简易核磁碳谱应用于有机锂试剂的结构信息探讨

利用简易核磁碳谱技术，在乙醚溶液体系中检测了多种有机锂试剂的碳谱与DEPT谱。实验结果表明有机锂试剂的化学位移不因浓度而改变，苯基锂的碳负离子不与苯环形成共振。化学位移数据显示由饱和以及芳香卤化物制备得的有机锂其碳负离子分别往高场以及低场迁移。由苯基锂碳负离子呈现的去屏蔽效应推论苯基锂左乙醚溶液申以双聚体头尾相并形式存在．     

固体碳的一种新形态——富勒烯

一富勒烯(Fullerene)的发现人类对碳元素的研究和应用亘古至今,源远流长。人们熟知碳有两种同素异形体——石墨和金刚石。直到80年代中期,发现了富勒烯碳原子簇,尤其是近年来,对富勒烯的结构、性质深入广泛地研究,确认碳元素还存在着第三种晶体形态,已是顺理成章了。碳原子簇的研究始于天体物理学家对宇宙尘埃形成的兴趣,为了模拟星际空间及恒星附近碳原子簇的形成过程,早在1942年O Hahn等用质谱法证实了原子簇C_n(n<15)的存在。1984年Rohlfing等用质谱仪研究在超声氦气流中以激光蒸发石墨所得产物时,发现碳可以形成n<200的C_n原子簇。当n>40时,簇中碳原子教仅为偶数,并且还发现C_(60)的质谱峰明显高     

平朔气煤DF5的组成特性及煤液体统计平均结构参数的相似性

Two kinds of coal liquid, the distilled fraction (270～340℃) (DF5) of low temperature carbonization tar and the extracts by heptane (PM1) and THF/MET (PM7) from Chinese Pingshuo bituminous coal were studied using GC-MS and　13C-NMR, and were compared with each other. The results show that the compounds in DF5 can be classified as paraffinic compounds and non-paraffinic compounds. The average molecular weight of the paraffinic compounds (MPC=303.03) is as same as that of the extract PM1 (MPM1=298.16), as well as their molecular weight distributions. The statistical average molecular structural parameters of the non-paraffinic compounds, such as aromatic carbon fa and the structure unit number MSP, were similar to that of the extract PM7.     

麦秸秆与黑龙江褐煤共热氧化法制备腐植酸及其结构分析

结合矿源腐植酸(HA)产率高及生化HA活性高的特点,本研究提出将低阶煤与生物质共热氧化制备复合型HA(MIXHA)的想法。将黑龙江褐煤(HL)及麦秸秆(WS)的混合物(MIX)在10%的HNO₃溶液中进行了共热氧化,制备了MIXHA。通过SEM、FT-IR、¹³C NMR等分析,重点从HA的宏观形貌及微观结构对比了MIXHA与HL、WS分别单独制备的矿源HA、生化HA,分析HL与WS在共热氧化过程的协同作用。结果表明,MIXHA含量高于理论值,HNO₃分子的分解产生的活性氧原子、氮氧化物进攻HL与WS的分子结构,由于氢键重排、糖苷键断裂、交联等作用,WS纤维素与半纤维素产生的大量烷基自由基结合在HL缩合芳环上被氧化产生的醌基、羧基的邻对位,从而将芳香环上的质子碳转化为脂肪取代碳。得到的MIXHA含氧官能团丰富、活性高,FT-IR谱图具有明显的特征峰。本研究为低阶煤与农林废弃物的分级、资源化利用提供了一种新思路。     

高灰煤中矿物质及碳结构的振动光谱分析

利用傅里叶变换红外光谱(FT-IR)、拉曼光谱和X射线衍射(XRD),分析了广西合山煤(GX)和平顶山煤(PD)及其酸洗煤的矿物质组分和碳结构。FT-IR谱图显示,GX和PD原煤的高岭石含量最为丰富,其次是石英和方解石,由二阶导数红外谱图发现,煤中还存在云母、蛇纹石、石膏和碱性长石。此外,从FT-IR谱图出现的三个层间水OH伸缩振动峰(3 695、3 651和3 619 cm^-1)判断煤中高岭石的结晶度不高。酸洗煤的FT-IR和XRD分别显示出清晰的芳香C=C官能团峰(1 600 cm^-1)和微晶碳(002)衍射峰;原煤的FT-IR和XRD都表明,矿物质完全掩盖了碳的信息。尽管如此,原煤及酸洗煤的拉曼谱图显示出清晰的缺陷碳峰(D峰)和石墨碳峰(G峰),而矿物质的信息完全被信号更强的碳峰掩盖。酸洗处理对煤的碳结构有较弱的影响,酸洗煤的碳结构有序度略低于原煤。     

煤液化沥青分析表征及结构模型

对从煤液化残渣中萃取出的沥青类物质进行了固体13C-CP/MAS NMR分析、元素分析、红外光谱分析(FT-IR)和光电子能谱(XPS)分析,得到煤液化沥青的芳香结构单元信息及相关结构参数信息。结果表明,煤液化沥青芳香桥碳与周碳之比为0.115,芳香碳原子的存在形式以苯结构为主;脂肪结构多以甲基和环状亚甲基形式存在;氧主要以羰基、酯基的形式存在;氮主要以吡咯的形式存在。利用结构参数和分析表征结果构建了煤液化沥青的大分子结构模型,并运用13C-NMR预测软件ACD/CNMR Predictor计算了煤精制沥青大分子结构模型的13C化学位移。根据计算结果对大分子结构模型进行了修正,获得了与实验谱图吻合较好的大分子结构模型。     

弱粘结煤的高温结构变化及其对合成SiC的影响

用弱粘结煤与石英砂以Acheson工艺合成了SiC ,用SEM研究了弱粘结煤高温焦炭的孔隙结构 ,并对弱粘结煤 80 0℃～ 1 60 0℃的焦炭进行了X射线衍射分析 ,计算了各温度下的微晶结构参数。研究表明 ,弱粘结煤高温焦炭孔隙率、长径比和表面积大 ,反应性好 ,可为SiC快速、大范围生长提供有利条件。微晶活化温度范围也和SiC的最佳合成温度范围基本一致。     

低维金属固体化合物的能带结构及化学键研究──（Ⅰ）低维固体的离域d－pπ键与导电性

通过对一系列层状及链状金属化合物能带结构的计算和理论分析，指出其分子结构的低维性是导致金属原子与主族桥原子间离域ｄ－ｐπ键的存在的主要原因，并阐述了其所形成的ｄ－ｐπ（π）能带的性质。通过对该能带的研究，建立了以ｄ电子数判断固体导电性的简便方法，阐明了电荷转移现象及其对导电性的影响，并指出了ｄ电子巡游性的本质。     

NMR imaging studies of coal

The permeation, transportation and swelling behavior of solvents into coal are investigated by NMR imaging using pyridine-ds and acetone-d6. Images of coal swollen with deuterated solvents illuminate proton distributions of mobile phases within the coal macromolecular networks. More information about the chemical and physical structure of coal can be obtained using NMR imaging techniques.     

Modern solid state NMR techniques and concepts in structural studies of synthetic polymers

In this mini‐review, we present the solid state nuclear magnetic resonance (NMR) methods which trace the new tendency in structural studies of synthetic polymers. The review is organized into three sections. In the first part, short theoretical background and introduction to very fast magic angle spinning NMR technique with sample rotation 60 kHz are shown. The second part presents method for enhancing the sensitivity of NMR experiments by application of dynamic nuclear polarization magic angle spinning technique. In the third section, the power of the NMR crystallography approach which can be used for fine refinement of polymers structure on the atomic level is discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

高温下煤焦的碳微晶及孔结构的演变行为

以贵州煤为原料,在热解温度950℃~1400℃制备了各种慢速和快速热解焦,主要对高温热解过程中煤焦的碳微晶和孔结构的演变行为进行了研究,同时也研究了高温气化过程中煤焦的孔结构变化规律。结果表明,慢速热解焦和快速热解焦的C和H含量明显不同;随热解温度的升高,煤焦的碳微晶结构向有序化方向发展,但慢速热解煤焦比快速热解煤焦的"石墨化"程度大;快速热解煤焦的微孔比表面积和微孔容积明显高于慢速热解煤焦,即快速热解煤焦的孔隙结构明显比慢速热解煤焦发达;在气化反应初期,煤焦的微孔比表面积下降,微中孔比表面积增加,反应后期煤焦的总比表面积快速下降。     

Supramolecular aspects of polymer science: a challenge for solid state NMR

Recent developments in structural elucidation of supramolecular systems by advanced solid state NMR are described. Special emphasis is placed on hydrogen-bonded sytems and columnar stacks of aromatic moieties. In imidazole-based proton conductores spatially separated regions of high and low mobility are identified. In stacks of alkyl-substituted hexabenzocoronenes maximum charge carrier mobility is observed for crystal-like stacking of the discs.     

中温煤沥青基碳量子点的制备与结构解析

以中温煤沥青为碳源，采用HNO₃预处理结合球磨过程及双氧水氧化刻蚀的方法制备沥青基荧光碳量子点，以CQDs的收率和荧光量子产率为目标，获得最优制备条件：反应时间6 h、H₂O₂加入量100 mL （c-CQDs），此时，CQDs收率和荧光量子产率分别为6.3%和11.2%，且尺寸均匀、粒径分布在4-14 nm。延长反应时间至8 h （a-CQDs），碳量子点团聚；H₂O₂用量增加至120 mL （b-CQDs）则导致碳量子点氧化过度，颗粒小且杂乱无章。对不同条件下所制备的CQDs进行XPS、红外光谱、热重、¹³C NMR、Raman和晶相分析，探究反应条件对CQDs结构的影响规律。结果表明，就碳含量而言，a-CQDs > b-CQDs > c-CQDs，氧元素含量则为b-CQDs > c-CQDs > a-CQDs。各CQDs结构中C主要以芳碳形式存在，c-CQDs的C=O、O-C=O含量最高，而b-CQDs的C-O含量最高，¹³C NMR分析发现CQDs中表征平均芳环尺寸大小的X_b约为0.5，相应地，其平均芳环数约为3。     

Peroxidic perfluoropolyether from tetrafluoroethylene oxidation: micro structural analysis by NMR spectroscopy and mechanistic considerations

The oxypolymerization reaction of perfluoro olefins is one of the industrial routes for the synthesis of perfluoropolyethers (PFPEs). The distinctive feature of this radically initiated process is that one obtains peroxidic perfluoropolyethers from the oxypolymerization reaction. In the particular case of tetrafluoroethylene (TFE), due to the high reactivity of the olefin, it is possible to obtain peroxidic polymers with variable amounts of peroxide units. It is, therefore of great interest to know in detail the micro structure of this peroxidic polymer with ¹⁹F and ¹³C NMR spectroscopy by far the most suitable techniques for the analysis. A recent investigation on samples with variable peroxide content using a 400 MHz instrument allowed a significant improvement in the analysis of the peroxidic sequences. The results have been discussed in terms of reaction mechanism and kinetics.     

Investigation of 205Tl NMR shielding,structural, and electronical properties in thallium halides by applying PBE-GGA,YS-PBE0 and mBJ functionals

We report the structural, electronical, and heavy nuclear ²⁰⁵Tl Nuclear Magnetic Resonance (NMR) shielding properties of thallium halides TlX (X = F, Cl, Br, and I) by the first principles calculation. The Perdew–Burke–Ernzerhof Generalized Gradient Approximation, Yukawa Screened-PBE0 hybrid functional, and modified Becke–Johnson (mBJ) functionals including the relativistic and spin-orbit coupling effects are applied for calculation of the exchange-correlation potentials. Calculated PDOS spectra display that the valence band is composed of the X-s, Tl-5d, X-p, and Tl-6s states, and these states play an important role in ²⁰⁵Tl NMR shielding. Our findings indicate that the nuclear magnetic shielding parameters depend on the electronic properties. Obtained results by mBJ show that there is a close agreement between the experimental and the calculated NMR parameters.     

Peroxidic perfluoropolyether from tetrafluoroethylene oxidation: micro structural analysis by NMR spectroscopy and mechanistic considerations

The oxypolymerization reaction of perfluoro olefins is one of the industrial routes for the synthesis of perfluoropolyethers (PFPEs). The distinctive feature of this radically initiated process is that one obtains peroxidic perfluoropolyethers from the oxypolymerization reaction. In the particular case of tetrafluoroethylene (TFE), due to the high reactivity of the olefin, it is possible to obtain peroxidic polymers with variable amounts of peroxide units. It is, therefore of great interest to know in detail the micro structure of this peroxidic polymer with ¹⁹F and ¹³C NMR spectroscopy by far the most suitable techniques for the analysis. A recent investigation on samples with variable peroxide content using a 400 MHz instrument allowed a significant improvement in the analysis of the peroxidic sequences. The results have been discussed in terms of reaction mechanism and kinetics.     

Study of nucleation induced structure modification in isotactic polypropylene by DMTA and solid state NMR

Isotactic polypropylene (iPP) modified by heterogeneous nucleation and molten state drawing was investigated using the DMTA and NMR methods. The nucleation was realized by specific α and β nucleating agents, 1,3,2,4-bis(3,4-dimetylobenzylideno) sorbitol (Millad 3988, Miliken) leading to the creation of the α phase, and N,N′-dicyklohexylo-2,6-naftaleno dikarboxy amid (NJ100) as the β phase promoter. The processing induced modification was performed by molten state drawing during an extrusion in the range between the die exit and the calibration unit. An increase of the glass transition temperature of iPP was found to be drawing independent for the β-nucleated samples, and dependent in the case of the α-iPP. Changes in the macromolecular mobility, depending on the α/β iPP structure and molten state drawing, was found by NMR lineshape and second moment measurements.