An infrared and <Superscript>1</Superscript>H MAS NMR investigation of strong hydrogen bonding in ussingite,Na<Subscript>2</Subscript>AlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>(OH)

The mineral ussingite, Na₂AlSi₃O₈(OH), an interrupted tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm^–1, and a possible OH librational bending mode at 1295 cm^–1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the ¹H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and ¹H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5–8% Al–Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and ¹H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.     

多尺度孔隙岩石的核磁共振扩散耦合现象及其探测方法

油藏岩石的孔隙连通性是反映流体渗流难易程度的重要参数,对渗透率、有效孔隙度等岩石物理参数的评价具有重要作用.连通的孔隙中,核磁共振(NMR)弛豫的交换会产生扩散耦合现象,可作为孔隙连通性的表征和探测方法.本文提出利用横向弛豫T 2-T 2脉冲序列测量岩石的扩散耦合现象.运用随机游走方法模拟多孔岩石的核磁共振响应特征,分析扩散耦合的影响因素,推导表征扩散耦合强度的弛豫交换速率计算公式.结果表明:孔隙间的扩散耦合强度与T 2-T 2脉冲序列的混合时间呈正相关性,基于双孔弛豫交换模型推导的弛豫交换速率计算公式能够准确表征双尺度孔隙系统的扩散耦合强度.在孔隙尺寸不满足快扩散条件时,会出现与扩散耦合无关的非对角峰信号.针对含多类型孔隙的碳酸盐岩模型,随混合时间的增加,扩散耦合强度变大,一维T 2谱的形态畸变程度加重,在T 2-T 2二维谱中,代表微裂缝、粒间小孔、溶蚀大孔的信号能量变化趋势不同,反映不同类型孔隙间的连通性存在差异.本文的分析与讨论丰富了核磁共振弛豫在岩石物理性质评价中的应用方向,对利用核磁共振评价复杂孔隙岩石的孔隙结构和连通性提供了新思路和新方法.     

硅藻土中水的NMR研究

本文用ＮＭＲ技术研究硅藻土中水的存在状态和特征及灼烧条件下的脱水和室温大气下的重吸水过程。样品包括一个宝石级单矿物蛋白石和采自雷州半岛地区的海康卜昌和徐闻九亩的硅藻土地表样和它们经不同温度自理后的产物。     

核磁共振技术应用的新领域——探查地下水

利用核磁共振（ＮｕｃｌｅａｒＭａｇｎｅｔｉｃＲｅｓｏｎａｎｃｅ缩写为ＮＭＲ）技术探查地下水仅有二十多年的历史,文中简要介绍了ＮＭＲ找水方法的发展状况,原理和方法特点,重点介绍了中国地质大学（武汉）利用ＮＭＲ找水方法在中国一些地区找水取得的成效,最后指出了ＮＭＲ找水方法的发展趋势。     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Dissolved Organic Carbon Fractions Formed during Composting of Municipal Solid Waste: Properties and Significance

The properties and transformation of dissolved organic matter (DOM) extracted (10 L water per kilogram compost) from municipal solid waste (MSW) compost at five stages (days 47, 77, 105, 126, and 187) of composting were investigated. The DOM was fractionated into hydrophobic or hydrophilic neutrals, acids, and bases. The unfractionated DOM, the hydrophobic acids and neutrals (HoA and HoN, respectively), and the hydrophilic neutrals (HiN) fractions were studied using solid-state ¹³C-NMR, FTIR, and DRIFT spectroscopy. The HoA fraction was found to be the dominant (percentage of total DOM) hydrophobic fraction, exhibiting a moderate increase during composting. The HoN fraction increased sharply from less than 1% to 18% of the total DOM during 187 days of composting, while the hydrophobic bases (HoB) exhibited the opposite trend. The HiN represented the major fraction of the hydrophiles up to 120 days of composting, decreasing thereafter by 38%. The relative concentration of the hydrophilic acids and bases (HiA and HiB, respectively) exhibited no consistent trend during composting. DRIFT spectra of the unfractionated DOM taken from the composting MSW revealed a decreasing level of polysaccharide structures with time. The ¹³C-NMR and FTIR spectra of the HoA fraction exhibited a polyphenol-humic structure, whereas the HoN spectra exhibited strong aliphatic features. The spectra of the HiN fraction confirmed its polysaccharide nature. During the final stage of composting, the DOM concentration was steady, while a relative decrease of HiN concomitant with an increase of HoA and HoN fractions was observed. These indicate that the DOM contained a low concentration of biodegradable organic matter and a higher content of macromolecules related to humic substances. The biological significance and heavy metal binding of these fractions are being studied based on earlier observations showing enhanced plant growth in the presence of DOM extracted from mature as opposed to immature compost.     

缩短核磁共振测定冻土未冻水含量实验时间的方法

为利用核磁共振(NMR)技术更快地测试得到冻土中未冻水的含量, 首先对传统的单试样测试方法进行了分析, 探究了其实验时间过长的原因. 然后, 基于传热学中的集总参数法, 研究了小体积试样在空气中以自然对流传热为冷却方式的温度变化特征. 根据试样温度与时间的对应关系, 提出了多试样连续测试法. 最后, 以一种黏土为例, 分别利用多试样连续测试法和单试样测试法测量了土样冻结过程中NMR信号强度随温度变化的关系. 实验结果表明: 二者的测量结果非常接近, 但连续测试法耗费的时间非常少. 综合比较两种利用NMR技术所耗费的时间和实验结果的精确程度, 多试样连续测试法是可行的.     

GC-MS联合二维核磁对文蛤多糖Fr.2A组分结构的解析

采用GC-MS联合二维核磁的方法,对文蛤均多糖结构进行解析。运用双酶辅助水提的方法,提取文蛤粗多糖(MMPX),分离纯化得到文蛤均多糖,并通过气质联用技术(GC-MS)和核磁共振波谱(1D,2D NMR),对文蛤均多糖的结构进行了分析。结果表明,从文蛤中提取得到文蛤粗多糖(MMPX),经分离纯化得到高纯度文蛤均多糖Fr.2A,其单糖组成为葡萄糖(Glc)。GC-MS分析发现,Fr.2A存在三种残基单元1,4-Glcp、T-Glcp和1,4,6-Glcp,摩尔比为5.58︰1.26︰1.0;核磁共振波谱分析表明,Fr.2A是以α-(1→4)与少量α-(1→6)连接为主链,并存在少量的α-(1→6)和β-(1→4)支链的新型水溶性D型吡喃葡聚糖。     

基于SVD和BRD的二维核磁共振测井正则化反演算法研究

二维核磁共振能从"弛豫-扩散"两个维度上展现流体性质,在识别稠油储层方面具有理论优势,是当前核磁共振测井技术的研究热点.本文深入研究二维核磁共振测井原理,系统分析CPMG-DE脉冲序列测量扩散系数与弛豫时间的方法,结合核磁共振二维谱数理模型,提出一种基于SVD和BRD的正则化反演算法.该算法通过SVD压缩数据,采用带非负约束的Tikhonov正则化方法求解流体"弛豫-扩散"分布,并基于BRD算法迭代确定最佳正则化因子.模拟实验与数值分析表明,该算法无需先验信息、运算效率高、相对误差小,在原始数据信噪比低至50时,仍可有效获取流体(T₂,D)二维分布.在二维核磁共振测井数据实时解释应用中,该方法较传统反演算法(如TSVD)具有较大优势.同时,在自主研发的核磁共振测井仪测量CuSO₄溶液(T₂,D)分布的实验显示,本文设计算法对弛豫时间和扩散系数的反演误差分别仅为2%和4%,较TSVD算法有较大改善.