Chain conformation of polyethylene in the solid state as studied by 13C cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy

High-resolution ¹³C nuclear magnetic resonance (n.m.r.) spectra of melt-quenched polyethylene and polyethylene single crystals are measured by the cross-polarization/magic angle spinning technique. Melt-quenched polyethylene and polyethylene single crystals have four small upfield peaks, a shoulder on the main peak and three small peaks, respectively. Based on the ¹³C n.m.r. resonance lines of cyclic paraffin C₆₄H₁₂₈ reported previously, it is concluded that the main peak and the three upfield peaks arise from the trans zigzag structure region and the folded structure region, respectively. From these peak intensities, it is estimated that the stem length of polyethylene single crystals is approximately 125 Å. Taking into account an error in the estimation of the small peak intensities, the calculated stem length of 125 Å is consistent with the crystal thickness (120–150 Å) observed directly by electron microscopy. It can be concluded, therefore, that polyethylene single crystals mainly contain sharply folded structure. Melt-quenched polyethylene may contain sharply folded structure to some extent in addition to loose loops.     

Microstructure study of styrene/n-butyl acrylate emulsion copolymers by 13C nuclear magnetic resonance spectroscopy

A detailed study of the sequence distribution in styrene (S)/n-butyl acrylate (A) emulsion copolymers using ¹³C nuclear magnetic resonance spectroscopy is reported. From the interpretation of the spectra of the homopolymers and copolymers, assignment of the carbonyl (A) and quaternary (S) carbon atom resonances has been made. This provides a quantitative estimation of the compositional triad distributions in the copolymers. The results were found to be in relatively good agreement with calculated triad fractions deduced from a simulation program taking into account the actual reactivity ratios and type of emulsion process.     

Structure determination of long-chain polyunsaturated triacylgyycerols by high-resolution13C nuclear magnetic resonance

The application of¹³C nuclear magnetic resonance to determine the positional distribution of fatty acids on the glycerol backbone has been investigated. A systematic approach and synthetic triacylglycerols were used to measure the effect on the carbonyl chemical shifts of triacylglycerols by the positional distribution on the glycerol backbone and the number and position of the double bonds within the fatty acids. The correlation of¹³C carbonyl chemical shift to the molecular structure of triacylglycerol was delineated. The assignments for the chemical shifts of the carbonyl nuclei of monoacyltriacylglycerol standards were compiled. The resonance from the carbonyl carbons at the 1,3 positions is resolved from that at the 2 position. The¹³C carbonyl chemical shift was more dependent on the position of the double bonds than the degree of unsaturation of the fatty acids. In particular, little effect was observed in the chemical shifts for fatty acids containing more than two double bonds. However, the chemical shifts were influenced significantly by the position of the first double bond. The difference in the chemical shift of the unsaturated species from that of the saturated species was plotted against the position of the first double bond. A natural logarithmic relationship was found between carbon numbers 5 and 11. Inflection points were found outside of this region at carbon numbers 4 and 13. In addition, the resonances from the saturated species, independent of their chainlength, were degenerate in oil systems, even though small differences were observed in the standards. The applicability of this method was demonstrated in the determination of the composition and positional distribution of the fatty acids in borage and evening primrose oils.     

Structural characterization by 13C nuclear magnetic resonance of hydrolysed carboxymethylcellulose

Summary In order to characterize heavyweight carboxymethylcellulose (C.M.C) by ¹³C NMR it is necessary to hydrolysis them. This paper proposes and compares three different ways of degradation: acidic hydrolysis, sonication and enzymatic degradation. Acidic hydrolysis leads to poor results due to a strong alteration of the sample. Sonication gives quite good results but the enzymatic degradation is the most efficient method for degrading C.M.C under good conditions.After hydrolysis, the sample was analysed by ¹³C NMR and HPLC to obtain structural information such as substitution degree, preferential substitution sites and regularity of the substitution along the polymeric chain.     

Chemical characterization of solid coals through magic-angle 13C nuclear magnetic resonance

Recently developed ¹³C n.m.r. techniques for high resolution in solids are applied to native coals. The quantity and distribution of hydroxyl groups in the samples are determined by combining chemical modification through acetylation with the n.m.r. measurements. Spectral subtraction isolates the reaction product resonances. Spectroscopic separation of protonated and non-protonated carbons through pulse programming techniques is also demonstrated. Finally, the susceptibility of the aliphatic carbons in coals to low-temperature oxidation is shown clearly by subtraction of spectra of the oxidized and unoxidized materials.     

Identification and classification of olive oils by high-resolution13C nuclear magnetic resonance

Unsaponifiable matter from 19 olive and olive pomace oils were studied by high-resolution¹³C nuclear magnetic resonance spectroscopy. Their spectra showed characteristic peaks that corresponded to molecular substructures rather than the individual constituents present in the unsaponifiable matter. The presence of squalene and other hydrocarbons, sterols and triterpenic alcohols, in addition to other groups of minor compounds, were observed. Based on the analysis of these spectra, it was possible to distinguish among different grades of olive oils by using stepwise discriminant analysis. This direct method of analysis is suggested to be used in artificial neural networks to define oil identity and quality.     

Oxidation in fish lipids during thermal stress as studied by 13C nuclear magnetic resonance spectroscopy

¹³C Nuclear magnetic resonance spectroscopy has been applied to elucidate the mechanism of lipid oxidation occurring during thermal treatment of fish. Effects of temperature and time of processing have been studied by means of a model system of lipids, extracted from salmon (Salmo salar) muscle, to simulate industrial conditions of canning. Unsaturated fatty acids located at the sn-2 position of the glycerol moiety were the most prone to oxidative damage. Regarding the mechanism of the reaction, results inferred from olefinic and methylenic resonances indicated a higher susceptibility of the allylic sites closest to the carbonyl group, followed by those placed near the methyl terminal group. Unsaturations located in the middle of the carbon chain did not show much damage. The glyceryl region provided an unusual resonance at 53.4 ppm, which could be assigned to a hydroxylic compound formed during process.     

1H and 13C nuclear magnetic resonance studies of the synthesis of linear segmented polyurethane elastomers

Linear segmented polyurethane elastomers have been prepared by reaction of polyethyleneoxide with 4,4′-diphenylmethanediisocyanate and the product was subsequently cured with diamines. Chemical analysis of the prepolymer formed using stoichiometric ratios of polyol and diisocyanate indicated that the product was deficient in ‘free’ isocyanate. A number of side reactions can lead to a reduction in the amount of isocyanate available for the chain extension reaction. Infrared, ¹H- and ¹³C-n.m.r. spectroscopy were used to follow the initial end-capping and subsequent chain extension reactions. In order that an unambiguous assignment of the weak peaks observed in the prepolymer and final elastomer spectra could be made, a number of model compounds associated with the side reactions were synthesized and their spectra characterized. It was concluded that the loss of ‘free’ isocyanate in the formation of the prepolymer can be predominantly attributed to the effects of traces of water in the initial reaction mixture.     

The composition of hydrogenated fats by high-resolution13C nuclear magnetic resonance spectroscopy

The high-resolution¹³C nuclear magnetic resonance spectra of twelve hydrogenated fats have been examined. Each spectrum contains 50–100 signals and reveals much about the nature of the acyl chains of both double-bond position and configuration. The signals for the ω1, ω2 and ω3 carbon atoms give information on thecis andtrans isomers of the Δ15, Δ14, Δ13 and Δ12 18:1 esters, respectively. Allylic signals distinguish betweencis andtrans esters, and the proportion of totalcis to totaltrans isomers can be obtained from these. Olefinic signals are the most informative, and most of these have been assigned. This leads to a semi-quantitative estimate of the various 18:1 isomers present. Assignments are based mainly on information already in the literature, but some were confirmed after urea fractionation of the acids from a hydrogenated oil in whichcis andtrans monoene acids were separately concentrated.     

Identification of cyclopentenyl fatty acids by 1H and 13C nuclear magnetic resonance

Gorlic, chaulmoogric and hydnocarpic fatty acids, specific to the seed oil of the genus Hydnocarpus sp. (Flacourtiaceae), are determined only with difficulty by gas chromatography. These fatty acids were isolated in their methyl ester form by a combination of different chromatographic techniques (thin-layer chromatography/Ag⁺ and high-pressure liquid chromatography). The proton and carbon nuclear magnetic resonance analysis of these fatty acid methyl esters showed some characteristic signals of the cyclopentenyl ring. The presence of these signals in the proton and/or carbon nuclear magnetic resonance spectrum of an oil thus will allow us to confirm the presence of these cyclopentenyl fatty acids in lipids.     

Measuring stereoselectivity in lipase-catalyzed acidolysis reactions by ultra-high resolution 13C nuclear magnetic resonance

Elucidating the stereoselectivity of lipases in synthetic reactions of triacylglycerols has hitherto been carried out using traditional analytical techniques to determine the composition of the reaction products. These methods are laborious and are not always appropriate for analysis of certain triacylglycerol types. A direct method, utilizing a stereospecific deuterium-labeled triacylglycerol substrate, has been developed where the stereoisomeric composition of the reaction product is determined by ultra-high resolution ¹³C nuclear magnetic resonance (NMR) spectroscopy. Through lipase-catalyzed transesterification of deuterium-labeled trilauroylglycerol with oleic acid, chemical shifts were induced in the ¹³C NMR spectrum by the deuterium atom and olefinic double bonds, enabling unambiguous stereospecific assignment of triacylglycerol species. By this method of analysis, we found an effect of the degree of reaction conversion on the extent of stereoisomerism in the triacylglycerol product. Stereoselectivity was greatest (for sn-1) with lipase from Rhizomucor miehei. Lipases from Rhizopus niveus, Candida rugosa, Carica papaya, and the cutinase from Fusarium sp. were also found to exhibit stereoselectivity, with preference for either sn-1 or sn-3 acyl exchange.     

香茶菜属植物二萜化合物核磁共振碳谱模拟

将原子电性作用矢量(AEIV)和原子杂化状态指数(AHSI)应用于香茶菜属植物二萜化合物核磁共振碳谱(13C NMR)模拟。分别利用多元线性回归(MLR)和人工神经网络(CNN)建立定量结构波谱相关(QSSR)模型,同时采用内部及外部双重验证的办法对所得模型稳定性能进行了深入分析和检验。建模计算值、留一法(LOO)交互校验(CV)预测值和外部样本预测值的复相关系数分别为Rcum=0.9724, QLOO=0.9723, Qext=0.9738(MLR); Rcum=0.9957,Qext=0.9956(CNN)。结果表明：AEIV,AHSI与13C NMR谱化学位移显著相关,且CNN所建模型明显优于MLR。     

Analysis of thermal properties of polymeric biomaterials. I. Ultrahigh-molecular-weight polyethylene

The effects of sample size and heating and cooling rates on thermal transitions of ultrahigh-molecular-weight polyethylene (UHMWPE) were investigated. The thermal parameters were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). While heating rates and sample size had strong effects on thermal properties, the influences of cooling rates were minor. For DSC, broad melting transitions were obtained at faster heating and/or slower cooling rates and larger sample sizes. Higher melting temperatures were obtained when heating rates and sample size were increased. Slower cooling rates also produced higher melting and crystallization temperatures. Faster cooling rates yielded lower heats of fusion during melting and also lower heats of crystallization. The dependence of peak melting and crystallization temperatures on the heating and cooling rates are illustrated by two empirical formulas. For TGA, it is found that faster heating rates and larger sample sizes produced higher decomposition temperatures. This detailed analysis may explain the large variations in the reported data on thermal properties and crystallinity of UHMWPE and provide solutions to the current clinical problems associated with polymeric biomaterials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1353–1361, 1998     

双向拉伸聚乙烯的微观结构及热学表征

采用红外光谱、核磁共振波谱和高温凝胶色谱对2个双向拉伸聚乙烯试样(分别记作M1,M2)的链结构进行了表征,确定了试样的共聚单体类型、支化度、相对分子质量及其分布。利用差示扫描量热法(DSC)研究了试样的熔融和结晶行为。通过连续自成核退火热分级法测定了不同共聚物中亚甲基序列长度(MSL)的分布。结果表明:M1以短链支化为主,M2则以长链支化为主;M1的总支化度略高于M2,与红外光谱测试结果一致;MSL分布随MSL的增加呈单调递增趋势,M2的MSL集中在198,其峰面积占总峰面积的52.4%;M1的MSL分布呈现2个峰值,在MSL为61处有小峰,峰面积占总峰面积的8.3%,MSL为273处的峰面积占总峰面积的35.1%,与DSC测试的双熔点相对应。     

Solid state 13C nuclear magnetic resonance of heavy oil/bitumen-derived solids

Solid state ¹³C n.m.r. analysis of the insoluble organic matter associated with the clay mineral, silica, and heavy metal minerals of heavy oils/bitumen is reported. The conditions under which these measurements can be made are related to the concentration of organic matter found, the nature and amount of paramagnetic constituents, and contact times. The data are related to changes in hydrophilic/hydrophobic surface properties of the solids. The relationship with bitumen losses in recovery processes is also discussed.     

Use of high-resolution 13C nuclear magnetic resonance spectroscopy for the screening of virgin olive oils

¹³C Nuclear magnetic resonance (NMR) spectra of 104 oil samples were obtained and analyzed in order to study the use of this technique for routine screening of virgin olive oils. The oils studied included the following: virgin olive oils from different cultivars and regions of Europe and north Africa, and refined olive, “lampante” olive, refined olive pomace, high-oleic sunflower, hazelnut, sunflower, corn, soybean, rapeseed, grapeseed, and peanut oils, as well as mixtures of virgin olive oils from different geographical origins and mixtures of 5–50% hazelnut oil in virgin olive oil. The analysis of the spectra allowed us to distinguish among virgin olive oils, oils with a high content of oleic acid, and oils with a high content of linoleic acid, by using stepwise discriminant analysis. This parametric method gave 97.1% correct validated classifications for the oils. In addition, it classified correctly all the hazelnut oil samples and the mixtures of hazelnut oil in virgin olive oil assayed. All of these results suggested that ¹³C NMR may be used satisfactorily for discriminating some specific groups of oils, but to obtain 100% correct classifications for the different oils and mixtures, more information than that obtained from the direct spectra of the oils is needed.     

Hypothetical average structures of two coal liquid asphaltenes from solid state 13 C nuclear magnetic resonance and 1 H nuclear magnetic resonance data

The hypothetical average structures of two coal liquid asphaltenes were determined using solid state 13 C NMR and 1 H NMR data. From the 1 H NMR data average molecular structural parameters were obtained using the Brown-Ladner method to get a general average structure. From the solid state 13 C NMR data, estimations of percentages of tertiary and quaternary aromatic carbons and secondary/tertiary and primary/quaternary aliphatic carbons were made. The hypothetical average molecules obtained agreed closely with experimental results.     

13C nuclear magnetic resonance spectroscopic analysis of the triacylglycerol composition of some margarines

The triacylglycerol fraction of three samples of margarine, namely “Flora” (Holland), “Kaliakra” (Bulgaria), and “Corona” (Holland), were studied by¹³C nuclear magnetic resonance spectroscopy. By examining the various carbon chemical shifts of the saturated and unsaturated carbon nuclei, “Flora” margarine was shown to contain a mixture of hydrogenated and unhydrogenated vegetable oils. This technique allowed all major acyl groups (saturated, oleate, linoleate, and linolenate) and minor acyl components [different positional isomers of long-chain (E)- and (Z)-monoenoic moieties, arising as by-products during catalytic hydrogenation] to be identified. The amount of each fatty acid present in the margarine was also estimated from the relative intensities of the corresponding signals. “Kaliakra” margarine consisted of a blend of unhydrogenated natural fats and oils that contained saturated fatty acids, oleate, and linoleate. There were no signs in the spectrum of “Kaliakra” of any (E)-isomers, nor signals associated with positional unsaturated acyl groups (other than oleate and linoleate). The sample of “Corona” margarine consisted of a mixture of hydrogenated and unhydrogenated vegetable oils and butter (1.3%). The presence of butter in this sample was identified by the characteristic carbon shifts of the C-1 to C-4 carbon atoms of butyrate. The distribution of the fatty acids on the glycerol “backbone” also was estimated by this technique.