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.     

柳枝稷木素分离与结构表征的研究

采用球磨法分离纯化原木素的方法, 运用13C核磁共振方法研究了4个不同品种柳枝稷Panicum virgatum的原木素结构,并研究了其酸溶木素与酸不溶木素含量,结果得出： 4个品种的木素包含3种基本的木素单元,即对羟苯基H、愈疮木基G和紫丁香基S,各单体的含量都较多;酸不溶木素（Klason）含量为20%～23%,酸溶木素含量为2%～3%。 4个品种柳枝稷的原木素结构相似,木素含量相近,结果表明不同种类柳枝稷木素结构及含量较稳定。     

核磁共振磷谱在有机化合物草甘膦合成过程中的监控

磷谱是核磁共振的一项重要应用,它在有机化学的定性、定量以及合成过程的监控实验中具有非常重要的作用。本文开发了利用核磁共振磷谱进行有机农药草甘磷部分合成过程监控的实验方法。为草甘膦质量控制和品质提升提供方法支持,同时为进一步扩大核磁共振在有机农药化合物研究领域中的应用提供参考。     

土壤腐殖质结构的光谱学研究进展

有机质光谱分析法在土壤腐殖质结构研究中的应用,已使土壤腐殖质的研究取得了相当大的进展。它的应用能快速确定很多有机化合物的复杂结构,从而使腐殖质的结构研究提高到了新的水平。但由于腐殖质结的复杂性和研究手段的局限性,人们对土壤腐殖酸的结构仍然不甚清楚。为克服腐殖质提取和热解过程对结构的影响,弄清光谱分析方法在这一研究过程中的不足,未来的优先研究领域是:(1)土壤腐殖质分离。不同提取剂、甲基化、水解、氧化和还原作用都会对腐殖质化学结构产生影响,从而影响结构的精确性;(2)土壤腐殖质结构对环境的响应。同一土壤腐殖质的结构,化学性质也随着气候、母质、海拔、植被类型、土壤管理等不同而不同;(3)土壤腐殖质的化学分析测试手段的研制。每种光谱分析法都有一定的局限性,样品制备、分析技术和操作条件,都会对腐殖质结构产生一定影响,标准谱图也有待发展,并没有囊括所有腐殖质。     

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

通过双 [2 -羟基 - 3-溴 (氯 ) - 5-氯 (溴 )代苯基 ]甲烷 4 A(4 B)与 P4 S10在三乙胺存在下关环 ,得到中间体 6 -硫 -巯基 - 4 ,8-二溴 (氯 ) - 2 ,10 -二氯 (溴 ) - 12 H -双苯并 [ d,g ][1,3,2 ]-二氧磷杂八环三乙胺盐 5A(5B)。后者与卤代物反应得到了一系列相应的酯 6。测试并讨论了合成的 6的 1H、31P、13 C NMR、MS及抑菌活性。     

土壤腐殖质结构的光谱学研究进展

有机质光谱分析法在土壤腐殖质结构研究中的应用,已使土壤腐殖质的研究取得了相当大的进展。它的应用能快速确定很多有机化合物的复杂结构,从而使腐殖质的结构研究提高到了新的水平。但由于腐殖质结的复杂性和研究手段的局限性,人们对土壤腐殖酸的结构仍然不甚清楚。为克服腐殖质提取和热解过程对结构的影响,弄清光谱分析方法在这一研究过程中的不足,未来的优先研究领域是：（1）土壤腐殖质分离。不同提取剂、甲基化、水解、氧化和还原作用都会对腐殖质化学结构产生影响,从而影响结构的精确性;（2）土壤腐殖质结构对环境的响应。同一土壤腐殖质的结构,化学性质也随着气候、母质、海拔、植被类型、土壤管理等不同而不同;（3）土壤腐殖质的化学分析测试手段的研制。每种光谱分析法都有一定的局限性,样品制备、分析技术和操作条件,都会对腐殖质结构产生一定影响,标准谱图也有待发展,并没有囊括所有腐殖质     

Role of aleurone cell walls in water diffusion and distribution within cereal grains

Wheat (Triticum aestivum L) and barley (Hordeum vulgare L) are two important cereals cultivated worldwide. The effect of aleurone cell wall structure on water diffusion and distribution within wheat and barley grains was evaluated at different relative humidity levels. Time domain nuclear magnetic resonance was used to measure the transverse relaxation time T₂ of grains. Two water states were distinguished within grains, namely W₁ (lower mobility) and W₂ (higher mobility). Grains with thicker aleurone layer cell walls had a higher W₂. The water-absorption and desorption rates were mainly determined by the thickness of the aleurone cell walls and decreased with increasing cell wall thickness. The higher W₂ values observed in grains with thicker aleurone cell walls with the a water content of 2.0% (w/w) and 12.1% (w/w) were probably related to a higher water motion within the grains, in response to higher porosity. Arabinoxylan and (1,3)(1,4)-β-glucan alternating multilayer films were prepared, each film had 20 layers, one layer was approximately 1 μm thick. The film was used as a model to simulate the aleurone layers. These results show that cell walls of the aleurone layer regulate the diffusion and distribution of water within grains.