Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H•••O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

被引:151
作者
Sato, H
Dybal, J
Murakami, R
Noda, I
Ozaki, Y [1 ]
机构
[1] Kwansei Gakuin Univ, Dept Chem, Sch Sci & Technol, Sanda 6691337, Japan
[2] Kwansei Gakuin Univ, Res Ctr Environm Friendly Polymers, Sanda 6691337, Japan
[3] Acad Sci Czech Republic, Inst Macromol Chem, Prague, Czech Republic
[4] Procter & Gamble Co, W Chester, OH 45069 USA
关键词
infrared and Raman spectroscopy; quantum chemical calculation; C-H center dot center dot center dot O hydrogen bonding; thermal behaviour; biodegradable polyhydroxyalkanoate;
D O I
10.1016/j.molstruc.2004.10.069
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This review paper reports infrared (IR) and Raman spectroscopy and quantum chemistry calculation studies of C-H center dot center dot center dot O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoates. IR and Raman spectra were measured for poly(3-hydroxybutyrate) (PHB) and a new type of bacterial copolyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), P(HB-co-HHx) (HHx = 12 mol%) over a temperature range of 20 T to higher temperatures (PHB, 200 degrees C; HHx = 12 mol%, 140 degrees C) to explore their structure and thermal behavior. One of bands due to the CH3 asymmetric stretching modes appears near 3010 cm(-1) in the IR and Raman spectra of PHB and P(HB-co-HHx) at 20 T. These frequencies of IR and Raman CH3 asymmetric stretching bands are much higher than usual. These anomalous frequencies of the CH3 asymmetric stretching bands together with the X-ray crystallographic structure of PHB have suggested that there is an inter- or intramolecular C-H... 0 hydrogen bond between the C=O group in one helical structure and the CH3 group in the other helical structure in PHB and P(HB-co-HHx). The quantum chemical calculation of model compounds of PHB also has suggested the existence of C-H... 0 hydrogen bonds in PHB and P(HB-co-HHx). It is very likely that a chain of C-H... 0 hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR and Raman spectral variations have revealed that the crystallinity of P(HB-co-HHx) (HHx = 12 mol%) decreases gradually from a fairly low temperature (about 60 T), while the crystallinity of PHB remains almost unchanged until just below its melting temperature. It has also been found from the IR and Raman studies that for both PHB and P(HB-co-HHx) the weakening of the C-H... 0 hydrogen bonds starts from just above room temperature, but the deformation of helical structures occurs after the weakening of the C-H... 0 hydrogen bonds advances to some extent. (c) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:35 / 46
页数:12
相关论文
共 54 条
[1]   Solid-state structures and enzymatic degradabilities for melt-crystallized films of copolymers of (R)-3-hydroxybutyric acid with different hydroxyalkanoic acids [J].
Abe, H ;
Doi, Y ;
Aoki, H ;
Akehata, T .
MACROMOLECULES, 1998, 31 (06) :1791-1797
[2]   OCCURRENCE, METABOLISM, METABOLIC ROLE, AND INDUSTRIAL USES OF BACTERIAL POLYHYDROXYALKANOATES [J].
ANDERSON, AJ ;
DAWES, EA .
MICROBIOLOGICAL REVIEWS, 1990, 54 (04) :450-472
[3]   INVESTIGATION OF THE MOLECULAR-STRUCTURE AND CONFORMATION OF 1,2-DIMETHOXYETHANE, CH3-O-CH2-CH2-O-CH3, IN THE GAS-PHASE [J].
ASTRUP, EE .
ACTA CHEMICA SCANDINAVICA SERIES A-PHYSICAL AND INORGANIC CHEMISTRY, 1979, 33 (09) :655-664
[4]   Raman spectroscopic evidence for cooperative C-H•••O interactions in the acetaldehyde-CO2 complex [J].
Blatchford, MA ;
Raveendran, P ;
Wallen, SL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) :14818-14819
[5]   Reversal of the usual ν(C-H/D) spectral shift of haloforms in some hydrogen-bonded complexes [J].
Boldeskul, IE ;
Tsymbal, IF ;
Ryltsev, EV ;
Latajka, Z ;
Barnes, AJ .
JOURNAL OF MOLECULAR STRUCTURE, 1997, 437 :167-171
[6]  
CORNIBERT J, 1972, J MOL BIOL, V71, P735
[7]  
Dawes E.A., 1990, Novel biodegradable microbial polymers, V1st
[8]   Blue shifting hydrogen bonding in the complexes of chlorofluoro haloforms with acetone-d6 and oxirane-d4 [J].
Delanoye, SN ;
Herrebout, WA ;
van der Veken, BJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (40) :11854-11855
[9]  
Desiraju G. R, 1999, WEAK HYDROGEN BOND
[10]  
DOI Y, 1995, MACROMOLECULES, V28, P4822, DOI 10.1021/ma00118a007