茯苓硫酸酯化多糖的制备及其核磁共振波谱分析

[目的]用不同方法制备3种茯苓多糖硫酸酯（Pachyman sulfate,PS）,并对其进行核磁共振波谱对比分析,为多糖硫酸化提供基础数据。[方法]以氯磺酸为磺化试剂硫酸化茯苓多糖制备茯苓多糖硫酸酯PS—I和PSII,以氨基磺酸为磺化试剂制备PS-Ⅲ,分析磺化反应前后和不同硫酸根取代度（Degree of sulfation,DS）的多糖碳原子化学位移的变化规律。[结果]PS—I（DS=2．80）分子所有自由羟基均发生取代反应;PS—H（DS=1．55）C-6羟基被全部酯化,C-2和C-4羟基发生部分酯化反应;PS-Ⅲ（DS=0．95）C-6和C-2羟基发生部分硫酸酯化反应。[结论]发生取代反应的碳原子化学位移移动的距离与PS的DS呈正相关,核磁共振技术能够提供多糖结构解析的关键数据。     

亚热带不同林分土壤表层有机碳组成及其稳定性

在浙江临安玲珑山选取了常绿阔叶林、马尾松林、板栗林和雷竹林4种林分,采用传统的化学方法与固态13C核磁共振(NMR)技术研究其土壤有机碳在不同粒径土壤颗粒中的分布规律和结构特征,探讨林分类别和管理措施对土壤有机碳含量及其结构的影响,为亚热带地区森林固碳和土壤碳库管理提供科学依据.结果显示:(1)土壤表层(0-20 cm)有机碳含量按以下次序递减:雷竹林＞常绿阔叶林＞马尾松林＞板栗林,且板栗林以粉黏粒结合态碳为主,其他林分土壤则以粗砂结合态碳为主;(2)13C NMR结果表明,阔叶林和马尾松林土壤有机碳中烷基碳所占比例最大,而雷竹林和板栗林则是烷氧碳比例最大,表明人工经营措施改变了土壤有机碳的成分组成;(3)随着土壤颗粒变细,有机碳中烷基碳比例增加,烷氧碳比例减少,A/O-A值和疏水碳/亲水碳值逐渐增大,表明颗粒越细,其结合的有机碳结构稳定性越高.     

1-O-Alkylglycerol Ethers from the Marine Sponge Guitarra abbotti and Their Cytotoxic Activity

The cytotoxicity-bioassay-guided fractionation of the ethanol extract from the marine sponge Guitarra abbotti, whose 1-O-alkyl-sn-glycerol ethers (AGEs) have not been investigated so far, led to the isolation of a complex lipid fraction containing, along with previously known compounds, six new lipids of the AGE type. The composition of the AGE fraction as well as the structures of 6 new and 22 previously known compounds were established using ¹H and ¹³C NMR, GC/MS, and chemical conversion methods. The new AGEs were identified as: 1-O-(Z-docos-15-enyl)-sn-glycerol (1), 1-O-(Z-docos-17-enyl)-sn-glycerol (2), 1-O-(Z-tricos-15-enyl)-sn-glycerol (3), 1-O-(Z-tricos-16-enyl)-sn-glycerol (4), 1-O-(Z-tricos-17-enyl)-sn-glycerol (5), and 1-O-(Z-tetracos-15-enyl)-sn-glycerol (6). The isolated AGEs show weak cytotoxic activity in THP-1, HL-60, HeLa, DLD-1, SNU C4, SK-MEL-28, and MDA-MB-231 human cancer cells. A further cytotoxicity analysis in JB6 P⁺ Cl41 cells bearing mutated MAP kinase genes revealed that ERK2 and JNK1 play a cytoprotective role in the cellular response to the AGE-induced cytotoxic effects.     

IWSF-FA模袋混凝土抗压强度、孔隙结构和物质组成

为优化模袋混凝土衬砌性能,合理利用当地粉煤灰和废弃硅粉代替部分水泥制备模袋混凝土衬砌.通过抗压强度试验、固体紫外试验、核磁共振和热重试验研究双掺粉煤灰-工业废弃硅粉替代适量水泥后对模袋混凝土抗压特性、内部孔隙结构和水化物质组成的影响.结果表明：合理双掺工业废弃硅粉和粉煤灰(如FA15S4)可以提高模袋混凝土的抗压强度;紫外吸收光谱表明其水化产物C-S-H和CH组成优于其他组别;核磁共振T₂谱分布呈现“三峰结构”,左峰信号幅度最高,双掺工业废弃硅粉-粉煤灰有利于改善其内部孔隙结构.并且双掺工业废弃硅粉和粉煤灰后,热学性质良好.建立了基于BP神经网络理论的模袋混凝土早期抗压强度预测模型,预测结果与试验测试值的最大相对误差为2.7%.研究结果可为工业废弃硅粉和粉煤灰混凝土在水工衬砌工程中的应用提供参考依据.     

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.     

Biohydrogel induced soil–water interactions: how to untangle the gel effect? A review

Biohydrogels such as microbial exudates and root‐derived mucilage are soil‐born cross‐linked polymers, able to form porous three‐dimensional networks during water uptake. The gel effect is the variation of soil properties, such as soil hydrology and soil structural stability, resulting from biohydrogel swelling in soil. Conventionally, soil–water–hydrogel interactions are investigated by measuring soil bulk properties such as water retention curves and porosity, without further analyzing the effect of biohydrogel phases in soil on a quantitative basis. Therefore, the evaluation of advanced and novel methods for the characterization of biohydrogel phases in soil and soil–water–hydrogel interactions is necessary. This review evaluates currently available methods for their potential to analyze processes associated to the gel effect. A promising approach to investigate the spatio‐temporal distribution of biohydrogel phases in porous media is based on Nuclear Magnetic Resonance (NMR) such as ¹H‐NMR relaxometry, as well as on imaging techniques such as Environmental Scanning Electron Microscopy (ESEM). Especially NMR techniques enable the identification of different water populations based on their differences in the relaxation, and thus the mobility of water molecules in biohydrogels and non‐gel water in soil pores. Rheology measures the flow behavior of biohydrogels, providing information on the structural behavior of the hydrogel network and its gelling mechanism. Soil rheology further quantifies the effect of the biohydrogel phases on the interactions between soil particles, and thus the impact on soil microstructural stability. However, rheology does not elucidate the spatio‐temporal distribution and structural state of biohydrogel phases in soil. All in all, a systematic combination of rheology, NMR and suitable imaging methods seems promising and necessary in order to elucidate the still widely unknown gel effect in soil.     

Comparative study of organic solvent-soluble and water-soluble lipophilic extractives from wheat straw 2: spectroscopic and thermal analysis

As a continuing study of six organic solventsoluble lipophilic extractives and one water-soluble lipophilic extract from wheat straw, seven extracts were further compared using Fourier transform-infrared (FT-IR) analysis,¹H and¹³C nuclear magnetic resonance (NMR) spectroscopy, and thermal analysis. In the FT-IR spectra of two-thirds chloroform/one-third methanol, methyltertbutyl ether (MTBE), hexane, petroleum ether, and dichloromethane extracts, a strong band at 1746cm^–1 is indicative of the ester carbonyl of triglycerides or steryl esters or waxes, whereas the occurrence of carboxylic carbonyl of free fatty acids or resin acids at 1712–1719 cm^–1 is verified in the spectra of two-thirds toluene/one-third ethanol and hot water extracts. Signals at 187.9,178.4, and 173.3 ppm in the¹³C NMR spectrum of MTBE extract correspond to carbonyl groups of resin acids, fatty acids, and fatty acid/steryl esters, respectively. All the extractives were to varying degrees thermally unstable at a temperature of about 200°C, and the melting temperature occurred at about 54°C.     

利用核磁共振自由感应衰减曲线测定木材含水率

为定量测定木材含水率,以水分子中的质子为探针,利用核磁共振技术探究木材内部水分的变化情况。通过对胡桃木、红橡木和水曲柳解吸过程中,水分变化的核磁共振自由感应衰减曲线（FID）进行分析,发现木材的含水率与核磁共振的FID信号量高度线性相关,相关系数均超过0.99;因此,可以通过建立含水率与核磁共振FID信号的标准曲线实现木材含水率的核磁共振定量测量。同时,可以根据绝干木材的核磁共振FID信号量比较不同材种基本密度的大小。      

Integrated standardization concept for Angelica botanicals using quantitative NMR

Despite numerous in vitro/vivo and phytochemical studies, the active constituents of Angelica sinensis (AS) have not been conclusively identified for the standardization to bioactive markers. Phytochemical analyses of AS extracts and fractions that demonstrate activity in a panel of in vitro bioassays, have repeatedly pointed to ligustilide as being (associated with) the active principle(s). Due to the chemical instability of ligustilide and related issues in GC/LC analyses, new methods capable of quantifying ligustilide in mixtures that do not rely on an identical reference standard are in high demand. This study demonstrates how NMR can satisfy the requirement for simultaneous, multi-target quantification and qualitative identification. First, the AS activity was concentrated into a single fraction by RP-solid-phase extraction, as confirmed by an alkaline phosphatase, (anti-)estrogenicity and cytotoxicity assay. Next, a quantitative ¹H NMR (qHNMR) method was established and validated using standard compounds and comparing processing methods. Subsequent 1D/2D NMR and qHNMR analysis led to the identification and quantification of ligustilide and other minor components in the active fraction, and to the development of quality criteria for authentic AS preparations. The absolute and relative quantities of ligustilide, six minor alkyl phthalides, and groups of phenylpropanoids, polyynes, and poly-unsaturated fatty acids were measured by a combination of qHNMR and 2D COSY. The qNMR approach enables multi-target quality control of the bioactive fraction, and enables the integrated biological and chemical standardization of AS botanicals. This methodology can potentially be transferred to other botanicals with active principles that act synergistically, or that contain closely related and/or constituents, which have not been conclusively identified as the active principles.