Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d(6)/pyridine-d(5).

Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d(6)/pyridine-d(5).
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DOI:
10.1039/b916070a
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发表时间:
2010-02-07
影响因子:
3.2
通讯作者:
Ralph J
Ralph J
中科院分区:
化学3区
文献类型:
--
作者:
Kim H;Ralph J

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最近已经描述了在DMSO中溶胀的细碎植物细胞壁的组分的NMR指纹。细胞壁凝胶,直接在NMR管中产生的全氘-二甲基亚砜,允许收购以及解析/分散的2D 13 C-1H相关的溶液状态NMR光谱的整个阵列的壁聚合物,而不需要组分分馏。也就是说,在没有实际溶解的情况下,并且在没有明显的结构修饰的情况下,除了球磨和超声处理步骤所造成的结构修饰之外,可以获得令人满意的可解释的光谱,其揭示了关于壁中的多糖和木质素组分的组成和结构细节。在此,通过使用全氘代DMSO和吡啶(4:1,v/v)的混合物改进了分析方法。加入吡啶不仅提供了更容易的样品处理,因为更好的流动性相比,只有DMSO-d 6系统,但也大大提高了强度和改善的分辨率的NMR光谱,由于增强的细胞壁的溶胀。因此,这种改进提供了一种比目前可用的更快速的植物细胞壁比较结构评价方法。我们研究了火炬松(火炬松,裸子植物)、白杨(白杨,被子植物)、红麻(红麻,草本植物)和玉米(玉米,草,即,来自禾本科)。原则上,木质素组成(值得注意的是,双辛基:愈创木基:对羟基苯基比率)可以在不需要木质素分离的情况下定量。在玉米样品中的p-香豆酸单位的相关性很容易看到,和各种阿魏酸的相关性也得到很好的解决;阿魏酸是重要的组成部分,负责细胞壁交联草。基于标准样品和各种文献数据,对每个植物样品的多糖端基异构体相关性进行了初步分配。随着使用2D NMR指纹的化学计量学分析的新潜力,这种凝胶状态方法可以为提供用于选择生物质系和用于优化生物质加工和转化效率的二次筛选的有吸引力的方法提供基础。
NMR fingerprinting of the components of finely divided plant cell walls swelled in DMSO has been recently described. Cell wall gels, produced directly in the NMR tube with perdeutero-dimethylsulfoxide, allowed the acquisition of well resolved/dispersed 2D 13C–1H correlated solution-state NMR spectra of the entire array of wall polymers, without the need for component fractionation. That is, without actual solubilization, and without apparent structural modification beyond that inflicted by the ball milling and ultrasonication steps, satisfactorily interpretable spectra can be acquired that reveal compositional and structural details regarding the polysaccharide and lignin components in the wall. Here, the profiling method has been improved by using a mixture of perdeuterated DMSO and pyridine (4:1, v/v). Adding pyridine provided not only easier sample handling because of the better mobility compared to the DMSO-d6-only system but also considerably elevated intensities and improved resolution of the NMR spectra due to the enhanced swelling of the cell walls. This modification therefore provides a more rapid method for comparative structural evaluation of plant cell walls than is currently available. We examined loblolly pine (Pinus taeda, a gymnosperm), aspen (Populus tremuloides, an angiosperm), kenaf (Hibiscus cannabinus, an herbaceous plant), and corn (Zea mays L., a grass, i.e., from the Poaceae family). In principle, lignin composition (notably, the syringyl : guaiacyl : p-hydroxyphenyl ratio) can be quantified without the need for lignin isolation. Correlations for p-coumarate units in the corn sample are readily seen, and a variety of the ferulate correlations are also well resolved; ferulates are important components responsible for cell wall cross-linking in grasses. Polysaccharide anomeric correlations were tentatively assigned for each plant sample based on standard samples and various literature data. With the new potential for chemometric analysis using the 2D NMR fingerprint, this gel-state method may provide the basis for an attractive approach to providing a secondary screen for selecting biomass lines and for optimizing biomass processing and conversion efficiencies.
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