程津培
物理有机化学
个性化签名
- 姓名:程津培
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学术头衔:
博士生导师, 中国科学院院士
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学科领域:
物理化学
- 研究兴趣:物理有机化学
程津培院士1981年获南开大学化学系硕士学位,1987年获美国西北大学博士学位,1987年至1988年在美国杜克大学做博士后研究。1988年回国在南开大学任教,先后任南开大学副教授、教授、博士生导师。1995年任南开大学副校长。2001年当选中国科学院院士。现任南开大学化学学院教授,中科院化学所兼职研究员,科技部副部长。兼任国务院学位委员会委员,中国化学会副理事长,国家自然科学基金委员会委员,教育部教学指导委员会委员等职。 自1978年至今的20多年来一直从事以物理有机化学为主要方向的基础研究。回国以来承担多项国家自然科学基金课题(含"八五"重大、"九五"重点、"十五"重点各一项),其间担任我校"物理有机化学"等课程主讲教师十余年。
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2399
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376
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成果数
10
程津培, Sanzhong Luo, † Peng George Wang, § and Jin-Pei Cheng*, †‡
J. Org. Chem. 2004, 69, 555-558,-0001,():
-1年11月30日
The Baylis-Hilman reaction of cyclic enones was gretly accelerated in basic water solution withs imidazoles as catalysts, which resulted in short reactiion time. High yields, and expanding substrate scopes. Bicarbonate solution was shown to be the optimal reaction medium for thereaction in this study. The apparent "enhanced basicity" of imidaxles accounted for the rate increase in alkaline solution.
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【期刊论文】Ferrocenyl-Bearing Cyclopseudopeptiodes as Redox-Swotjcjable Cation Receptors
程津培, Hai Huang, Linjing Mu, Jiaqi He, and Jin-Pei Cheng*
J. Org. Chem. 2003, 68, 7605-7611,-0001,():
-1年11月30日
A family of ferrocenyl-bearing cyclpsudopeptides (1-10) designed for redox-switchable receptors of cations was synthesized. Circular dichrosim (CD) and cyclic valtammetry (CV) studies of cation biding properties in both the reduced (K1) and oxidized (K2) forms revealed that the binding preferecne is mainly governed by the charges and radius of theguest cation as well as by the suitability f the host to accommodate the guest. Particularly worth mehtioning is the fact that some synthesized cycpseudopeptieds showed high binding affinityand selectivity toward alcalineearthions. For example. the K1 of compound 2 binding with Ca2+ is 4.37×106mol-1·L and its Ca2+/K+ selectivityis 3.1×105:1, both values are much greater than those of an excelent natural ionophore, valinomycin (1×105mol/-1·L and 0.33:1, respectively). The inear relationship between the shifts of half-wave phtentials (△E1/2) and theradius/charge [r/(+)] ratios suggests that the sensitivity of electorchemicalresponses to cation complexation be dominated by repulsion factors between the redx center and the incoming cation guest.
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程津培, Zucheng Li*, † and Jin-Pei Chemg*, ‡
J. Org. Chem. 2003, 68, 37350-7360,-0001,():
-1年11月30日
The N-H bond dissociation enthalpies (BDE's) of 40 anilines (ρGC6H4NHY) from series series 1 to 4 with α-y and ρ-G substiturents and the stability of related rabicals (ρGC6H4NHY) were studied using ab inito (MP2) and density functional methods (B3LYP) with large basis stets. The results show that both methods reproduce earlier experimental BDEs within 2-3kca/mol and satisfactoryly predict the α and remote substiutent effects on BDEs (△BDEs), as they reproduced the experimental △BDEs within less than 1kcal/mol. Furthermore. the conventional radical stabilization enthalpy (RSE=-△BDE) was fjound to be invalid to represent the trend of the radical stabilization enthalpy the molecule effect (ME) can contribute more to RSE than the radical effect (RE) for certain series (1 and 4). These radicals are in fact stabilized by electron-withdrawing gruop (EWGs) but destabilized by electro-donating groups (EDGs). a phenomenon just opposite to the observed O-behavior of many other aromatic heteroatomic radicals studied so far. These radicals are thus assigned as a new rdical class counter-O (or Ō) according to Walter's terminology. Moreover. theexcelent multi-parmetric Hammett-type correlations indicated that the para substituent effects on BDEs originate mainy from polar effects. but those onradical stability originate from both spin delocalization and polar effects. The atomic charge and spin population variations at a radical center due to ρ-G substitution were also found to correlate satifactorily with REs. These results and radical stabilizatiion effects. Finally, an overall subsituent effect scale forradical strability has been proposed, and the overall substituent effect on the N-radicals was found to conform to the Capto-dative Principle.
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程津培, Baolian Zhang, † Xiao-Qing Zhu, *† Jin-Yong Lu, † Jiaqi He, † Peng G. Wang, ‡ and Jin-Pei Cheng*, †
J. Org. Chem. 2003, 68, 3295-3298,-0001,():
-1年11月30日
A new polysiloxane-supported NAD(P)H mdel, 1-benzyl-1, 4-dihydronicotinamide, was desigend and synthesized, wchich can efflclently reduce many activated olefins under mild conditions. The most advantageous features of this new polysitions. The most advantageous features of this new polysiloxane-si[[prted redictsamd are (1) easu wprli[amd s[aratopm pf tje reactopm [rpdicts amd (ii) good potental for recling use of the reductant, which makes this new polysiloxane-supported NAD(P)H model a promising alternative both in research laboratories and in indust rial processes.
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程津培, Xiao-Qing Zhu, * Yuan Yang, Ming Zhang, and Jin-Pei Cheng*
J. AM. CHEM. SOC. 2003, 125, 15298-15299,-0001,():
-1年11月30日
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程津培, Xiao-Qing Zhu, * Qian Li, Wei-Fang Hao, and Jin-Pei Cheng*
J. AM. CHEM. SOC. 2002, 124, 9887-9893,-0001,():
-1年11月30日
The first two series of Co-NO bond dissociation enthalpie inbenzonitrile solution were determined for 12 cobalt (Ⅱ) nitrosyl porphyins and for 12 cobalt (Ⅲ) nitrosyl porphyrins by trtiation calorimetry with suitable thermdyamic cycles. The results display that the energy scales of the heterolytic CnⅢ-NP bpd dosspcoation, the homolytic CoⅢ-NO bond bond dissociation, and the homolytic CoⅡ-NO bond dissociation indicates that the thernidynamic stability of cobalt (Ⅱ) nitrosyl porphyrins is larger than that of the corresponding cobalt (Ⅲ) nitrosyl porphyirins for homolysis in bezonitrile solution but also suggests that both cobalt (Ⅲ) nirtosyl porphyrins are also excellnet NO+ contributors Hammett-type linear free energy analyses suggest that the nitrosyl group carries negative charges of 0.49±0.06 and 0.27±0.04 in T (G) PPCnⅡNO and T (G) OOCoⅢNO, respectivel, which indicates that nitric oxide is an electron-withdrawing group both in T (G) PPCoⅡNO and in T (G) OOCoⅢNO, behaving in a manner similar to Lewis acids rather than to Lewis bases. The energetic and strutural information disclosed inthe present work is believed to furnish hints to the undersanding of cobalt nitrosvl porphvris'biological functions in vivo.
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程津培, Jian-Ming Lǖ, † Joanne M. Wittgrodt, ‡ Kun Wang, †‡ Zjpmg Wem, ‡ H. Bernhard Schelgel, ‡ Peng George Wang, *, ‡ and Jin-Pei Cheng, *, †
,-0001,():
-1年11月30日
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程津培, Xiao-Qing Zhu, * Hai-Rong Li, Qian Li, Teng Ai, Jin-Yong Lu, Yuan Yang, and Jin-Pei Cheng*|a|
,-0001,():
-1年11月30日
Heterolytic and homolytic bond dissocation energies of the C4-H bonds in tem NADH models (seven 1, 4-dihydronicotinamide deriatives, two Hantzch 1, 4-dihydropyridine derivative, and 9, 10-dihydroacridine) and their radical cations in acetonitrile were evalated by titration calorimetry and electrocemistry, according to the four thermodynamic cycles constructed from the reaction of the NADH models with N, N, N', N'-tetramethyl-p-phenylenediamine radical cation percorate in acetonitrile (note: C9-H bond rather than C4-H bond for 9, 10-dihydroacridine; however, unless specified, the C9-H bond will be described as a C4-H bond forconvenience). The results show that the energetic scales of the heterolytic and homolytic bond dissociation energies ofthe C4-H bonds cover ranges of 64.2-81.1 and 67.9-73.7 kcalmol-1 for the neutral NADH models, respectively, and the energetic scales of the heterolytic and homolytic bond dissociation energies of the (C4-H)*+ bjonds cover ranges of 4.1-4.9 and 31.4-43.5 kcalmol-1 for the radical cations of the NADH models, respectively. Detailed comparsion of the two stes of C4-H bond dissociation energies in 1-benzyl-1, 4-dihydronicotinamide (BNAH), Hantzsch 1, 4-dihydripyridine (HEH), and 9, 10-dihydrioacridine (AcrH2) (as the three most typical NADH models) shows that for BNAH and AcrH2, the heterolytic C4-H bond dissociation energies are smaller (by 3.62kcalmol-1) and larger (by 7.4 kcalmol-1), respectivel, than the correspoding homolytic C4-H bond homolytic C4-H bond dissociation energy. However, for HEH, the heterolytic C4-H bond dissociation energy (69.3kcalmol-1) is very close to the corresponding homolytic C4-H bond dissociation energy (69-4kcalmol-1). These results suggests that the hydride is released more easily than the corresponding hydrogen atom from BNAH and vice versa for AcrH2, and that there are two almost equal posibilities for the hydride and the hydrigen atom transfers from HEH. Examination of the two sets of the (C4-H)*+ bond dissociation energies shows that the homlytic (C4-H)*+ bond dissociation energies are mcuh larger than corresponding heterolytic (C4-H)*+ bond dissociatiion energies for the ten NADH models by 23.3-34.4 kcalmol-1; this suggests that if the hydride transfer from the NADH models is initiated by a one-electrom transfer, the proton transfer should be more likely totake place transfer shuld bemore likely to take placed than the corresponding hydrogen atom transfer in the second step. In addition, some elusive structural information about the reaction intermediates of the Nadh models was obtained by using Hammett-type linear free-energy analysis.
bond energy
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程津培, Xiao-Qing Zhu, * Lei Cao, Yang Liu, Yuan Yang, Jin-Yong Lu, Jian-Shuang Wang, and Jin-pei Cheng-|a|
Chem Eur. J. 2003, 9, 3937-3945,-0001,():
-1年11月30日
Five 1-(p-substituted phenyl)-1, 4-dihydronicotinamides (GPNAH-1, 4-H2) and five 1-(p-substituted phenyl)-1, 2-dihydronicotiamides (GPNAH-1, 2-H2) were sumtjeszed, which were used to mimic NAD(P)H coenzyme and its 1, 2-dihydoisoer reductions, respectively. When the 1, 4-dihydropridine (GPNAH-1, 4-H2) and the 1, 2-dihydroisomer (GPNAH-1, 2-H2) were treated with P-trifluoromethylbenzylidene maonoitrile (S) as a hydride acceptor, both reactions gave the same products: pyridinium derivative (GPAN+) and carbanion SH- by a hydride one-step transfer. Thermodynamic analysis on the two reactions shows that the hydride transfer form the 1, 2-dihydropyridine is much more favoraable than the hydride tranfer from the correponding 1, 4-dihydroisomer, but the kinetic examination displays that the former reaction is remarkably slower than the latter reaction, which is mainy due to much more negative activati entropy for the former reaction. Wen the formed pyridinium DERIVATIVE (GPNA+) was treated with SH-, the major reduced product was the corresponding 1, 4-dihydropyridine along with a trace of the 1, 2-dihydroisomer. Thermodynamic and kinetic analyses on the hyddride transfer from SH- to GPNA+ all suggest that the 4-[psotopm pm tje [urodomoi, romg om GPNA+ is much easier to accept the hydride than the 2-position, which indicates that when the 1, 4-dihydropyridines is used the hydride donor to react with S, the formed pyridinium derivative GPNA+ may return to the 1, 4-dihydropyridine by a hydride transfer cycle; but when the 1, 2-dihydropyridine is used as the hydride donor, the formed pyridinium derivative can not reutrn to the 1, 2-dojudropyridine by the hydride reverse transfer form SH- to GPNA+. These results clearly show that the hydridetranfer cycle is favorable for the 1, 4-dihydronicotinamides, but unfavorable for the cxorrpsponding 1, 2-dihydroisomers.
hydride transfer
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程津培, Zhenming Yin, Ling Jiang, Jiaqi He and Jin-Pei Cheng*
CHEM. COMMUN., 2003, 2326-2327,-0001,():
-1年11月30日
A new type of weak bond, i.e., the N…O=C interaction, that determines the crystal packing of N-oxalyl 2,4-dintroanilde (1) in coperation with C-H…O hydroge bonds, has been fund and is rationalized by ad initio calculatins as being the result of electrostatic interactions.
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