2)-CN)and phthalonitrile end-capped polyarylene ether nitrile(PEN-Ph)are firstly prepared.After being cast into TiO_(2)-CN/PEN nanocomposite films,these composites self-crosslink upon heating at 320℃for 4 h,forming the polyarylene ether nitrile and titanium dioxide hybrids(TiO_(2)-PEN).Improved dielectric constants which are stable from room temperature to 200℃of these hybrids are observed,indicating the potential application of the hybrids as thermal resistant dielectrics.
基金Supported by the Foundation for the Authors of National Excellent Doctoral Dissertation of China (200345)the National High Technology Research and Development Program of China (2007AA02Z201)the National Basic Research Program of China (2007CB714304)
文摘Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile.The deactivation kinetics of NHases in free resting cells of Rhodococcus sp.was presented based on a bi-steady state assumption.Effects of hydration temperature,product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics.The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions.When acrylamide concentration was higher than 250 g·L1,the deactivation of NHases became serious and the bi-steady state assumption was not applicable.When the hydration temperature was controlled at a relatively higher level such as 28°C,the total deactivation rate constant was about 2.8-fold of that at 20°C.
基金Bu-Ali Sina University Research Council(No.32-1716) for financial support of this work
文摘A simple and direct method has been developed for synthesis of nitriles based on one-pot reaction of aromatic aldehydes with three different kind of reagents： CeCl3.7H20/KI/H2O2, CeCl3.7H2O/KI/UHP and （NH4）2Ce（NO3）6/KI/H2O2 in aqueous ammonia.
基金Bu-Ali Sina University, Center of Excellence and Development of Chemical Methods (CEDCM) for fnancial support
文摘N,N,N＇,N＇-Tetrabromobenzene-1,3-disulfonamide （TBBDA）/triphenylphosphine and N,N,N＇,N＇-tetra- chlorobenzene-1,3-disulfonamide （TCBDA）/triphenylphosphine have been introduced as highly efficient systems for the versatile conversion of aldoxime derivatives into nitriles. The process reported here is operationally simple and reactions have been mildly performed in dichloromethane at room temperature.
基金supported by the U.S.Army Research Office(ARO)(W911NF-18-1-0016)supported by the Basic Science Research Program(2021R1A2B5B03001615,2021M3H4A1A02099355)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and Future Planning,the Technology Innovation Program(20010960,20012216)funded by the Ministry of Trade,Industry&Energy(MOTIE)the R&D program for Forest Science Technology(FTIS 2021354D10-2123-AC03)provided by Korea Forest Service(Korea Forestry Promotion Institute).
文摘Challenges facing high-voltage/high-capacity cathodes,in addition to the longstanding problems pertinent to lithium(Li)-metal anodes,should be addressed to develop high-energy-density Li-metal batteries.This issue mostly stems from interfacial instability between electrodes and electrolytes.Conventional carbonate-or ether-based liquid electrolytes suffer from not only volatility and flammability but also limited electrochemical stability window.Here,we report a nitrile electrolyte strategy based on concentrated nitrile electrolytes(CNEs)with co-additives.The CNE consists of high-concentration lithium bis(fluorosulfonyl)imide(LiFSI)in a solvent mixture of succinonitrile(SN)/acetonitrile(AN).The SN/AN solvent mixture is designed to ensure high oxidation stability along with thermal stability,which are prerequisites for high-voltage Li-metal cells.The CNE exhibits interfacial stability with Li metals due to the coordinated solvation structure.Lithium nitrate(LiNO_(3))and indium fluoride(InF_(3))are incorporated in the CNE as synergistic co-additives to further stabilize solid-electrolyte interphase(SEI)on Li metals.The resulting electrolyte(CNE+LiNO_(3)/InF_(3))enables stable cycling performance in Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)and 4.9 V-class Li||LiNi_(0.5)Mn_(1.5)O_(4)cells.Notably,the Li||LiNi_(0.5)Mn_(1.5)O_(4)cell maintains its electrochemical activity at high temperature(100℃)and even in flame without fire or explosion.
基金financially supported by the National Natural Science Foundation of China (Nos. 2127222, 91213303, 21172205, J1030412)
文摘The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction conditions. Herein, we report a new and efficient access to aryl nitriles by an electrochemical synthesis. Compared with the conventional synthetic methods, this electrochemical synthesis is more environmentally friendly and easier to handle.
基金the Universidad Nacional del Litoral (UNL)Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT ), Argentina, for the financial support of this work
文摘The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni^0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni^2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni^0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.
文摘Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. From these experimental data, the excess available volume, E a V , excess free volume, E f V , excess isothermal compressibility, E T β , excess thermal expansion coefficient, E α , and excess internal pressure, E i π , are calculated. The variation of these properties with composition and temperature are discussed in terms of molecular interactions between unlike molecules of the mixtures. It is found that the values of E a V , E f V , E T β and E α are positive and those of E i π are negative for all the mixtures at each temperature studied, indicating the presence of weak interactions between 2M2P and AN/PN/BN molecules. The variations of E a V , E f V , E T β , E α and E i π values with composition indicate that the interactions in these mixtures follow the order: AN<PN<BN, i.e., the 2M2P-nitrile interaction decreases with the increase of alkyl chain length in these nitrile molecules. In addition, the theoretical ultrasonic velocity is calculated using the scaled particle theory and compared with the experimental values.
基金supported by the Islamic Azad University,Ayatollah Amoli Branch
文摘A simple,efficient,and general method has been developed for the synthesis ofα-amino nitriles.Oxalic acid as a BrФnsted acid promotes the addition of TMSCN to various imines（generated in situ）.
基金Supported by the National Nature Science Foundation of China(Nos.21306039,21276060,21276062)the Natural Science Foundation of Hebei Province(B2015202082,B2016202027)the Tianjin City High School Science&Technology Fund Planning Project(20140513)
文摘Cross-linked enzyme aggregates(CLEAs) of nitrile hydratase(NHase) ES-NHT-118 from Escherichia coli were prepared by using ammonium sulfate as precipitating agent followed by cross-linking with dextran polyaldehyde for the first time. In this process, egg white was added as protein feeder for facilitating the formation of CLEAs. The optimal conditions of the immobilization process were determined. Michaelis constants(Km) of free NHase and NHase CLEAs were also determined. The NHase CLEAs exhibited increased stability at varied pH and temperature conditions compared to its free counterpart. When exposed to high concentrations of acrylamide, NHase CLEAs also exhibited effective catalytic activity.
基金Supported by the National Natural Science Foundation of China （No.20466002）, the Program for New Century Excellent Talents in University （NCET-04-089） and the Key Research Projects in the Uygur Autonomous Region of Xinjiang （No.200332109）.
文摘Inducing expression and the reaction characteristic of nitrile hydratase （NHase） from Rhodococcus sp. SHZ-1 were investigated. The results showed that the expression of NHase was greatly enhanced with the cooperation of acrylonitrile and ammonium chloride as inducer in the medium and the specific activity of NHase was increased of 44%. Then the temperature, pH, concentration of acrylonitrile and acrylamide were evaluated, which affected the activity and reaction characteristic of NHase. It was found that the temperature and concentration of acrylarnide were the most important factors for the catalyzation of NHase. The optimal catalysis temperature of NHase from Rhodococcus sp. SHZ-1 was 30℃, and the activation energy of the hydration of NHase was 90.2kJ·mol^-1 in the temperature range from 5℃ to 30℃. Kmof NHase was 0.095mol·L^-1 using acrylonitrile（AN） as substrate, and NHase activity was inhibited seriously when acrylonitrile concentration was up to 40g·L^-1, the substrate inhibition constant Ki is 0.283mol·L^-1. Moreover, the NHase from Rhodococcus sp. SHZ-1 had very strong tolerance to acrylamide, in which the final concentration of acrylamide reached to 642g·L^-1 and the residual activity of NHase still maintained 8.6% of the initial enzyme activity.
文摘A mixture of nine biphenyl nitrile compounds with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 min. The buffer system contained 100 mmol/L sodium dodecyl sulfate (SDS), 80 mmol/L sodium cholate (SC), 0.81% heptane, 7.5% n-butanol, 10% acetonitrile and 10 mmol/L borate. The addition of SC, organic modifiers, sample preparation and temperature all showed remarkable effect on the separation. Meanwhile, the MEEKC method was briefly compared with micellar electrokinetic chromatography (MEKC) method.
