Synthesis, separation and NMR analysis of geometrical isomers of 3-benzylidene-indolin-2-one derivatives

A series of E and Z-isomers of 3-（4＇-substituted benzylidene）-indolin-2-one derivatives were synthesized and separated. Based on their 1H NMR characterization, an unusual counterintuitive deshielding phenomenon for the protons presenting in the shielding zone of phenyl ring was observed and analyzed for the first time.

Sensor design and implementation for a downhole NMR fluid analysis laboratory

This paper tries to build a multi-functional downhole nuclear magnetic resonance （NMR） fluid analysis laboratory that can evaluate fluid information in real time at reservoir conditions at a depth of several thousand meters. The aim is to monitor the pollution of the formation fluids and quantitatively evaluate NMR characteristics of the fluids. It focuses on the design of the structure and parameters of a sensor with zero stray fields. Two separate coils are designed to measure NMR characteristics of flowing or static fluids. A method is proposed to use the Bloch equation, to guide the optimization of the NMR sensor. Finally, the measured results confirm that the design is reasonable. There is a homogeneous static field （perpendicular to the axial direction） in the center of the sensor, and there are no stray external fields. The novel design of pre-polarization magnet improves the signal to noise ratio, while shortening the sensor length.

NMR diffusion analysis of catalytic conversion mixtures from lignocellulose biomass using PSYCHE-iDOSY

The component analysis and structure characterization of complex mixtures of biomass conversion remain a challenging work.Hence,developing effective and easy to use techniques is necessary.Diffusion-ordered NMR spectroscopy(DOSY)is a non-selective and non-invasive method capable of achieving pseudo-separation and structure assignments of individual compounds from biomass mixtures by providing diffusion coefficients(D)of the components.However,the conventional 1H DOSY NMR is limited by crowded resonances when analyzing complex mixtures containing similar chemical structure resulting in similar coefficient.Herein we describe the application of an advanced diffusion NMR method,Pure Shift Yielded by CHirp Excitation DOSY(PSYCHE-iDOSY),which can record high-resolution signal diffusion spectra efficiently separating compounds in model and genuine mixture samples from cellulose,hemicellulose and lignin.Complicated sets of isomers(D-glucose/D-fructose/D-mannose and 1,2-/1,5-pentadiol),homologous compounds(ethylene glycol and 1,2-propylene glycol),model compounds of lignin,and a genuine reaction system(furfuryl alcohol hydrogenolysis with ring opening)were successfully separated in the diffusion dimension.The results show that the ultrahigh-resolution DOSY technique is capable of detecting and pseudo-separating the mixture components of C_(5)/C_(6) sugar conversion products and its derivative hydrogenation/hydrogenolysis from lignocellulose biomass.

NMR-based metabolomics pro!le analysis in understanding metabolic variations of Bra LTP1-overexpressing Brassica napus

BraLTP1 is an important member of lipid transfer protein family in Brassica napus.The aim of current study was to detect, classify and follow variations in metabolite profiling of B. napus with overexpression of BraLTP1. In this study, metabolic change in leaves of BraLTP1-overexpressing B. napus plants (BraLTP1-22) and negative control (BraLTP1-22N) was investigated using nuclear magnetic resonance (NMR). Statistical strategy of principle component analysis (PCA) was performed to identify related difference metabolites. PCA score plots indicated not only high reproducibility of various treatments, but also significant difference of metabolite levels between different treatments. PCA loading plots indicated main responsible metabolites and a total of 50 metabolites were quantitatively determined. A wide range of metabolites were detected due to BraLTP1 overexpression,including biosynthesis and metabolism of sugars, amino acids, ammoniums compounds and organic acids. Furthermore, concentrations of 17 amino acids were determined for other set of samples by amino acids component analysis assay. The link between metabolite variations and phenotype were also discussed in BraLTP1-overexpressing B. napus.This work will help to gain insight into BraLTP1 function in B. napus in metabolism.

Enantiodifferentiation of chiral diols and diphenols via recognition-enabled chromatographic^(19)F NMR

A novel and efficient method for distinguishing between chiral diols and diphenols has been established through the use of^(19)F NMR spectroscopy.Central to this system's efficacy is a chiral amine,strategically modified with a CF_(3)group.This amine reacts in-situ with 2-formylphenylboronic acid to create a chiral^(19)F-labeled probe.This probe demonstrates discriminatory capabilities by interacting with hydroxy-containing analytes to form boronic esters.These esters produce distinct^(19)F NMR signals that vary according to their stereoconfiguration,facilitating accurate chiral differentiation.The method's resolution capacity was demonstrated by successfully identifying 12 distinct chiral analytes(six pairs of enantiomers)in complex mixtures,highlighting its extensive potential in diverse chiral analysis applications.

Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

一种双香豆蒽衍生物的NMR研究

应用核磁共振技术(1HNMR,13CNMR,DEPT,1H-1HCOSY,HSQC,HMBC),确定了7-(4-溴苯甲基)-7H-吡喃[3,2-c5,6-c′]二香豆蒽-6,8二酮的结构,排除了其他可能结构,准确归属了它的1H,13C信号.

利用核磁共振(NMR)测井资料评价储层孔隙结构方法的对比研究

文中介绍了四种利用核磁共振测井T2弛豫时间分布定量评价储层孔隙结构的方法,结合胜利油田A井实际资料的处理,对各种方法的适用性进行了对比分析。结果表明,三孔隙度组分百分比法、相似对比法和平均饱和度误差最小值法没有考虑储层孔隙含烃对T2谱形态特征的影响。三孔隙度组分百分比法适用于孔隙结构较好或较差的储层和水层中评价储层孔隙结构,而对于孔隙结构中等的储层则失去其作用;相似对比法和平均饱和度误差最小值法只能用于水层中构造核磁毛管压力曲线以评价储层孔隙结构;而基于Swanson参数的核磁毛管压力曲线构造方法采用实际测量的核磁共振测井资料,适用于各种不同类型的储集层中评价储层孔隙结构。通过与岩心资料对比,其结果的可靠性得到验证,具有一定的推广应用价值。

茶叶的^1H NMR指纹图谱研究

用1H NMR分析测定35种从福建、云南、广州、江西等地采集及购买的不同种类的茶叶.检测出约20种物质,包括多种氨基酸、茶氨酸、多种儿茶素(表没食子儿茶素(EGC)、表儿茶素(EC)、表没食子儿茶素没食子酸酯(EGCG)、表儿茶素没食子酸酯(ECG)和一些未知的儿茶素)、蔗糖、未知糖类、脂肪酸、咖啡因等.所得谱图经主成分分析,实现了不同种类的茶叶以及铁观音产地的区分,并且发现了引起区分的化学成分:红茶和黑茶与绿茶和乌龙茶相比,部分氨基酸和一些未知成分的含量较高,而儿茶素的含量较低;安溪西坪铁观音与安溪祥华和感德铁观音相比,部分氨基酸、咖啡因、EGCG、ECG以及一些未知成分的含量较高,而EC、EGC含量相对低.另外,谱图的聚类分析也显示了与主成分分析类似的结果.

大黄素的高效提取及其NMR结构探索研究

目的通过NMR定性研究大黄素的结构以及大黄素结构中的活泼性部位,为大黄素的化学结构修饰提供依据。方法从虎杖中高效提取了蒽醌类化合物大黄素,采用1D和2D-NMR的分析方法对大黄素结构进行鉴定,通过NMR变温技术及NOESY技术研究活泼性部位。结果以DMSO为溶剂、TMS作内标,采用1HNMR,13CNMR,DEPT,1H-1H COSY,NOESY,HSQC,HMBC等多种核磁共振方法对大黄素氢谱、碳谱进行完整归属,并通过NMR变温技术及NOESY的研究确定了其结构的活泼性部位。结论大黄素的3位羟基为其活泼性部位,该信息为大黄素的结构修饰以及衍生物的设计与抗肿瘤活性研究提供了物质基础。

泽泻盐制前后成分转化的^1HNMR分析

泽泻为临床常用中药,是五苓散、龙胆泻肝丸及六味地黄丸等经典方剂的主要组成.我国药典收载了泽泻的两种饮片,即生饮片和盐制片.传统理论认为泽泻生饮片和盐制片功效不同,生饮片偏重于利水泄热,盐制后泄热作用缓和,小剂量可用于补益剂,但其物质基础还不清楚,难以有效控制饮片的制备工艺和成品质量.为了深入揭示泽泻生饮片和盐制片的成分差异,以及盐制过程中成分的转化,该研究运用基于核磁共振氢谱(1H NMR)技术的代谢组学方法研究了泽泻生饮片与盐制片的化学成分差异及盐制过程中的成分变化.结果表明,泽泻生饮片与盐制片成分差异较大,而且随着盐制时间的延长成分变化愈加明显.采用偏最小二乘法判别分析(PLS-DA)显示,d_H 1.34信号对泽泻生饮片和盐制饮片在主成分1(t[1])方向的分离贡献最大.不同盐制时间条件下d_H 3.82、3.78、3.66、1.34、0.92和1.30处的泽泻醇类成分特征信号变化明显,提示泽泻盐制过程中原萜烷型泽泻醇类成分可能发生脱水、脱乙酰基和氧化反应.该文为深入了解泽泻盐制过程成分转化提供了可靠依据.

SNIF-NMR和IRMS技术在葡萄酒质量评价中的初步研究

利用SNIF-NMR和IRMS技术测定葡萄酒中稳定性同位素D/H和18O/16O的比值。结果表明,通过测定乙醇分子中甲基位(D/H)Ⅰ和次甲基位点(D/H)Ⅱ的含量,可判断葡萄酒在酿造前是否进行了加糖操作,而通过测定葡萄酒水分中18O/16O的比值,可鉴别全汁葡萄酒和半汁葡萄酒。研究结果为中国葡萄酒的质量评价提供了一种新的技术手段。

核桃壳木质素的^1H—NMR分析

在核桃壳磨木木质素(MW L)提取纯化的基础上,对纯化的核桃壳磨木木质素进行了C、H、O及OCH3含量的测定,并利用1H-NMR对核桃壳木质素基本化学结构进行研究。结果表明:(1)核桃壳木质素的C、H、O含量分别为67.15%、5.73%和27.12%,甲氧基含量为18.19%;(2)核桃壳木质素C9经验式为C9H9.22O1.99(OCH3)1.05,其C9单元结构的相对分子量为181.61;(3)核桃壳木质素属GS型木质素,其中G型木质素占多数,为80.68%;(4)核桃壳木质素中酚羟基(OHph)和脂肪族羟基(OHaliph)分别占总羟基数的32.21%和67.79%;(5)核桃壳木质素中存在较多的-βO-4、-β5和β-β结构。

用^13C—NMR及DEPT技术分析气煤加氢产物中沥青烯段分的组成结构

用１３￣Ｃ－ＮＭＲ及ＤＥＰＴ技术，对抚顺老虎台气煤吡啶抽提残煤热解加氢产物中沥青烯段分进行了表征。结果表明：各组分平均分子结构中的芳环并非完全缩聚，而且有亚甲基或联苯型键所连接的小芳香单元。计算得到了各组分的平均分子结构中含有的芳香环数、芳核片数和平均取代度。这些结果对于推断原始媒的大分子结构具有参考价值。

乌头碱对大鼠尿样代谢产物影响的NMR研究

将NMR谱和主成分分析（principal component analysis，PCA）相结合用于研究不同剂量下乌头碱（aconitine，AC）急性毒性作用后大鼠尿样的代谢特征．结果表明灌胃给药后代表能量代谢的柠檬酸（citrate），2-酮戊二酸（2-oxoglutarate）和顺乌火酸（cis—aconitate），反应肠道菌群代谢状况的马尿酸盐（hippurate）和苯乙尿酸（phenylacetylglycine）出现异常，并且这些变化在给药后O～8h达到最大，16h后基本恢复正常．且给药剂量越大代谢物异常越明显，需要的恢复时间也越长．实验中发现2-oxoglutarate的异常增加可能与AC的神经毒性有关，或与2-oxoglutarate的代谢异常有关．这些信息为进一步阐明AC的毒理学机制和临床毒性监测都会有一定的帮助．

高温1HNMR鉴别8种海参硫酸软骨素

提取了8种海参中的粗多糖,经DEAE-52阴离子交换柱分离纯化得到其中的海参硫酸软骨素(SC-CHS),除日本刺参CHS外其余均为首次获得的海参多糖。对获得的SC-CHS进行分子量、单糖组成及硫酸基含量等基本性质分析后,利用高温1HNMR对SC-CHS结构进行初步鉴别。结果表明,高温条件下SC-CHS的1HNMR图谱具有较好的分辨度。对其支链硫酸化岩藻糖的异头氢进行归属和比较,并以此为指标鉴别不同种类海参硫酸软骨素的结构差异,建立了一种以海参硫酸软骨素结构特征为指标的海参指纹图谱;初步探讨了不同海域生长的海参中硫酸软骨素支链岩藻糖硫酸基的特点,比较发现:寒带海域海参的硫酸软骨素岩藻糖上硫酸基取代以2,4-di OSO3、3,4-di OSO3双取代为主,含部分4-OSO3单取代;温带海域海参以2,4-di OSO3双取代为主,含部分4-OSO3单硫酸基取代;热带亚热带海域海参以2,4-di OSO3双取代和4-OSO单取代为主。这将为海参构效关系的进一步分析鉴定提供理论依据。

低场NMR对羊肉贮藏过程中pH值和TVB-N的预测及验证

为探讨不同贮藏条件下羊肉新鲜度检测的方法,采用低场核磁共振(LF-NMR)技术通过分析冷冻(-18℃)与冷藏(4℃)条件下羊肉的LF-NMR弛豫特性变化,及测定羊肉的pH值和挥发性盐基氮(TVB-N)含量的变化对其新鲜度进行分析检测。在此基础上,利用多元回归分析建立羊肉pH值、TVBN含量与其LF-NMR弛豫特性的相关性模型,并对其进行验证。结果表明,不同贮藏条件下,随着贮藏时间的增加,羊肉中pH值、TVB-N含量均逐渐增大并符合二项式关系,且相关系数分别为R^2>0.99和R^2>0.97。横向弛豫时间T_(22)、T_(23)随贮藏时间的延长显著缩短,T_(22)与贮藏时间呈线性关系(R^2>0.98),T_(23)与贮藏时间呈良好二项式关系(R^2>0.97),T_(2b)、T_(21)变化无规律且不显著。随贮藏时间的延长,峰面积比例S_(22)逐渐下降、S_(23)呈上升趋势(R^2>0.97),S_(2b)、S_(21)无明显变化规律。由多元线性回归分析可知,TVB-N含量与T_(23)、T_2,pH值与T_(22)、T_2可建立良好的相关性模型(R^2>0.96)。模型验证合理,表明利用LF-NMR弛豫特性对不同贮藏条件下羊肉pH和TVB-N含量预测是可行的,这为通过LF-NMR弛豫特性对羊肉的新鲜度的检测提供了一定的理论依据。

不同生长期当归^1H NMR指纹图谱的研究

利用1 H NMR法测定27个不同生长期的当归提取物,对当归的主要活性成分阿魏酸、藁本内酯、当归多糖进行了初步归属,用特征峰相对峰面积表示3种活性成分的相对含量,并对它们在生长过程中的含量变化进行分析.数据分析显示,当归中阿魏酸、藁本内酯、当归多糖的含量在第1年变化较为平稳,第2年和第3年变化相对较为活跃,而在当归的生长周期内,当归多糖的含量变化明显大于其他两种活性成分,为参与代谢活动的主要活性成分.结果证实,通过对照1 H NMR指纹图谱,将相对含量法与主成分分析法相结合,能对不同生长期的当归药材中的活性成分进行宏观评价和分析,可作为植物药材代谢组学的研究方法.

一种新的免疫抑制剂FTY720的NMR研究

应用核磁共振技术(1H NMR,13C NMR,DEPT,HSQC,HMBC)确定了一种新的免疫抑制剂FTY720(2-氨基-[2-(4-辛基苯基)乙基]-1,3-丙二醇盐酸盐)的结构,准确归属了它的1H,13C信号.

^(13)C CP/MAS NMR光谱法分析烟草果胶的含量和结构

采用CP/MAS^(13)C NMR光谱法分析烟草果胶的含量和结构。对烟草果胶进行了优化提取后,再对其^(13)C NMR光谱图C-6吸收峰区域进行了详细研究,用于计算果胶中半乳糖醛酸(Gal A)、甲酯度(DM)和乙酰度(DA)的含量,并就建立的定量方法与经典的色谱法和重量法进行了比较。结果表明,CP/MAS ^(13)C NMR光谱法测定烟草样品中果胶的含量是可靠的,化学位移和峰面积可用来计算烟草果胶分子的组成、甲酯度和乙酰度,同步实现烟草中果胶的含量和结构分析。