Three dimensional structure prediction and proton nuclear magnetic resonance analysis of toxic pesticides in human blood plasma

The purpose of this study was to investigate the nuclear magnetic resonance （NMR） assignments of hydrolyzed products extracted from human blood plasma. The correlations between chemical, functional and structural prop- erties of highly toxic pesticides were investigated using the PreADME analysis. We observed that toxic pesticides possessed higher molecular weight and, more hydrogen bond donors and acceptors when compared with less toxic pesticides. The occurrence of functional groups and structural properties was analyzed using ~H-NMR. The ~H- NMR spectra of the phosphomethoxy class of pesticides were characterized by methyl resonances at 3.7-3.9 ppm （8） with the coupling constants of 11-16 Hz （Je-cns）. In phosphoethoxy pesticides, the methyl resonance was about 1.4 ppm （8） with the coupling constant of 10 Hz （Je-cH2） and the methylene resonances was 4.2-4.4 ppm （8） with the coupling constant of 0.8 Hz （Jp-cH3）, respectively. Our study shows that the values of four parameters such as chemical shift, coupling constant, integration and relaxation time correlated with the concentration of toxic pesticides, and can be used to characterise the proton groups in the molecular structures of toxic pesticides.

利用^(13)C探头测^(27)Al核磁共振谱

对于８０ＭＨｚ的核磁共振仪，１３Ｃ与２７Ａｌ的共振频率差为０．７３８ＭＨｚ。由于１３Ｃ核磁共振谱测定时需要较宽的频带，选择合适的参数，用１３Ｃ１０ｍｍ单探头或１３Ｃ－１Ｈ５ｍｍ双探头都可以测得２７Ａｌ核磁共振谱。当［Ａｌ３＋］＝０．１ｍｏｌ／Ｌ时，对于１３Ｃ１０ｍｍ探头灵敏度为４２，线宽４．８Ｈｚ；对１３Ｃ－１Ｈ５ｍｍ双探头，灵敏度为２４．８，线宽为３．２Ｈｚ。

Cu_(15)-Al_(85)混合粉末机械合金化反应的^(27)Al核磁共振研究

测量了经过不同时间球磨的Cu1 5-Al85混合粉末的2 7Al核磁共振 (NMR)谱 ,通过分析2 7AlNMR谱的特征参量随球磨时间的变化来研究Cu1 5-Al85混合粉末机械合金化反应的微观过程 样品在球磨过程中发生了真正的合金化反应 ;

Fingerprinting Analysis of Rhizoma Chuanxiong of Commercial Types using ~1H Nuclear Magnetic Resonance Spectroscopy and High Performance Liquid Chromatography Method

The ^1 H nuclear magnetic resonance （^1 H NMR） fingerprints of fractionated non-polar extracts （control substance for a plant drug （CSPD） A） from Rhizoma chuanxiong, the rhizomes of Ligusticum chuanxiong Hort., of seven specimens from different sources were measured on Fourier Transform （FT）-NMR spectrometer and assigned by comparing them with the ^1 H NMR spectra of the isolated pure compounds. The ^1 H NMR fingerprints showed exclusively characteristic resonance signals of the major special constituents of the plant. Although the differences in the relative intensity of the ^1H NMR signals due to a discrepancy in the ratio of the major constituents among these samples could be confirmed by high performance liquid chromatography analysis, the general features of the ^1H NMR fingerprint established for an authentic sample of the rhizomes of L. chuanxiong e. hibited exclusive data from those special compounds and can be used for authenticating L. Chuanxiong species.

Simulation of ^(13)C NMR chemical shifts of carbinol carbon atoms using quantitative structure-spectrum relationships

A quantitative structure-spectrum relationship (QSSR) model was developed to simulate 13C nuclear magnetic resonance (NMR) spectra of carbinol carbon atoms for 55 alcohols. The proposed model,using multiple linear regression,contained four descriptors solely extracted from the molecular structure of compounds. The statistical results of the final model show that R2= 0.982 4 and S=0.869 8 (where R is the correlation coefficient and S is the standard deviation). To test its predictive ability,the model was further used to predict the 13C NMR spectra of the carbinol carbon atoms of other nine compounds which were not included in the developed model. The average relative errors are 0.94% and 1.70%,respectively,for the training set and the predictive set. The model is statistically significant and shows good stability for data variation as tested by the leave-one-out (LOO) cross-validation. The comparison with other approaches also reveals good performance of this method.

Prediction of Vapor-Liquid Equilibria of Alcohol-Hydrocarbon Systems by ^1H NMR and Azeotropic Point

With the energy parameters obtained from1H nuclear magnetic resonance(NMR)chemical shifts data by local composition model and coupled with azeotropic point,the low-pressure vapor-liquid equilibrium is satisfactorily predicted for alcohol+hexane,alcohol+cyclohexane,and alcohol+benzene binary systems at different temperatures.The relationship between the spectroscopic information and thermodynamic property is presented.

^13C NMR and ^1H NMR Spectroscopic Analysis of Adansonia digitata, Albizia lebbeck and Daniellia ofiveri Oils

Oils of AD （Adansonia digitata）, AL （Albizia lebbeck） and DO （Daniellia oliveri） were studied using ^13C NMR （nuclear magnetic resonance） and ^1H NMR. The gated decoupled high resolution ^13C NMR spectra revealed the presence of both saturated and unsaturated triacylglycerides. However, there is a higher percentage of unsaturation in AL seed oil. The peaks at 0.7 ppm to 0.9 ppm which correspond to the terminal methyl groups in the fatty acid and that at 1.2 ppm to 1.3 ppm are more intense and bigger in DO which show that it is more saturated than AD and AL oils. The results obtained by ^13C NMR and ^1H NMR are compared favorably with those obtained by gas chromatographic analysis.

Al-Ferron逐时络合比色光度法测定聚合铝溶液中Al_a,Al_b和Al_c三种铝形态的时间界限研究

AlFerron逐时络合比色法是研究聚合铝溶液中铝的形态分布及其转化规律的基本方法。但在具体操作过程中,由于Ala,Alb和Alc三种铝形态时间界限划分的随意性和武断性,使得许多实验结果难以重复。造成这种差别的原因主要是因为这三种铝形态的具体组分与Ferron反应时具有不同的反应机理和动力学,同时也由于不同OH/Al摩尔比的Alb具体形态之间与Ferron反应时的动力学反应速率存在差异。文章应用ExpAssoc分布对AlFerron逐时络合动力学曲线进行了定量模拟,用外推法求得了实验手工操作中难以获取的1min单核铝测定值Ala,以实验曲线达到水平平台作为Alb和Alc的时间界限,用微波消解技术快速测定了聚合铝的总铝AlT浓度。借助于这些方法,我们可以方便地定量计算单核铝Ala、聚合铝Alb和凝胶Alc含量,从而为克服以往测定三种铝形态的随意性、武断性以及Ala和Alb的重叠计算等问题提供了一种新方法。

AlMCM-41介孔分子筛的合成及表征

以拟薄水铝石为铝源、水玻璃为硅源、十六烷基三甲基溴化铵为模板剂,在110℃时水热晶化合成了含Al的MCM-41介孔分子筛.采用X射线衍射(XRD)、N2吸附-脱附、固体29Si、27Al魔角旋转核磁共振技术(MASNMR)、扫描电镜(SEM)及吡啶吸附傅里叶变换红外(FTIR)光谱技术对AlMCM-41分子筛进行了表征.结果表明:AlMCM-41分子筛具有六方排列的孔道结构,同时具有很高的相对结晶度、比表面积和孔容,且孔分布单一;AlMCM-41分子筛中Si原子在骨架内键合的程度更高,使AlMCM-41分子筛具有更好的骨架晶化程度;同时具有四配位骨架铝,使AlMCM-41介孔分子筛具有适当的酸性.

Mg-Al-O复合氧化物催化剂的表面酸碱性质(Ⅲ):体相结构研究

研究了在不同温度下焙烧Mg -Al-O复合氧化物催化剂的体相结构与表面酸碱性质的关系。固态MAS2 7AlNMR结果显示在 673K、873K和 10 73K焙烧的样品出现了明显的物相过渡态 ,该过渡态在确定样品的表面酸碱性质是很重要的。XPS测定样品中Al2S和OIS的结合能 ,结果表明 。

Composition and mineralization of soil organic carbon pools in four single-tree species forest soils

Forest soil carbon （C） is an important compo- nent of the global C cycle. However, the mechanism by which tree species influence soil organic C （SOC） pool composition and mineralization is poorly understood. To understand the effect of tree species on soil C cycling, we assessed total, labile, and recalcitrant SOC pools, SOC chemical composition by 13C nuclear magnetic resonance spectroscopy, and SOC mineralization in four monoculture plantations. Labile and recalcitrant SOC pools in surface （0-10 cm） and deep （40-60 cm） soils in the four forests contained similar content. In contrast, these SOC pools exhibited differences in the subsurface soil （from 10 to 20 cm and from 20 to 40 cm）. The alkyl C and O-alkyl C intensities of SOC were higher in Schima superba and Michelia macclurei forests than in Cunninghamia lanceolata and Pinus massoniana forests. In surface soil, S. superba and M. macclurei forests exhibited higher SOC mineralization rates than did P. massoniana and C.lanceolata forests. The slope of the straight line between C60 and labile SOC was steeper than that between C60 and total SOC. Our results suggest that roots affected the composition of SOC pools. Labile SOC pools also affected SOC mineralization to a greater extent than total SOC pools.

Soil Phosphorus Composition and Phosphatase Activities along Altitudes of Alpine Tundra in Changbai Mountains,China

Alpine tundra ecosystems have specific vegetation and environmental conditions that may affect soil phosphorus （P） composition and phosphatase activities. However, these effects are poody understood. This study used NaOH-EDTA extraction and solution ^31P nuclear magnetic resonance （NMR） spectroscopy to determine soil P composition and phosphatase activities, including acid phosphomonoesterase （AcP）, phosphodiesterase （PD） and inorganic pyrophosphatase （IPP）, in the alpine tundra of the Changbai Mountains at seven different altitudinal gradients （i.e., 2000 m, 2100 m, 2200 m, 2300 m, 2400 m, 2500 m, and 2600 m）. The results show that total P （TP）, organic P （OP）, OP/TP, NaOH-EDTA extracted P and AcP, PD, and IPP activities over the altitude range of 2500-2600 m are significantly lower than those below 2400 m. The dominant extracted form of P is OP （73%0-83%） with a large proportion of monoesters （65%0-72%）, whereas inorganic P is present in lower proportions （17%-27%）. The activity of AcP is significantly positively correlated with the contents of soil OP, total carbon （TC）, total nitrogen （TN）, and TP （P 〈 0.05）, indicating that the AcP is a more sensitive index for responding P nutrient storage than PD and IPP. Soil properties, P composition, and phosphatase activities decrease with increased altitude and soil pH. Our results indicate that the distribution of soil P composition and phosphatase activities along altitude and AcP may play an important role in P hydrolysis as well as have the potential to be an indicator of soil quality.

Nitrogen Forms of Maillard Polymers Derived from Xylose and ^(15)N-Labelled Glycine

Water-soluble, nondialyzable Maillard polymers were prepared by reacting D-xylose with 15N-glycine (and/or glycine) at 68 ℃ and pH 8.0 at equimolar concentrations of 1, 0.5 and 0.1 mol L-1, respectively,for 13 days and partitioned into acid-insoluble (MHA) and acid-soluble (MFA) fractions. The nitrogen forms in these polymers were studied by using the 15N cross polarization-magic angle spinning nuclear magnetic resonance (CPMAS NMR) technique in combination with chemical methods. The 15N nuclear magnetic resonance (NMR) data showed that while the yield, especially the MHA/MFA ratio, varied considerably with the concentrations of the reactants, the nitrogen distribution patterns of these polymers were quite similar.From 65% to 70% of nitrogen in them was in the secondary amide and/or indole form with 24%~25% present as aliphatic and/or aromatic ammes and 5% to 11% as pyrrole and/or pyrrole-like nitrogen. More than half (50%~77%) of the N in these polymers were nonhydrolyzable. The role of Maillard reaction in the formation of nonhydrolyzable nitrogen in soil organic matter is discussed.

The parallel tetrameric DNA G-quadruplex formed by the two-repeat C9orf72 GGGGCC sequence in solution Dedicated to Professor Chaohui Ye on the occasion of his 80th birthday

The abnormal expansion of G-rich hexanucleotide repeat,GGGGCC(G4C2),in chromosome 9 open reading frame 72(C9orf72)is known to be the prevailing genetic cause of two fatal degenerative neurological diseases,amyotrophic lateral sclerosis(ALS)and frontotemporal dementia(FTD).It is well known that the DNA G4C2 repeat expansion with different lengths can form G-quadruplexes which affect gene transcription related to ALS/FTD,therefore it is crucial to understand DNA G4C2 G-quadruplex structures.Herein,by utilizing nuclear magnetic resonance(NMR)spectroscopy,we examined DNA G-quadruplex structure adopted by two G4C2 hexanucleotide repeats with an inosine substitution at position 4,d(G4C2)2-I4.We show that d(G4C2)2-I4 folds into an eight-layer parallel tetrameric G-quadruplex containing two parallel dimeric G-quadruplexes stacking together through p-p interaction via 50-to-50 mode in solution.Each dimeric G-quadruplex unit involves two propeller loops composed of two cytosine bases.This result is consistent with the observation in the crystal structure of d(G4C2)2.Our work not only sheds light on the structural diversity of G-quadruplexes adopted by d(G4C2)n but also provides a structural basis for drug design in treatment of ALS and FTD.

铝交联蒙脱土合成条件的研究

铝交联蒙脱土合成条件的研究李栋藩姜贤郑禄彬（中国科学院大连化学物理研究所，大连１１６０２３）关键词交联蒙脱土，铝交联柱，２７Ａｌ核磁共振，Ｘ射线衍射重油深度加工是实现重油轻质化的重要途径．重油的特征是原料油分子较大，因此重油加工催化剂的孔结构大小具有...

柠檬酸铝溶液中铝的形态研究

采用27AlNMR法、渗析法与原子吸收分光光度法,研究了柠檬酸铝(AlCit)溶液中铝的形态及pH值的影响.结果表明,在AlCit溶液中存在两种形态的Al,一种是分子态AlCit,另一种是胶态Al,pH值增加时,分子态AlCit的量减少而胶态Al的量增加.

柠檬酸铝结构形态及其对部分水解聚丙烯酰胺柠檬酸铝体系交联性质的影响

通过分析27Al核磁共振波谱、自旋晶格弛豫时间,结合数字拟合方法、渗析法和原子吸收分光光度法,对柠檬酸铝的形态结构及其影响因素进行了研究;利用转变压法研究了pH值对部分水解聚丙烯酰胺与柠檬酸铝体系交联过程的影响。结果表明,柠檬酸铝溶液中pH值增加时,Al(1)化学位移减少;pH值降低时,Al(2)化学位移减少。在柠檬酸铝溶液中存在两种形态的铝,一种是分子态,另一种是胶态。pH值增加时,分子态铝的量减少,而胶态铝的量增加。对部分水解聚丙烯酰胺与柠檬酸铝形成低聚合物浓度体系交联过程的研究表明,该反应所需柠檬酸铝为最佳形态结构时,溶液的pH值为5.0～7.0。

XRD法测定沸石分子筛中硅铝比

用 X射线衍射外推函数法测定 Na Y超稳分子筛的晶胞参数 ,用 2 9Si、2 7Al固体 NMR方法测定分子筛骨架中的硅铝比 ,提出了 Na Y超稳分子筛硅铝比与晶胞参数关联的经验公式。通过测定分子筛的晶胞参数即可得到 Na Y超稳分子筛的硅铝比。该方法测得的 Na Y超稳分子筛硅铝比 ,比通常采用的化学分析方法省时、简便。

氧化硼掺杂锂铝硅玻璃的结构分析

采用高温熔融法制备了硼含量可变的锂铝硅玻璃,并利用^(27)Al、^(11)B、^(29)Si核磁共振谱和拉曼光谱对玻璃样品进行表征。研究表明:随硼含量增加,网络中铝和硼以四配位为主,铝的配位不受硼影响,铝离子高配位比例偏高;BO_(4)的含量从57.1%增到64.4%。通过桥氧相连的铝氧硅键的数量减少,硅氧硅键数量从34.8%增加到46.1%。氧化硼的掺入增强了网络结构的聚合度,提升了玻璃力学性能。

固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布

具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位,且铝取代T位具有一定的倾向性.本文结合固体核磁共振(NMR)技术(^(27)Al/^(23)Na MQ MAS NMR),以及密度泛函理论(DFT)计算,研究了不同硅铝比Na-SSZ-39分子筛中的Na^(+)落位和铝分布.在孤立铝分布的情况下,铝原子优先占据于T3位,Na^(+)主要落位于AEI笼中的SIIa0和SIII’a0位点上,其中SIII’a0位点的优先度较高,此外少部分Na^(+)还落位于六棱柱内部的SIa0.当铝对存在时,AlSiSiAl分布的铝对占据六元环的对位(T3-T3),对应的Na^(+)分别落位于SIIa1和SⅢ’a1位点.随着分子筛结构的部分破坏,游离的Na^(+)可能形成明显的SIII’b位点.本文可加深对SSZ-39分子筛构效关系的理解,为更好地调控催化性能奠定基础.