Biointerphases
·
2022
·Vol. 17
·期 6
·
IF 1.916
Wang Li,Cui Baocheng,Qiu Keyuan,Huang Jiao,Liang Changhai
Nitrile hydratase (NHase, EC 4.2.1.84) is an excellent biocatalyst that catalyzes the hydration of nitrile substances to their corresponding amides. Given its catalytic specificity and eco-friendliness, NHase has extensive applications in the chemical, pharmaceutical, and cosmetic industries. To improve the affinity between Rhodococcus erythropolis CCM2595-derived NHase ( Re NHase) and adiponitrile, this study used a semirational design to improve the efficiency of Re NHase in catalyzing the generation of 5-cyanopentanamide from adiponitrile. Enzyme kinetics analysis showed that Km of the mutant Re NHase B:G196Y was 3.265 mmol l −1 , which was lower than that of the wild-type NHase. The affinity of the mutant Re NHase B:G196Y to adiponitrile was increased by 36.35%, and the efficiency of the mutant Re NHase B:G196Y in catalyzing adiponitrile to 5-cyanopentamide was increased by 10.11%. The analysis of the enzyme-substrate interaction showed that the hydrogen bond length of the mutant Re NHase B:G196Y to adiponitrile was shortened by 0.59 Å, which enhanced the interaction between the mutant and adiponitrile and, thereby, increased the substrate affinity. Similarly, the structural analysis showed that the amino acid flexibility near the mutation site of Re NHase B:G196Y was increased, which enhanced the binding force between the enzyme and adiponitrile. Our work may provide a new theoretical basis for the modification of substrate affinity of NHase and increase the possibility of industrial applications of the enzyme.
研究领域:
生物化学
·
工业酶学
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产品关联
DOI
PubMed
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2025
·
IF 7.4
Zixuan Zheng,John Lou Yao,Qiang Yao
To elucidate chemistry taking place during thermal degradation of polyamide 66 in the presence of phosphorus flame retardants and understand how commonly used phosphorus flame retardants achieve their flame retardancy, PA66 and a series of model compounds which include N,N'-dibutylhexanediamide, 1-butylazepane-2,7-dione and 1,8-diazacyclotetradecane-2,7‑dione have been subjected to thermal treatments together with melamine polyphosphate, aluminum diethylphosphinate or their combination respectively. Analyses of degradation products indicate that aluminum diethylphosphinate accelerates a cyclization reaction but does not change degradation mechanisms of polyamide 66 and its model compounds while melamine polyphosphate significantly shifts their degradation pathways to dehydration via a modified Hofmann elimination reaction which produces adiponitrile and water. Adiponitrile intumesces strongly when heated with polyphosphoric acid. Water hydrolyzes amides to amines, accompanied by the formation of amino-6-oxohexanoic acid which cyclizes to cyclopentanone. Water and amines together convert aluminum diethylphosphinate to diethylphosphinic acid. On the basis of the identification and transformation of reactive species, modes of flame retardant action of the combination of aluminum diethylphosphinate and melamine polyphosphate for PA66 have been proposed.
研究领域:
材料科学
·
化学工程
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2022
·
IF 3.119
Mengyang Guo,Ye Jiang,Yonghong Li,Yanyu Wei,Hanxi Li
The isobaric vapor–liquid equilibria (VLE) of two binary mixtures (adiponitrile + 2-methylglutaronitrile and adiponitrile + trans-3-pentenenitrile) at 5 and 10 kPa were measured using a modified Rose–Williams still. The thermodynamic consistency of the VLE data was tested by the Wisniak method and the Fredenslund method. The isobaric VLE data were correlated with four activity coefficient models of Margules, van Laar, Wilson, and NRTL, and the parameters of the models were obtained by the ordinary least-squares method. The isobaric VLE data were compared with the original UNIFAC predictive model. Furthermore, the excess Gibbs free energy of studied mixtures was determined. The RMST and RMSy1 were determined to evaluate the regression results. The results show that the Wilson model has a better correlation effect than other models.
研究领域:
化学工程
·
热力学
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DOI
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Shiyou Li,Dongni Zhao,Peng Wang,Xiaoling Cui,Fengjuan Tang
To satisfy the need of 5 V high-voltage cathode materials, lithium difluoro(oxalato)borate (LiDFOB) with excellent film-forming property has been chosen as lithium salt , and adiponitrile (ADN) with stable electrochemical performance has been evaluated as functional additive. An electrochemical investigation of this novel electrolyte solution shows a wide electrochemical oxidation window of nearly 6.0 V vs Li + /Li. Due to the positive effect of ADN on the cathode/electrolyte interface, LiNi 0.5 Mn 1.5 O 4 /Li half-cell with ADN-adding electrolyte exhibits prominent rate capability and cyclability. It is believed that the improvement of electrochemical performances has benefitted greatly from interfacial impedance reducing. Two modeling hypotheses have been used to explain interfacial interaction between ADN and LiNi 0.5 Mn 1.5 O 4 , by the means of analysis of X-ray photoelectron spectroscopy and theoretical calculation. Results show that ADN can enrich the surface of cathode material to hinder the further decomposition of the electrolyte, and contribute to the formation of a cathode-electrolyte interface passivation film with protective and conductive properties.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Liying Xu,Zhenlei Wang,Saidi Wang,Yanrong Liu,Xingmei Lu,Bing Yang,Ke Wang,Lijun Han,Jiayu Xin,Suojiang Zhang
The electrochemical dimerization of acrylonitrile (AN) to adiponitrile (ADN) is an essential process for nylon-66 production, but this process still faces many challenges such as low energy conversion efficiency and poor selectivity. Herein, various ionic liquids (ILs) were used as electrolyte additives to evaluate their effects on the electrochemical dimerization of AN. The addition of IL significantly enhanced the performance of the electrolytic reaction and inhibited the hydrogen evolution reaction (HER). The electrolyte containing Tetrabutylphosphonium bromide (TBPB) showed the highest faraday efficiency of adiponitrile (FEADN) of 84.5% and excellent stability at an optimal current density of 200 mA cm–2. Molecular dynamics (MD) simulations revealed that TBPB was uniformly dispersed in the electrolyte and formed a “long brush” hydrophobic layer with appropriate wettability on the electrodes. Moreover, it was observed that ILs with a more symmetrical cationic structure exhibited a better hydrophobic layer effect, favoring the dimerization of AN to ADN.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
AICHE JOURNAL
·
2024
·
IF 3.5
Le Zhou,Xin Zhang,Yu Han,Xin Li,Ze-Quan Zeng,Hai-Kui Zou,Yong Luo
The Co@NC catalyst exhibits significant protic solvent preference for hydrogenation of nitriles to primary amines. However, the effect of mixed protic solvents on catalytic hydrogenation has received little attention. Herein, the synergetic solvent effect has been proposed to accelerate the hydrogenation of adiponitrile (ADN) to hexamethylenediamine through H 2 O-ethanol hydrogen bond networks on Co@NC catalyst. Experimental screenings on solvents showed that ADN conversion in H 2 O-ethanol was 1.6 ~ 5.1 times greater than in single solvents. Kinetic models in H 2 O/ethanol ( v W = 0.6), H 2 O, and ethanol showed that the solvents effected on H 2 transformation dominated the reaction. Isotope labelling and kinetic experiments revealed that H 2 O and ethanol acted as co-catalysts through exchanging and transferring hydrogen via hydroxyl groups. Density functional theory calculations confirmed that the energy barrier for proton transfer mediated by H₂O–ethanol was reduced by 0.18 eV compared to proton transfer mediated by H₂O–H₂O dimers.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Jie Huang,Wenhao Yang,Sen Zhang,Jingjie Luo,Changhai Liang
Catalytic hydrogenation of adiponitrile to hexamethylenediamine (HMDA) via alkali-free processes is essential to produce high-value downstream chemicals. In this work, we synthesized a series of Co@C CNT x catalysts using CNT promotion to strength the carbon skeleton derived by ZIF-67. Compared to the Co@C without CNT promotion, great enhancement of HMDA yield was achieved by Co@C CNT x . Characterizations suggested that CNT in the precursor modified the crystallization of the active Co centers as well as the surface composition in the Co@C CNT x . Strong Co-carbon interaction was formed via Co-N coordination caused by the facilitated re-dispersion of N- containing functionalities. The ethanol contact angle on Co@C CNT x was changed for better mass transfer and diffusion of reaction liquid on the catalyst. As a final result, the oxidation of cobalt sites was greatly suppressed in Co@C CNT 0.3 and Co@C CNT 0.5 , which was proved an essential factor for their fast reaction rates. 88 % yield of HMDA with the rate of 4.5 mol HMDA /mol Co /h was reached under a much higher utilization rate of Co center.
研究领域:
化学工程
·
催化化学
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产品关联
DOI
高影响因子
Catalysts
·
2022
·Vol. 12
·期 7
·694
·
IF 4.501
Ji Qi,Ziying An,Xiao Chen,Chuang Li,Yan Du,Xiuhong Zhang,Changhai Liang
The classic acrylonitrile (AN) electrohydrodimerization (EHD) to adiponitrile (ADN) process produces oxygen on the anode side. The oxygen evolution reaction (OER) is energy consuming, and O2is of low value and has security issues while directly contacting with organic molecules. Herein, by replacing OER with 5-hydroxymethylfurfural oxidation reaction (HMFOR), we report paired electrolysis of AN and HMF for simultaneous generation of ADN and 2,5-furandicarboxylic acid (FDCA). On the anode side, the electrodeposited amorphous NiMoP film-covered nickel foam efficiently boosted HMFOR activity by enlarging the electrochemically active surface area (ECSA) via in situ selective removal of Mo and P on the surface. On the cathode side, addition of dimethylformamide (DMF) as a cosolvent enhanced the reaction efficiency of ANEHD by forming a single-phase electrolyte that offers better interaction between AN and the electrode. The ANEHD–HMFOR paired system shows excellent generation rates of FDCA (0.018 gFDCA·h−1·cm−2) and ADN (0.017 gADN·h−1·cm−2) at a high cell current (160 mA). An amount of 1 kWh of electricity can produce 2.91 mol of ADN and 0.53 mol of FDCA with 107.1% Faraday efficiency.Keywords:paired electrolysis;5-hydroxymethylfurfural oxidation;acrylonitrile electrohydrodimerization;adiponitrile;2,5-furandicarboxylic acid;dimethylformamide cosolvent
研究领域:
化学工程
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2026
·Vol. 71
·期 8
·3341-3352
·
IF 2.4
Zhang Lilei,Wang Ye,Ni Xuanyi,Wang Mengxin,Zhou Jingyuan,Qiu Yongsheng,Bu Youzhu,Chen Qingxi,Ma Ning
This study presents a comprehensive investigation of
the molecular
interactions in the binary system of dimethyl carbonate and adiponitrile
(ADN) by integrating thermodynamic measurements, spectroscopic analyses,
and molecular dynamics (MD) simulations. Experimental data on density,
speed of sound, and refractive index were collected across a temperature
range of 293.15 K–318.15 K, revealing significant nonideal
mixing behavior, including negative excess molar volumes and positive
deviations in speed of sound and refractive index, which intensify
with rising temperature due to enhanced intermolecular interactions.
MD simulations and spectroscopic evidence (Fourier transform infrared
and 1 H NMR) confirm the formation of weak C–H···O
and C–H···N hydrogen-bond-like contacts, providing
a molecular-level explanation for the observed macroscopic properties.
These findings underscore the role of specific dipole–dipole
and charge-transfer effects in governing the system’s behavior,
offering valuable insights for applications in solvent design and
molecular engineering.
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Yijing Qiu,Dongsheng Lu,Yunyan Gai,Yuepeng Cai
Adiponitrile (ADN) is studied as an additive of commercial carbonate electrolyte for a graphite/NCM811 Li-ion cell in this work. Compared with the cell using a baseline electrolyte, the cycling stability of the cells using 0.2, 0.5, 1, and 2 wt % ADN-added electrolytes is significantly improved. Among them, the effect is most prominent when the ADN content is 0.5 wt %, and the capacity retention rate of the cell after 200 cycles at 0.3 C is increased by 17.6%. Scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses confirm that ADN can make the coating layer formed on the cathode and anode surfaces of the cell denser and uniform. The formation of the cathodic coating layer does not obey the usual mechanism of adsorption between the nitrile group and metal ions, but it may be due to the polymerization of ADN initiated by carbocations from the oxidation of solvent molecules (ethylene carbonate/ethyl methyl carbonate) in the electrolyte. The cathodic coating layer greatly decreases the oxidation of the electrolyte so that a stable coating layer (also called solid electrolyte interface/SEI) can be formed on the anode, which is the reason for improvement of the cycling performance of the cell. However, the formation of the anode SEI layer is almost independent of ADN, and it still depends on the common reduction reaction of the electrolyte.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Omega
·
2020
·
IF 2.87
Li Wang,Shengxian Liu,Wenjing Du,Tongyi Dou,Changhai Liang
5-Cyanovaleramide (5-CVAM) is an important intermediate of a herbicide and chemical raw material. Herein, we found a novel nitrile hydratase from the strain Rhodococcus erythropolis CCM2595, exhibiting high regioselectivity with higher substrate specificity toward dinitriles than mononitriles. In the past, the strain was shown to degrade only phenol, hydroxybenzoate, p-chlorophenol, aniline, and other aromatic compounds. In our study, 20 mM adiponitrile was completely consumed within 10 min with 95% selectivity to 5-CVAM and 5% selectivity to adipamide. In addition to its high regioselectivity, our recombinant Escherichia coli showed a higher substrate tolerance of up to 200 mM adiponitrile even after 3 h when compared with two reported strains with their cyano-tolerance concentrations of up to 100 mM, which is considered to be the highest cyano-tolerance. Such a robust biocatalyst is a desirable attribute of a biocatalyst intended for use in commercial applications of 5-CVAM.
研究领域:
生物催化
·
生物化学
·
化学工程
·
酶技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Tao Guo,Fang-You Yan,Yao-Feng Wang,Xiao-Feng Xu,Qing-Zhu Jia,Bao-Hua Xu
To reach highly active and selective gas-phase nitrilation of dimethyl adipate (DMA) with NH 3 , a series of Nb x W 10-x (x = 10, 9, 7, 5 and 0) composite were fabricated by a sol–gel method to approach the homogeneous combination of NbO x and WO x . As a result, the single-pass yield of adiponitrile (ADN) reached 85.2% over Nb 9 W 1 under lower reaction temperature and lower NH 3 /DMA molar ratio. Consequently, the space–time yield (STY) of ADN over Nb 9 W 1 was 1.7 ∼ 30 times higher than that of previous catalysts. Mechanistic experiments demonstrated the activity strongly correlates the interaction between the carbonyl functionality and the composite. Further, a significant synergistic effect between W and Nb was disclosed, wherein the Nb-based domains account for activating DMA while the W-based domains mainly adsorb and activate NH 3 feedstock.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
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