|本期目录/Table of Contents|

[1]赵 宇,王 艳,王佐成*,等.水环境下扶椅型单臂碳纳米管内缬氨酸旋光异构及羟自由基致损伤机理[J].厦门大学学报(自然科学版),2019,58(03):307-316.[doi:10.6043/j.issn.0438-0479.201806027]
 ZHAO Yu,WANG Yan,WANG Zuocheng*,et al.Mechanism of optical isomerization and damage of valine moleculesinduced by hydroxyl radicals in armchair single-walled carbon nanotubes in water environment[J].Journal of Xiamen University(Natural Science),2019,58(03):307-316.[doi:10.6043/j.issn.0438-0479.201806027]
点击复制

水环境下扶椅型单臂碳纳米管内缬氨酸旋光异构及羟自由基致损伤机理(PDF/HTML)
分享到:

《厦门大学学报(自然科学版)》[ISSN:0438-0479/CN:35-1070/N]

卷:
58卷
期数:
2019年03期
页码:
307-316
栏目:
研究论文
出版日期:
2019-05-28

文章信息/Info

Title:
Mechanism of optical isomerization and damage of valine moleculesinduced by hydroxyl radicals in armchair single-walled carbon nanotubes in water environment
文章编号:
0438-0479(2019)03-307-10
作者:
赵 宇1王 艳2王佐成3*佟 华3绳绍旭3白 杰3张新楠3
1.白城师范学院计算机科学学院,吉林 白城 137000; 2.白城师范学院土木工程学院,吉林 白城 137000; 3.白城师范学院物理学院,吉林 白城 137000
Author(s):
ZHAO Yu1WANG Yan2WANG Zuocheng3*TONG Hua3SHENG Shaoxu3BAI Jie3ZHANG Xinnan3
1.College of Computer Science,Baicheng Normal University,Baicheng 137000,China; 2.College of Civil Engineering,Baicheng Normal University,Baicheng 137000,China; 3.College of Physics,Baicheng Normal University,Baicheng 137000,China
关键词:
缬氨酸 旋光异构 损伤 碳纳米管 ONIOM方法
Keywords:
valine optical isomerism damage carbon nanotubes ONIOM method
分类号:
O 641.12
DOI:
10.6043/j.issn.0438-0479.201806027
文献标志码:
A
摘要:
用量子力学与分子力学组合的ONIOM方法,结合自洽反应场的SMD(slovation model density)模型方法,对水环境下单臂碳纳米管(SWCNT)内缬氨酸的旋光异构及羟自由基致损伤机理进行了研究.势能面计算表明:以2个水分子簇作传递质子媒介,氨基氮作质子迁移桥梁时,缬氨酸限域在SWCNT(8,8)和SWCNT(7,7)内旋光异构的决速步能垒分别是115.80和165.64 kJ/mol,水溶剂效应使这2个能垒降到104.34和150.07 kJ/mol.限域在SWCNT(8,8)内的缬氨酸,羟自由基抽氢致其损伤的能垒是13.31 kJ/mol,水分子辅助羟自由基抽氢致其损伤的能垒约15.00 kJ/mol,水溶剂效应使它们相应地上升至18.85和约20.00 kJ/mol.结果表明:SWCNT(8,8)和SWCNT(7,7)的限域对水环境下缬氨酸的旋光异构分别具有正催化和负催化作用,水溶剂具有助催化作用; SWCNT(8,8)的限域对水环境下羟自由基致缬氨酸损伤具有显著的催化作用,水溶剂则会阻碍羟自由基致缬氨酸损伤.
Abstract:
Using ONIOM method combined with quantum mechanics and molecular mechanics, as well as slovation model density(SMD)method based on the self consistent reaction field theory,the mechanism of optical isomerization and damage of valine induced by hydroxyl radicals in armchair single-walled carbon nanotubes(SWCNT)in water environment was studied.Calculations of potential energy surface showed that when valine was confined in SWCNT(8,8)and SWCNT(7,7)with two water molecular clusters as proton transfer medium and amino nitrogen as a proton transfer bridge,the energy barrier of the rate-determining step of optical isomerization was 115.80 kJ/mol and 165.64 kJ/mol,respectively,which decreased to 104.34 kJ/mol and 150.07 kJ/mol under water solvent effect.For valine molecules confined in SWCNT(8,8),the energy barrier of damage induced by H-atom abstraction of hydroxyl radicals was 13.31 kJ/mol,and the corresponding energy barrier of damage induced by H-atom abstraction of hydroxyl radicals assisted with water molecules was about 15.00 kJ/mol,which increased to 18.85 kJ/mol and about 20.00 kJ/mol,respectively under water solvent effect.The results showed that the confinement of SWCNT(8,8)and SWCNT(7,7)had respectively positive and negative catalytic effects on the optical isomerism of valine in water environment and the water solvent had an auxiliary catalytic effect.Moreover,the confinement of SWCNT(8,8)had a significant catalytic effect on the damage of valine induced by hydroxyl radicals in water environment,and the effect of water solvent hindered the damage of valine induced by hydroxyl radicals.

参考文献/References:

[1] 漆剑.L-脯氨酸和L-缬氨酸构型转换的研究[D].南昌:南昌大学,2006.
[2] CHOLEWINSKI A J,REID J C,MCDERMOTT A M,et al.Purification of astroglial-cell cultures from rat spinal cord:the use of D-valine to inhibit fibroblast growth[J].Neurochem Int,1989,15(3):365-369.
[3] 严传鸣.氟胺氰菊酯的合成[J].现代农药,2003,2(1):13-15.
[4] CARL P,KATZENELLENBOGEN L,JOHN A,et al.Hydrolyti-cenzyme-activatible pro-drugs:WO8101145[P].1981-04-30.
[5] NEUBERGER A.Stereochemistry of amino acids[J].Adv Protein Chem,1948,4:297-383.
[6] SMITH G G,SIVAKUA T.Mechanism of the racemization of amino acids.Kinetics of racemization of arylglycines[J].J Org Chem,1983,48(5):627-634.
[7] 闫红彦,王佐成,邹晶,等.缬氨酸分子的手性转变及水分子的催化机理[J].中山大学学报(自然科学版),2016,55(2):68-75.
[8] 赵宇,汤振宇,吴怡,等.水环境下具有氨基和羧基间双氢键的缬氨酸旋光异构及羟自由基致损伤的机理[J].中山大学学报(自然科学版),2018,57(3):96-107.
[9] 郝成欣,汤振宇,吴怡,等.具有氨基与羧基间单氢键的缬氨酸分子旋光异构及羟自由基致损伤的机理[J].复旦学报(自然科学版),2018,57(6):794-805,812.
[10] 马驰骋,蒲敏,卫敏,等.L-缬氨酸旋光异构的两种光反应可能途径[J].物理化学学报,2012,28(8):1830-1836.
[11] 高峰,潘宇,乔朝阳,等.扶手椅型单壁碳纳米管孔径对缬氨酸分子旋光异构的限域影响[J].武汉大学学报(理学版),2019,65(1):1-10.
[12] 孙大春,闫红彦,王佐成,等.水与扶手椅型SWCNT复合环境下α-Ala的手性转变机理[J].吉林大学学报(理学版),2016,54(4):892-901.
[13] SVENSSON M,HUMBEL S,FROESE R D J,et al.ONIOM:a multilayered integrated MO+MM method for geometry optimizations and single point energy predictions.A test for Diels-Alder reactions and Pt(P(t-Bu)3)2+H2 oxidtivae addition[J].Physical Chemistry,1996,100(50):19357-19363.
[14] CHAI J D,HEAD-GORDON M.Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections[J].Physical Chemistry Chemical Physics,2008,10(44):6615-6620.
[15] RAPPE A K,CASEWIT C J,COLWELL K S,et al.UFF,a full periodic table force field for molecular mechanics and molecular dynamics simulations[J].J Am Chem Soc,1992,114(25):10024-10035.
[16] GARRETT B C,TRUHLAR D G.Criterion of minimum state density in the transition state theory of bimolecular reactions[J].The Journal of Chemical Physics,1979,70(4):1593-1598.
[17] GONZALEZ C,SCHLEGEL H B.Reaction path following in mass-weighted internal coordinates[J].J Phys Chem,1990,94(14):5523-5527.
[18] BINKLEY J S,POPLE J A.M?eller-Plesset theory for atomic ground state energies[J].Int J Quantum Chem,1975,9(2):229-236.
[19] MARENICH A V,CRAMER C J,TRUHLAR D G.Universal slovation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions[J].J Phys Chem B,2009,113(18):6378-6396.
[20] FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09.Revision E.01[CP].Pittsburgh:Gaussian Inc.,2013.
[21] 黄志坚.氨基酸的构型和性质研究[D].合肥:中国科学技术大学,2006:11.
[22] GORB L,LESZCZYNSKI J.Intramolecular proton transfer in mono-and dihydrated tautomers of guanine:an ab initio post Hartree-Fock study[J].J Am Chem Soc,1998,120(20):5024-5032.

备注/Memo

备注/Memo:
收稿日期:2018-06-25 录用日期:2018-09-06
基金项目:吉林省科技发展计划(20160101308JC)
*通信作者:wangzc188@163.com
更新日期/Last Update: 1900-01-01