鬼臼毒素在两种溶剂中核磁共振谱图数据的比较

比较了微生物源的鬼臼毒素在氘代氯仿(CDCl3)和二甲亚砜(DMSO)2种溶剂中的核磁共振数据,结果表明:在溶剂DMSO中,核磁共振能提供更多可靠的信号;据解析,确定了在2种溶剂中所有13C NMR、1HNMR谱的信号归属。     

固体核磁共振法对低甲醛释放脲醛树脂化学结构的研究

在采用液体核磁对3种低甲醛释放脲醛树脂化学构造进行分析的基础上,利用13CCP/MASNMR对脲醛树脂固化产物的化学结构进行了研究.结果表明,不同固化体系下,3种低甲醛释放脲醛树脂胶黏剂的固化历程不同,固化后树脂的结构有所差别.不添加固化剂时,脲醛树脂的固化交联反应程度低,固化产物中羟甲基含量高,甲醛释放量也随之增加.加入固化剂后,促进了羟甲基的固化交联反应,脲醛树脂固化产物中羟甲基含量普遍降低.3种固化体系下,UF-3羟甲基含量最高;在氯化铵为固化剂的条件下,UF-2羟甲基含量最低,为0.0582;不添加固化剂和复合固化体系条件下,UF-1羟甲基含量最低,分别为0.0784和0.0713.不同固化体系对不同种类脲醛树脂的固化效果不同,固化后树脂的结构不同,其力学性能和甲醛释放能力也不同.     

Migration of methylene bis thiocyanate in wood and its effect on a wood degrading fungus

The mobility and concentrations of methylene bis thiocyanate (MBT) at different depths of wood billets (200 mm long, 40 mm in diameter) of Pinus radiata were determined using NMR spectroscopy and ICP-ASE. Results were then correlated with the effect of wood MBT concentrations on growth of O. floccosum in a bioassay using stereomicroscopy and confocal laser scanning microscopy (CLSM). The ¹³C NMR spectra showed the presence or the absence of MBT in wood but it was unable to detect small concentrations. ICP-ASE, however produced quantitative data across the depth (40 mm) of the wood billets tested. Within 7 days of storage, MBT penetrated from surface to pith but showed significantly higher concentrations of MBT in surface wood compared to pith wood. Present study highlighted the benefit of using CLSM for fungal detection in wood. The information obtained from ICP-ASE and CLSM analysis suggested to inhibit growth of O. floccosum, the MBT concentration needs to be >55 μg/g of dry wood. Due to its high detection capacity, ICP-ASE is identified as an excellent tool for MBT detection and quantification in wood.     

Isolation and NMR Study on Swainsonine from Locoweed, Astragalus strictus

Locoweed is a poisonous plant wildly distributed in most area of the world and can cause livestock poisoning or death with significant economic loss. The principal responsible for its toxicity is indolizidine alkaloid swainsonine, a new potential anticancer and antiviral drug. Astragalus strictus is mainly distributed in Tibet of China and is a serious hazard to the local livestock industry. To analyze its main toxic ingredients and supply more structural information and more accurate data, swainsonine has been isolated from this plant by D101 macroporous resin and the ^1H and ^13C chemical shifts of the compound has been assigned by 1D-NMR and 2D-NMR techniques. At the same time, complete assignments of swainsonine＇s ^13C spectral signals are reported.     

Structural changes in lignin of tropical woods during digestion by termite, <Emphasis Type="Italic">Cryptotermes brevis</Emphasis>

Wood samples of apitong (Dipterocarpus grandiflorua) and ilang-ilang (Ilang-Ilang C. dadloyi) and feces of termites [Cryptotermes brevis (Walker)] fed on these woods were collected from University of the Philippines, Los Baňos. Lignin of each sample was isolated by Björkman’s procedure. There was no significant difference in ¹H nuclear magnetic resonance (NMR) spectra or in the methoxyl content between Björkman lignins from original woods and termite feces. Differences were detected in the contents of aliphatic and unconjugated phenolic hydroxyl groups, suggesting minor structural changes of lignin during digestion by termites. In addition, the ratio of syringyl to guaiacyl nuclei of Björkman lignin from termite feces determined by ¹H NMR spectra was higher than those from the original woods. The molar ratio of syringyl to guaiacyl nuclei of termite feces was higher than those from the original woods as determined by alkaline nitrobenzene oxidation. These results suggest that the structural changes of lignin in the termite gut are due to the insignificant formation of C-C linkages in guaiacyl nuclei. It was concluded that there were minor changes in the structural features of lignin under mostly anaerobic conditions, in contrast to the significant changes that occur through biological modification under aerobic conditions.     

6-硫-6-烷硫基-12H-氯代双苯并[d,g][1,3,2]-二氧磷杂八环的合成

通过双- (2 -羟基 -氯代苯基 )甲烷 2与 P4S10 在三乙胺存在下的关环反应 ,得到了6 -硫 - 6巯基 - 12 H-氯代双苯并 [d,g][1,3,2 ]-二氧磷杂八环三乙胺盐 3,后者与卤代烷酯化得到了一系列 6 -硫 - 6 -烷硫基 - 12 H-氯代双苯并 [d,g][1,3,2 ]-二氧磷杂八环 4 ,测试并讨论了它们的1H和31P NMR数据。初步生物试验结果表明化合物 4对黄瓜霜霉病菌具有较好的抑制活性。     

Theonellamides J and K and 5-cis-Apoa-theopalauamide,Bicyclic Glycopeptides of the Red Sea Sponge Theonella swinhoei

Theonella swinhoei is a fairly common inhabitant of reefs throughout the Indian and Pacific Oceans. Metabolomic analyses of samples of T. swinhoei collected in different depths in the Gulf of Aqaba revealed two chemotypes differing in the profiles of the theonellamides they produce, some of which seem to be unknown. Driven by this finding, we examined a sample of T. swinhoei collected more than 40 years ago in the southern part of the Gulf of Aqaba. Large-scale extract of this sample yielded four theonellamides, the known theopalauamide (4), as the major component, and three new metabolites, theonellamide J (1), 5-cis-Apoa-theopalauamide (2), and theonellamide K (3), as the minor components. The planar structure of these complex cyclic glycopeptides was elucidated by combination of 1D and 2D NMR techniques and HRESIMS. The absolute configuration of the amino acids was established by Marfey’s and advanced Marfey’s methods, and the absolute configuration of its galactose unit using “Tanaka’s method” for monosaccharides. The biological activity of the pure compounds was tested for antibacterial activity and for cytotoxicity to HTC-116 cell line. The compounds presented significant cytotoxicity against the HTC-116 cell line, illuminating the importance of the Apoa subunit for the activity.     

NMR-Based Configurational Assignments of Natural Products: Gibbs Sampling and Bayesian Inference Using Floating Chirality Distance Geometry Calculations

Floating chirality restrained distance geometry (fc-rDG) calculations are used to directly evolve structures from NMR data such as NOE-derived intramolecular distances or anisotropic residual dipolar couplings (RDCs). In contrast to evaluating pre-calculated structures against NMR restraints, multiple configurations (diastereomers) and conformations are generated automatically within the experimental limits. In this report, we show that the “unphysical” rDG pseudo energies defined from NMR violations bear statistical significance, which allows assigning probabilities to configurational assignments made that are fully compatible with the method of Bayesian inference. These “diastereomeric differentiabilities” then even become almost independent of the actual values of the force constants used to model the restraints originating from NOE or RDC data.     

Long‐term effects of tillage,nutrient application and crop rotation on soil organic matter quality assessed by NMR spectroscopy

Crop and land management practices affect both the quality and quantity of soil organic matter (SOM) and hence are driving forces for soil organic carbon (SOC) sequestration. The objective of this study was to assess the long‐term effects of tillage, fertilizer application and crop rotation on SOC in an agricultural area of southern Norway, where a soil fertility and crop rotation experiment was initiated in 1953 and a second experiment on tillage practices was initiated in 1983. The first experiment comprised 6‐yr crop rotations with cereals only and 2‐yr cereal and 4‐yr grass rotations with recommended (base) and more than the recommended (above base) fertilizer application rates; the second experiment dealt with autumn‐ploughed (conventional‐till) plots and direct‐drilled plots (no‐till). Soil samples at 0–10 and 10–30 cm depths were collected in autumn 2009 and analysed for their C and N contents. The quality of SOM in the top layer was determined by ¹³C solid‐state NMR spectroscopy. The SOC stock did not differ significantly because of rotation or fertilizer application types, even after 56 yr. However, the no‐till system showed a significantly higher SOC stock than the conventional‐till system at the 0–10 cm depth after the 26 yr of experiment, but it was not significantly different at the 10–30 cm depth. In terms of quality, SOM was found to differ by tillage type, rate of fertilizer application and crop rotation. The no‐till system showed an abundance of O‐alkyl C, while conventional‐till system indicated an apparently indirect enrichment in alkyl C, suggesting a more advanced stage of SOM decomposition. The long‐term quantitative and qualitative effects on SOM suggest that adopting a no‐tillage system and including grass in crop rotation and farmyard manure in fertilizer application may contribute to preserve soil fertility and mitigate climate change.