The 13C-NMR Features of Natural Taxane Diterpenoid Compounds

The paper reviewed the 13C-NMR features of natural taxane diterpenoids according to their carbon-skeleton types. In the 13C-NMR it is easy to distinguish the 6/8/6 and 5/7/6 membered rings by observation of the 13C-NMR data of C-1 and C-15. The remarkable differences of the resonance of C -13 and C-12 were found. In addition, based on various chemical environments man y obscured chemical shifts of carbons can be distinguished, such as the oxygenat ed tertiary carbons of C-2, C-5, C-7, C-9 and C-13, and sometimes between C-9 an d C-10, as well as between aliphatic quaternary carbons of C-8 and C-15, and sec ondary carbons of C-6 and C-14. All the above-mentioned characteristics are helpful for structural elucidation and assignments of the carbon signals of taxoids.     

Studies on biological decomposition of wheat straw

Summary The incorporation of undecomposed wheat straw in the soil along-with the micro-organisms favourably increased the yield of groundnut crop. An increase of 37 per cent in yield was recorded when wheat straw was inoculated withPenicillium digitatum and the C:P ratio was adjusted to 65. Inoculated treatments of narrower C:P ratio gave a higher yield than wider C:P ratio treatments inoculated with the same cultures. An increase in nitrogen uptake by groundnut plants was recorded due to incorporation of straw alongwith the micro-organisms in soil. The organic carbon and nitrogen content of the soil increased with all the treatments except control. The highest increase in organic carbon and nitrogen of the soil was observed with a treatment of wheat straw of 65 C:P ratio inoculated withS. coccosporum. The yield of wheat crop after groundnut was significantly more with several treatments than control plots. The highest increase of 79 per cent in grain yield of wheat was observed in the plots previouslq received with wheat straw of 200 C:P ratio.This paper is based on the data presented at IV Southern Regional Conference on Microbial Inoculants, held at Parbhani during 3–4 July 1978.     

Motional dynamics of residues in a beta-hairpin peptide measured by 13C-NMR relaxation.

Structurally characterizing partially folded peptides is problematic given the nature of their transient conformational states. 13C-NMR relaxation data can provide information on the geometry of bond rotations, motional restrictions, and correlated bond rotations of the backbone and side chains and, therefore, is one approach that is useful to assess the presence of folded structure within a conformational ensemble. A peptide 12mer, R1GITVNG7KTYGR12, has been shown to partially fold in a relatively stable beta-hairpin conformation centered at NG. Here, five residues, G2, V5, G7, Y10, G11, were selectively 13C-enriched, and 13C-NMR relaxation experiments were performed to obtain auto- and cross-correlation motional order parameters, correlation times, bond rotation angular variances, and bond rotational correlation coefficients. Our results indicate that, of the three glycines, G7 within the hairpin beta-turn displays the most correlated phi(t),psi(t) rotations with its axis of rotation bisecting the angle defined by the H-C-H bonds. These positively correlated bond rotations give rise to "twisting" type motions of the HCH group. V5 and Y10 phi,psi bond rotations are also positively correlated, with their CbetaCalphaH groups undergoing similar "twisting" type motions. Motions of near-terminal residues G2 and G11 are less restricted and less correlated and are best described as wobbling-in-a-cone. V5 and Y10 side-chain motions, aside from being highly restricted, were found to be correlated with phi,psi bond rotations. At 303 K, where the hairpin is considered "unfolded," the peptide exists in a transient, collapsed state because backbone and side-chain motions of V5, G7, and Y10 remain relatively restricted, unlike their counterparts in GXG-based tripeptides. These results provide unique information toward understanding conformational variability in the unfolded state of proteins, which is necessary to solve the protein folding problem.     

Rice straw decomposition in rice-field soil

Rice straw, buried in a rice-field during the dry season decomposed at a rate of 0.0075 day-1. Seventy five percent of the biomass, 70 percent carbon, 50 percent nitrogen and 30 percent phosphorus remained after 139 days of decomposition. Rice straw decomposition furnished 33% N and 8% P of the total nitrogen and phosphorus provided by man.     

13C-NMR Investigation of the insertion of the bee venom melittin into lecithin vesicles

The orientation of melittin in lecithin membranes was investigated by means of ¹³C-NMR spectroscopy. Phospholipase-free melittin was labeled with ¹³C-methyl groups at the -amino side chains of lysine 7, 21, and 23. From the pH dependence of the corresponding ¹³C resonances, pK values of the lysine residues were derived that were different for free and membrane-bound melittin. The shift reagent Pr(NO₃)₃ induced shifts in the ¹³C resonance position of all three lysines when melittin and the shift reagent were added to a lecithin vesicle suspension, whereas Pr³⁺ ions included in the inner volume of the vesicles did not affect the ¹³C resonances of melittin bound to the outer vesicle membrane. A wedge-like structure was derived for the membrane-bound melittin, the lysine side chains of which are freely accessible to the aqueous solvent.Abbreviation NOE Nuclear Overhauser Enhancement     

Determination of membrane lipid phase transition temperature from C-NMR intensities

A new and simple approach for the determination of the temperature of gel-to-liquid crystalline phase transitions (T_C) of biological (chloroplast) membrane lipids from ¹³C-NMR resonance intensities is proposed. The variation of intensity of a temperature-sensitive NMR resonance is monitored by recording the spectra of the sample at a range of temperatures. From such a series of spectra recorded at different temperatures, a temperature-insensitive resonance is located. Then the ratio of the intensity of the temperature-sensitive to the intensity of the temperature-insensitive resonance is calculated from each spectrum to even out the procedural error, if any. The values of this ratio at different temperatures, when plotted against sample temperature, shows a break at T_C as confirmed by spin label ESR studies.     

Organosolv pulping of wheat straw by use of phenol

A central composite design was used to investigate the influence of the cooking conditions (time, temperature and phenol concentration) for wheat straw with phenol-water mixtures on the properties of the pulp obtained (yield and holocellulose, -cellulose, lignin and ethanol-benzene extractable contents) and the pH of the resulting wastewater. A second-order polynomial model consisting of three independent process variables was found to accurately describe the organosolv pulping of wheat straw. The equations derived predict the yield, the holocellulose, -cellulose, lignin and ethanol-benzene extractable contents of the pulp, and the pH of the wastewater with multiple-R, R² and adjusted-R² high values. The process variables must be set at low variables in order to ensure a high yield and pH. Conversely, if high holocellulose and -cellulose contents, and low lignin and ethanol-benzene extractable contents are desired, then a high temperature (200°C), long cooking time (120 min), and intermediate phenol concentration (65%) must be used.     

Decomposition of wheat straw and rye residues as affected by particle size

Effects of contact between the soil and crop residues on the processes of residue decomposition are still poorly understood. The objective of this study was to investigate the effects of residue particle size on the decomposition of wheat (Triticum aestivum L.) straw (C/N=270) and green rye (Secale cereale) residues (C/N=9). Residue particle size was used as a means to vary the contact between crop residues and the soil. Carbon mineralization was measured during 102 d for straw and 65 d for rye, on residues ranging in sizes from laboratory model (0.03 cm) to field-scale (10 cm). The soil was a silt (Typic Hapludalf) and the incubation was performed at 15 °C. The effects of particle size on C mineralization varied for the two residues. In the first two days of incubation, decomposition rate of rye increased with decreasing particle size but thereafter, the trend was reversed. In 65 days, 8% more C was decomposed in the 7-cm residues than in the 0.03-cm ones. For wheat straw, early decomposition (3–17 days) was faster for the small-sized particles (0.06 and 0.1 cm). Thereafter, the largest size classes (5 and 10 cm) decomposed faster. After 102 days, the very fine particles ( 0.1 cm) showed the greatest and the intermediate size classes (0.5 and 1 cm), the lowest amount of C mineralized. We hypothesized that greater availability and accessibility of N was responsible for the higher rates of decomposition observed for finely-ground wheat straw while a physical protection of finely ground residues was probably involved in the observed reverse effect for rye.     

1H- and13C-NMR spectroscopic studies of lipid extracts of the red algaGracilaria longa

Lipid extracts of the red algaGracilaria longa were studied by¹H- and¹³C-NMR spectroscopy. Peaks in the¹³C-NMR spectra attributable to sterols, chlorophylls and carotenoids allowed free and acylated cholesterol, chlorophylla and lutein to be identified as the most abundant components of these classes. A content of 0.5 ± 0.1 μmoles of total cholesterol/g wet alga was estimated from the¹H-NMR spectrum, which also allowed the determination of the phosphatidylcholine/total lipid molar ratio (9.5 ± 0.5%). The¹³C-NMR spectroscopic experiments provided information on the position of the double bonds on the fatty acid residues. A comparison between NMR spectra of lipid extracts obtained for wet and dried alga showed that the alga undergoes both a dramatic peroxidation and some glycolipid degradation during the drying process.     

玉米秸秆生物炭对秸秆腐熟进程、养分含量和CO2排放量的影响

生物炭具有良好的理化特性(富碳、呈碱性、孔隙丰富),能够有效调节其所在系统的理化性质.通过室内培养试验研究了玉米秸秆生物炭对玉米秸秆腐熟进程以及腐熟产物的理化性质、养分含量和CO₂气体排放的影响.试验设置4个处理:对照(CK);生物炭添加量5%(B₁,生物炭干基质量占玉米秸秆腐熟体系的干基质量分数);生物炭添加量10%(B₂);生物炭添加量20%(B₃).结果表明: 生物炭能够提高秸秆腐熟体系的升温速率和温度峰值,加快秸秆腐熟进程;生物炭能够提高秸秆腐熟过程中微生物活跃时期的pH值,提高秸秆腐熟体系的电导率(EC),为微生物降解有机物提供更适宜的环境;生物炭能够促进秸秆腐熟体系有机质的降解,增加秸秆腐熟体系的总养分含量,提高秸秆腐熟产物的品质.另外,随着生物炭添加量的提高,氮(N)含量没有显著变化,磷(P₂O₅)含量和钾(K₂O)含量都显著提高.其中,B₃处理的P₂O₅和K₂O含量较CK分别提高了0.2%和0.9%.生物炭添加能够提高秸秆腐熟体系CO₂的排放通量,且CO₂排放通量与温度的变化趋势一致,进一步说明生物炭能够提高微生物降解有机物的强度.     

Thermal decomposition kinetics of wheat straw treated by Phanerochaete chrysosporium

Combining biological pretreatment with thermal processing may offer an alternative strategy for efficient conversion of lignocellulosic biomass into fuels and chemicals. The thermal decomposition kinetics of biologically pretreated wheat straw by Phanerochaete chrysosporium was investigated in this study using thermogravimetry (TG) - deconvoluted thermogravimetry (DTG) techniques and the Friedman method. This study revealed that biological pretreatment reduced the thermal degradation temperature of the biomass significantly. Relying on the thermal behavior of the biologically pretreated wheat straw, we proposed two biomass degradation phases during the biological degradation of wheat straw. The first phase of biodegradation (within 10 days of biological pretreatment) improved the efficiency of pyrolysis by reducing the temperature demand. In the second phase (after 10 days), although the efficiency of pyrolysis displayed the similar trend as the first phase, it showed a significant increase in activation energy demand. This process is greatly influenced by the residual lignin and cellulose ratios in the biomass. These experimental results will be useful in developing a biological pretreatment based thermochemical conversion process for lignocellulosic biomass.     

转Bt基因水稻秸秆降解对土壤微生物可培养类群的影响

以高抗螟虫、已释放应用的 Bt水稻 (克螟稻 1号 )及其亲本 (非 Bt水稻 )为材料 ,在实验室条件下研究了转 Bt基因水稻及其亲本秸秆在降解过程中对土壤微生物主要类群的影响 ,这些类群包括细菌、真菌、放线菌、反硝化细菌、解磷微生物。结果表明 :(1)降解过程中 Bt蛋白浓度在前两周内迅速下降 ,随后降解速度变慢 ,17d以后至 5 3d,Bt蛋白浓度基本上保持在 6 .72 8～6 .196 ng/ g的水平。 (2 )秸秆降解过程中 ,不同处理细菌数量的变化趋势相似 ,转基因水稻与其亲本之间差异显著 ,非转基因细菌数量高于转基因细菌数量。(3)除降解初期第 3天、第 6天之外 ,其他取样时期的转基因水稻真菌数量要显著高于非转基因和对照。(4)放线菌数量没有明显变化规律 ,除第 6、9、2 6、35天外 ,非转基因数量显著高于转基因。(5 )非转基因秸秆降解反硝化细菌活性高于转基因 ,而解磷微生物活性处理之间无明显差异。     

Biomethanation of rice and wheat straw

When rice or wheat straw was added to cattle dung slurry and digested anaerobically, daily gas production increased from 176 to 331 l/kg total solids with 100% rice straw and to 194 l/kg total solids with 40% wheat straw. Not only was methane production enhanced by adding chopped crop residues but a greater biodegradability of organic matter in the straws was achieved.The authors are with the Microbiology and Molecular Genetics Unit, Tata Energy Research Institute, 158 Jor Bagh, New Delhi 110 003, India     

玉米秸秆生物炭对秸秆腐熟进程、养分含量和CO2排放量的影响

生物炭具有良好的理化特性(富碳、呈碱性、孔隙丰富),能够有效调节其所在系统的理化性质.通过室内培养试验研究了玉米秸秆生物炭对玉米秸秆腐熟进程以及腐熟产物的理化性质、养分含量和CO₂气体排放的影响.试验设置4个处理:对照(CK);生物炭添加量5%(B₁,生物炭干基质量占玉米秸秆腐熟体系的干基质量分数);生物炭添加量10%(B₂);生物炭添加量20%(B₃).结果表明: 生物炭能够提高秸秆腐熟体系的升温速率和温度峰值,加快秸秆腐熟进程;生物炭能够提高秸秆腐熟过程中微生物活跃时期的pH值,提高秸秆腐熟体系的电导率(EC),为微生物降解有机物提供更适宜的环境;生物炭能够促进秸秆腐熟体系有机质的降解,增加秸秆腐熟体系的总养分含量,提高秸秆腐熟产物的品质.另外,随着生物炭添加量的提高,氮(N)含量没有显著变化,磷(P₂O₅)含量和钾(K₂O)含量都显著提高.其中,B₃处理的P₂O₅和K₂O含量较CK分别提高了0.2%和0.9%.生物炭添加能够提高秸秆腐熟体系CO₂的排放通量,且CO₂排放通量与温度的变化趋势一致,进一步说明生物炭能够提高微生物降解有机物的强度.     

The influence of fertilizer nitrogen and season on the carbon-13 abundance of wheat straw

Carbon-13 abundance, expressed as δ¹³C in ‰, was measured in wheat straw grown between 1984 and 1989 on the Broadbalk Continuous Wheat Experiment at Rothamsted. In all six years, straw grown without fertilizer N contained less carbon-13 (i.e.δ¹³C was more negative) than straw grown with fertilizer, although the magnitude of this difference varied with year. In a dry year, when dry matter response to fertilizer N was relatively small, there was a large difference between the δ¹³C of straw grown with and without N. Conversely, in a wet year, when there was a marked response to N, there was little difference in the isotopic composition of N-fertilized and unfertilized straw. Over the six years, the difference between the δ¹³C value of straw grown with and without nitrogen (D ¹³C, in ‰) was related to drought, measured as the calculated soil water deficit on 15 July (W_j, in mm), by the equation D ¹³C=−0.299+0.01034 W_j (r=0.87). H Lambers Section editor     

Polyglucose synthesis in Chloroflexus aurantiacus studied by 13C-NMR

Chloroflexus aurantiacus OK-70 fl was grown photoautotrophically with hydrogen as electron source. The cultures were subjected to long term labelling experments with ¹³C-labelled acetate or alanine in the presence of sodium fluoroacetate. The presence of fluoroacetate caused the cells to accumulate large amounts of polyglucose which was hydrolysed and analysed by NMR. The labelling patterns of glucose were symmetric and in agreement with carbohydrate synthesis from acetate and CO₂ via pyruvate synthase. The content of carbon derived from added acetate was highest in C2 and C5 of glucose, at least 20% higher than in C1 and C6. About one third of the glucose carbon was derived from added acetate, the rest being from CO₂. Contrary to expectations, in glucose formed in the presence of C1-labelled acetate C1 and C6 contained more label than C2 and C5, and with C2-labelled acetate as the tracer glucose was mainly labelled in C2 and C5. Labelled CO₂ was formed from acetate labelled at either position. The labelling data indicate a new metabolic pathway in C. aurantiacus. It is suggested that the cells form C1-labelled acetyl-CoA from C2-labelled acetyl-CoA and vice versa by a cyclic mechanism involving concomitant CO₂ fixation and that this cycle is the part of the autotrophic CO₂ fixation pathways in C. aurantiacus in which acetyl-CoA is formed from CO₂.The polyglucose of C. aurantiacus appears to have predominantly (1–4)-linked structure with about 10% (1–6)-linkages as revealed by ¹³C-NMR.     

Carbon-13 as a tool for the study of carbohydrate structures,conformations and interactions

The application of ¹³C-NMR spectroscopy to problems involving the structures and interactions of carbohydrates is described. Both ¹³C-enriched and natural abundance compounds were used and some advantages of the use of the stable isotope are described. Carbon-carbon and carbon-proton coupling constants obtained from 1-¹³ C enriched carbohydrates were employed in the assignment of their chemical shifts and to establish solution conformation. In all cases studied thus far, C-3 couples to C-1 only in the β-anomers while C-5 couples to C-1 only in the α-anomers. C-6 and C-2 always couple to C-1 in both anomeric species. The alkaline degradation of glucose [1-¹³ C] to saccharinic acids was followed by ¹³C-NMR. The conversion of glucose [1-¹³ C] to fructose-1,6-bisphosphate [1,6-¹³ C] by enzymes of the glycolytic pathway was shown as an example of the use of ¹³C-enriched carbohydrates to elucidate biochemical pathways. In a large number of glycosyl phosphates the ³¹P to H-1 and ³¹P to C-2 coupling constants demonstrate that in the preferred conformation the phosphate group lies between the O-5 and the H-1 of the pyranose ring. The influence of paramagnetic Mn²⁺ ions on the proton decoupled ¹³C-NMR spectra of uridine diphosphate N-acetylglucosamine indicates that the Mn²⁺ interacts strongly with the pyrophosphate moiety and with the carbonyl groups of the uracil and N-acetyl groups.     

The use of 13C-NMR in the determination of structures: A correction of the structure of borjatriol

¹³C-NMR data of two borjatriol derivatives show that the carbocyclic hydroxyl function is placed on C-7, modifying the previous assignment on C-6.     

天然紫杉烷类二萜化合物的核磁共振碳谱规律的探讨

紫杉醇（ｔａｘｏｌ）［1］是一种结构新颖、抗肿瘤作用机制独特的新型抗肿瘤药,现已成为全世界研究的热点［2］。紫杉醇属于天然紫杉烷类二萜化合物,因此,许多学者试图从自然界中寻找抗肿瘤作用更强的紫杉烷类二萜成分［3］。迄今已发现这类化合物30 0多个,并发现了一些新的骨架类型［4 - 8］。紫杉烷类化合物骨架类型多,取代位置和取代基种类更多,且几乎都为含氧取代基,因而结构解析较为复杂。无疑,核磁共振技术的应用对解析结构起到至关重要的作用。氢谱、碳谱、ＮＯＥ、ＤＥＰＴ及各种二维技术（1Ｈ＿1ＨＣＯＳＹ、ＮＯＥＳＹ、…