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Professor Yun Lu's Personal Page


Experience:

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Research Interests:

  • Employing our recently established approach that determines the kinetics of the oxidation of alcohols via hydride transfer to organic carbocations, we are investigating the effects of various structures of alcohols on their ability to release a hydride ion to form the α–hydroxy-carbocations (C+-OH). Theoretical calculations are carried out in order to aid the understanding of the experimental results. We are also studying the catalytic effect of metal ions on these reactions that serve as alcohol dehydrogenase model reactions. In living organisms, the Zn(II) ion is believed to catalyze the alcohol deydrogenase reaction by the formation of a reactive zinc alkoxide intermediate through Lewis acid catalyzed deprotonation of the alcohol. This research will (1) provide chemists in organic chemistry and related areas with unprecedented structure-reactivity relationship data for alcohols to release a hydride ion, (2) enrich and develop the organic chemistry theory relating to carbocation chemistry, (3) enable a deeper understanding of the general hydride reduction of organic carbocations by alcohols, and (4) provide successful alcohol dehydrogenase model reactions to advance the understanding of the important biological hydride transfer reactions.

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Courses:

  • Organic chemistry 241a and 241b
  • The Organic chemistry of Enzyme Catalyzed Reactions 449/549
  • Graduate Seminar 575
  • Organic Lab 245 (coordinating)
  • General, Organic and Biol Chem Lab 124B (coordinating)
  • Nursing Chemistry Lab 124A (coordinating)

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Support:

  • “Non-Steady-State Kinetic Studies of Bimolecular Nucleophilic Substitution Reactions at Saturated Carbon in Solution” American Chemical Society, Petroleum Research Funds, August 2006 – August 2009, $35,000.
  • “MRI: An EPR Spectrometer for Teaching and Research” National Science Foundation, (Co-PI), 2008-2011, $173,360.
  • “Biomimetic Investigation of the Alcoholic Oxidations Mediated by Alcohol Dehydrogenases” SIUE Summer Research Fellowship, Summer 2008, $8,000.
  • “Biomimetic Investigation of the Alcoholic Oxidations Mediated by Alcohol Dehydrogenases” SIUE Funded University Research, July 2008 – July 2009, $3,279.
  • “Green Chemistry Synthesis of Azoxyarenes — Materials of Widespread Utility in Liquid crystals” SIUE Summer Research Fellowship, Summer 2007, $8,000.
  • “Green Chemistry Synthesis of Azoxyarenes — Materials of Widespread Utility in Liquid Crystals” SIUE Funded University Research, July 2006 – July 2007, $8,874.
  • “Non-Steady-State Kinetic Studies of Bimolecular Nucleophilic Substitution Reactions at Saturated Carbon in Solution” SIUE Summer Research Fellowship, Summer 2005, $6,000.
  • “Kinetics, thermodynamics and mechanism of NAD(P)H coenzyme model mediated reductions” National Science Foundation of China, 1997 – 2000, ¥110,000.

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Research Group:

  • Catherin Obal, undergrad (‘04-‘05)
  • Gary Diffee, undergrad (‘05-‘07)
  • Donald Endicott, undergrad and grad (‘05-‘08)
  • William Kuester, undergrad and grad (‘06-‘08)
  • Zahra Khedri, grad (‘06-‘07)
  • Daniel Cranford, undergrad (‘06)
  • Brian Morre, undergrad (07-08)
  • Joshua Bradshaw, undergrad (‘07-present)
  • Fengrui Qu, grad (‘06-‘08)
  • Ashia Small, undergrad and grad (‘07-present)
  • Eric Hellrung, undergrad (‘07-present)
  • Yu Zhao, grad (‘07-present)

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Publications:

37.

Yun Lu, Fengrui Qu, Brian Moore, Donald Endicott, William Kuester “Hydride Reduction of NAD+ Analogues by Isopropyl Alcohol: Kinetics, Deuterium Isotope Effects and Mechanism” J. Org. Chem. (Featured Article) 2008, 73, 4763.

36.

Yun Lu, Donald Endicott, William Kuester “Effective Thermal Oxidation of Isopropanol by an NAD+ model.” Tetrahedron Letters 2007, 48, 6356.

35.

Yun Lu, Jiancheng Liu, Garry Diffee, Diansheng Liu, Bo Liu “Reduction of Nitroarenes by Hydroxide Ion in Water Catalyzed by β-Cyclodextrin: Enhanced Reactivity of Hydroxide Ion.”    Tetrahedron Letters 2006, 47, 4597.

34.

Vernon D. Parker, Yun Lu, Yixing Zhao  “Proton Transfer Reactions of Methylanthracene Radical Cations with Nitrogen-Centered Bases under Non-Steady-State Conditions.  A Search for  the Possible Effect of Reactant Impurities upon the Kinetic Data.” J. Org. Chem. 2005, 70, 1350.

33.

Kishan L. Handoo, Yun Lu, Vernon D. Parker “Resolution of the Non-steady-state kinetics of the 2-step mechanism for the Diels-Alder reaction between anthracene and tetracyanoethylene in Acetonitrile” J. Am. Chem. Soc.  2003, 125, 9381.

32.

Yun Lu, Kishan L. Handoo, Vernon D. Parker “Non-steady-state study of the SN2 reaction between 4-nitrophenoxide ion and methyl iodide in aprotiuc solvents containing water. Evidence for a         2-step mechanism” Org. Biomol. Chem2003, 1, 36.

31.

Vernon D. Parker, Yun Lu  “Non-steady-state kinetic study of the SN2 reaction between p-nitrophenoxide ion and methyl iodide in acetonitrile” Org. Biomol. Chem. 2003, 1, 2621.

30.

Yun Lu, Yixing Zhao, Kishan L. Handoo, Vernon D. Parker “Hydride-exchange reactions between NADH and NAD+ model compounds under non-steady-state conditions. Apparent and Real kinetic isotope effects” Org. Biomol. Chem. 2003, 1, 173.

29.

Meng-Sheng Liao, Yun Lu, Vernon D. Parker, Steve Scheiner “DFT calculations and spectral measurements of charge-transfer complexes formed by aromatic amines and nitrogen heterocycles with tetracyanoethylene and with chloranil” J. Phys.Chem. A 2003, 107, 8939.

28.

Kishan L. Handoo, Yun Lu, Yixing Zhao, Vernon D. Parker “Resolution of the non-steady-state kinetics of the elimination of HBr from 2-(4-nitrophenyl)ethyl bromide in alcohol/alkoxide media)” Org. Biomol. Chem.  2003, 1, 24.

27.

Meng-Sheng Liao, Yun Lu, Steve Scheiner “Performance of Density-Functional Methods for Charge-Transfer Complexes” J. Comput. Chem. 2003, 24, 623.

26.

Martin Newcomb, Runnan Shen, Yun Lu, Minor J. Conn, Paul F. Hollenberg, Daniel A. Kopp, Stephen J. Lippard  “Evaluation of norcarane as  a probe for radicals in cytochrome P-450 and soluble Methane Monooxygenase- catalyzed hydroxylation reactions” J Am. Chem. Soc. 2002, 124, 6879.

25.

Yun Lu, Yixing Zhao, Vernon D. Parker “Proton-transfer reactions of methylarene radical cations with pyridine bases under non-steady-state conditions. Real kinetic isotope effect evidence for extensive tunneling” J Am. Chem. Soc. 2001, 123, 5900.

24.

Yixing Zhao, Yun Lu, Vernon D. Parker “Proton-transfer reactions between nitroalkanes and hydroxide ion under non-steady-state conditions. Apparent and real kinetic isotope effects” J Am. Chem. Soc. 2001, 123, 1579.

23.

Vernon D. Parker, Yixing Zhao, Yun Lu “Non-steady-state kinetics of the reactions of electrode generated intermediates. Resolution of the kinetics of proton transfer reactions of methylene radical cations.” Electrochemical Society Proceedings, 2001, 14, 1.

22.

Yixing Zhao, Yun Lu, Vernon D. Parker “Non-Steady-State Kinetic Studies of the Real Kinetic Isotope Effects and Arrehenius Activation Parameters for the Proton Transfer reactions of 9,10-Dimethylanthrance Radical Cation with Pyridine Bases” J Chem Soc, Perkin Trans 2. 2001, 1481.

21.

Jin-Pei Cheng, Yun Lu, Xiaoqing Zhu,Shun Yongkai, Feng Bi, He, Jiaqi  “Hetereolytic and Homolytic N-H Bond Dissociation Energies of 4-Substituted Hantzch2,6-dimethyl-1,4-dihydro-pyridines and the Effect of One-electron Transfer on the N-H Bond Activation” J. Org. Chem. 2000, 65, 3853.

20.

Bingjun Zhao, Xiaoqing Zhu, Yun Lu, Chizhong Xia, Jin-Pei Cheng “Kinetics and Mechanistic investigation on the Oxidation of Hantzsch 1,4-Dihydropyridines with the Tropylium Cation: A Model for NADH Oxidation.” Tetrahydron Lett. 2000, 41, 257.

19.

Yun Lu, Ming Xian, Xiaoqing Zhu, Kun Wang, Linjing Mu, Jin-Pei Cheng “Studies on the Structure-Activity Relationship of NAD(P)H Models: Electronic Effects of 3-Acyls” J. Chem. Chinese Univ. 1999, 19, 59.

18.

Jin-Pei Cheng, Bo Liu, Yongyu Zhao, Yongkai Sun, Xian-Man Zhang, Yun Lu,  “Effects of Adjacent Onium Cations and Remote Substituents on the H-A+ Bond Equilibrium Acidities in Dimethyl Sulfoxide Solution. An Extensive Ylide Thermodynamic Stability Scale and Implication for the Importance of Reasonance effect on Ylide Stabilities.” J Org. Chem. 1999, 64, 604.

17.

Jin-Pei Cheng, Yun Lu, Xiaoqing Zhu, LinJing Mu “Energetics of Multi-step vs. One-step Hydride Transfer Reactions of Reduced Nicotinamide Adenine Dinucleotide (NADH) Models with Organic Cations and p-Quinones” J. Org. Chem. 1998, 63, 6108.

16.

Vernon D. Parker, Yixing Zhao, Yun Lu, Gang Zheng “Application of Non-Steady-State Kinetics to Resolve the Kinetics of Proton Transfer Reactions between Methylarene Radical Cations and Pyridine Bases” J Am. Chem. Soc. 1998, 120, 12720.

15.

Jin-Pei Cheng, Kun Wang, Zheng Yin, Xiaoqing Zhu, Yun Lu “NO Affinity. The Driving force of Nitric Oxide (NO) Transfer in Biomimetic N-nitrosoacetanilide and N-nitrososulfoanilide Systems” Tetrahedron Lett.  1998, 39, 7925.

14.

Jin-Pei Cheng, Yun Lu, Bo Liu, Yongyu Zhao, Yongkai Sun, Difei Wang, Jianglin Mi “Effects of Double Substitution of the Thermodynamic Stabilities of Nitrogen Radicals” Science in China (series B)(Engl) 1998, 41, 215.

13.

Hongxing Wang, Jin-Pei Cheng, Wenxiang Gu, Gaojiu Zhang, Zhenwei Huan, Yun Lu “Reactions of fluorocarbenes with carbonyl compounds - The effects of para-substituents and pre-aromatic character on deoxygenation of aryl aldehydes and tetraphenyl-cyclopentadienone” J. Chem. Chinese Univ. 1998, 19(8), 723.

12.

Yun Lu, Duan Liu, Bingjun Zhao, Xiaoqing Zhu, Jin-Pei Cheng “Bond Dissociation Energies of N(C)-H Bond Cleavage of Substituted-1,4-dihydro-Hantzsch Pyridines and Corresponding Ion Radicals: An Application on the Mechanistic Studies of Hantzsch Ester Mediated Reductions” J. Chem. Chinese Univ. (suppl.)  1998, 19(8), 432.

11.

Jin-Pei Cheng, Yun Lu “Kinetic, Thermodynamic and Mechanistic Studies on the Reduction of Carbenium Ions by NAD(P)H Analogues” J. Phys. Org. Chem1997, 10, 577-584.

10.

 Yun Lu, Bo Liu, Jin-Pei Cheng “Studies on the Thermodynamics and Mechanism of the Acid-Catalysed Reductions of N-arylfluoreneimines by NAD(P)H Models” J. Chem. Chinese Univ. 1997, 18, 391.

9.

Yun Lu, Ming Xian, Jin-Pei Cheng “Investigation on the Reductions of Carbocations by BNAH -- Kinetics, Thermodynamics and Mechanism” Acta Chimica Sinica 1997, 55, 1145.

8.

Yun Lu, Ming Xian, Jin-Pei Cheng  “Studies on the Mg2+-Catalyzed Reductions of N-arylfluoreneimines by NAD(P)H Models” J. Chem. Chinese Univ. 1997. 18, 1484.

7.

Jin-Pei Cheng, Bo Liu, Yun Lu “Homolytic and Heterolytic Bond Dissociations of α-V, VI Group Cation-substituted Toluenes and Acetophenones” J. Chem. Chinese Univ. 1997, 18, 1080.

6.

Yun Lu, Jin-Pei Cheng “Structure, Reactivity and Mechanism: A Comparison of Reactivities of the Two NAD(P)H Models” Chinese Science Bulletin (Engl.) 1996, 41, 1881.

5.

Yun Lu, Jin-Pei Cheng “Studies on the Kinetics of the Reduction of Ferricynide Ion By 1-Benzyl-1,4-dihydronicotinamide (BNAH)” Chinese Science Bulletin 1996, 41, 2150.

4.

Yun Lu, Jin-Pei Cheng, Hongxing Wang, Chizhong Xia “Studies on the Acid-Catalyzed Reduction of N-Arylfluorenimines by NAD(P)H Models” J. Chem. Chinese Univ. 1996, 17, 731.

3.

Benzhi Qiao, Yun Lu, Chongsheng Xuan “Metal Complexes of Antibiotic Pipemidic Acid”J. Chem. Chinese Univ. (Engl.) 1994, 10, 341.

2.

Liang Chen, Yuxian Hu, Baojun Wang, Yun Lu “Coordination of 4,7-Diphenyl-1,10-phenanthroline with d10 configuration Metal Ions Zn(II), Cd(II) and Hg(II)” J. Chem. Chinese Univ. 1988, 9, 1141.

1.

Liang Chen, Yuxian Hu, Yun Lu, Baojun Wang “Carbon-13 NMR Study on Complex of Some Transition Metal Ions with Sudan I (1-phenyl-2-naphthol)” J. Chem. Chinese Univ. 1988, 9, 88.

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