ENERGY & FUELS
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2018
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IF 3.024
Zexiang Lyu,Fen-e Gao,Lizhu Wen,Kemeng Shi,Minjun Ma,Chunju Li,Yingxiong Wang,Yan Qiao
Analyzing the mixtures obtained from hydrogenation or hydrogenolysis reactions of biomass-derived platform chemicals is challenging work. With the development and improvement of NMR techniques, the NMR spectrometer proves to be an alternative and highly efficient piece of equipment for the rapid analysis of complex mixtures without the need for tedious purification. Herein, diffusion-ordered spectroscopy (DOSY) is applied in analyzing four model mixtures, which consist of the reactants and products from hydrogenation/hydrogenolysis reactions of biomass-derived platform chemicals. The results show that the DOSY technique can pseudoseparate most components in the model mixtures. The 1D selective gradient TOCSY technique is used as a supporting tool in the cases where the DOSY technique cannot clearly distinguish between the components of the mixtures. This is generally a problem when components in the mixture have very similar diffusion coefficients or severe overlap of peaks. The results show that DOSY and 1D selective gradient TOCSY techniques make a strong combination for complex mixture analyses.
研究领域:
分析化学
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生物化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2018
·
IF 3.956
Zexiang Lyu,Fen Yue,Xiuyin Yan,Jianfeng Shan,Danlei Xiang,Christian Marcus Pedersen,Chunju Li,Yingxiong Wang,Yan Qiao
Hydrogenolysis is necessary for preparing various value-added chemicals from glycerol. Routine methods like GC and HPLC are not sufficient for analysis the reaction mixtures because the products usually have high boiling or similar polarity, especially when new chromatographic peaks are found which requires other technologies such as NMR . Although they were developed for years, but either DOSY or 1D selective TOCSY NMR has nature limitations. Herein we took their advantages and combined them to analyse glycerol hydrogenolysis mixtures for the first time. A model reaction mixture was first pseudo separated in DOSY spectrum, and 1D selective gradient TOCSY was further applied to assign the overlapped signal which could not be confirmed just by DOSY. A genuine reaction mixture was tried afterwards, and main signals could be assigned well in DOSY diffusion dimension. Notably, n-propanol was found as by-product by 1D selective gradient TOCSY, which is not visible in DOSY spectrum. The experimental results demonstrate that the combination of these two NMR methods could provide a fast, effective, feasible and reliable way for the identification of glycerol hydrogenolysis mixtures and is expected to apply in other research areas.
研究领域:
化学
·
生物化学
·
分析化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Qi Zhao,Hui Ma,Christian M. Pedersen,Mengyu Dou,Yan Qiao,Xianglin Hou,Yongqin Qi,Yingxiong Wang
Pure shift, a novel nuclear magnetic resonance (NMR) spectroscopy technique is here applied to analyze the hydrogenation/hydrogenolysis products of the biomass-derived platform compounds. The complex and very overlapped 1H NMR signals of the model mixtures from several biomass hydrogenation/hydrogenolysis reactions, such as glucose hydrogenation, sorbitol hydrogenolysis, levulinic acid (LA) formation, tetrahydrofurfuryl alcohol hydrogenolysis, and a real reaction system, were successfully analyzed and assigned by suppressing homonuclear couplings. Thus, we can clearly achieve component analysis and distinguish most signals according to one-dimensional (1D) pure shift obtained by chirp excitation (PSYCHE) spectra. For sophisticated mixtures, e.g., α-d-glucose, sorbitol, and mannitol, or LA, γ-valerolactone, and 2-methyltetrahydrofuran, and finally the real reaction mixture, the 1D total correlation spectroscopy (TOCSY)-PSYCHE approach was used as a supplementary tool to obtain full signals in one component. This allowed us to further resolve the signals where the PSYCHE technique failed to distinguish the signals sufficiently. The results demonstrated that the combined use of 1D PSYCHE and 1D TOCSY-PSYCHE techniques successfully analyzed various catalytic hydrogenation/hydrogenolysis mixtures and enabled us to provide precise signal assignments. Therefore, the pure shift NMR tool (a combination of 1D PSYCHE and 1D TOCSY-PSYCHE) can significantly simplify and successfully be used to assign the NMR spectra of the biomass-derived complex mixture, such as hydrogenation/hydrogenolysis reaction mixtures.
研究领域:
化学
·
分析化学
·
生物化学
✓ 已验证
产品关联
DOI
高影响因子
ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Hui Ma,Jiankai Huang,Chao Luo,Weiguang Yang,Yan Chen,Feifeng Pang,Weibang Yu,Kefeng Wu,Yingxiong Wang,Qi Zhao
NMR spectroscopy is a powerful spectroscopic technique that permits the detailed study of the molecular structure elucidation and mixture component analysis, especially in the identification of complex mixtures. However, the conventional 1 H NMR generally suffers from crowded resonances when measuring and identifying carbohydrates of polysaccharide hydrolysis systems, which contain various chemically similar compounds and even multiple isomeric monosaccharides. Herein we describe the application of a targeted detection NMR approach, gradient-enhanced multiplet-selective targeted-observation NMR experiment GEMSTONE–TOCSY, exploited for studying polysaccharide hydrolysis mixtures by spectroscopically targeting the desired compounds in separate 1D NMR spectra. There are six model mixtures of natural bioactive polysaccharide hydrolysis (including 11 monosaccharides) and three real reaction systems (carob seed polysaccharide, tremella polysaccharide and stachyose hydrolysis), which are tested by GEMSTONE–TOCSY NMR showing satisfactory performance in monosaccharide identification and structure analysis even when proton signals are crowded and overlapped in conventional 1 H NMR. Moreover, GEMSTONE–TOCSY NMR uses a fast, single-scan method that allows selective excitation of the signals of a single proton multiplet and available for highly efficient analysis. The results demonstrate that GEMSTONE–TOCSY NMR technique is robust and reliable to analyze and identify monosaccharide composition of various polysaccharides from mixture systems, even providing efficient analysis tool for detecting the polysaccharide hydrolysis process.
✓ 已验证
DOI
高影响因子
ANALYTICA CHIMICA ACTA
·
2019
·
IF 5.256
Hui Ma,Christian Marcus Pedersen,Qi Zhao,Zexiang Lyu,Hui Chang,Yan Qiao,Xianglin Hou,Yingxiong Wang
The Fischer–Tropsch (FT) process is a practical approach to convert synthesis gas (CO and H 2 ) into hydrocarbons and oxygenates, and these product mixtures are usually well-characterized. However, the analysis of Fischer–Tropsch waste water (FTW) is still somewhat underdeveloped and the exact composition of FTW remains unclear. Herein, various qualitative NMR techniques, especially diffusion-ordered spectroscopy (DOSY) and one dimension (1D) selective gradient total correlation spectroscopy (SelTOCSY) were strategically applied in the analysis of FTW. The NMR results show that the DOSY technique can pseudo-separate most of components in complex mixtures over the diffusion dimension. The SelTOCSY technique is used as a supporting method in the cases where the DOSY technique cannot clearly distinguish overlapped signals. Moreover, the quantitative 1 H NMR (qNMR) was further used to quantify the components of the sample. These routine and advanced qualitative and quantitative NMR technique utilized here provide a fast, effective and feasible method for the identification of complex mixtures in FTW, which might be a powerful and fast alternative to gas chromatography or high performance liquid chromatography for FTW research.
研究领域:
化学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）