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[其他] 专题讨论尝试贴:核磁共振 (NMR)

NMR波谱法直接分析有机混合物(2)代谢物-血清成分

from:http://bbs.ok6ok.com/read.php?tid=232787

作者:汪茂田

NMR波谱法直接分析有机混合物-血清。

下面是我分析的一种血清的1HNMR,溶剂D2O,600兆NMR仪器.分析混合物,尤其像体液-血清这种样品尽可能使用高场NMR仪器,也就是说,600和600兆以上的仪器更好。由于成分复杂,不同成分的共振信号在500兆以下仪器的图谱中重合会严重些,不利于分析。
体液代谢物成分溶于水,且往往含量较低,所以1HNMR要使用水峰压制技术,实验次数要尽可能多以获得理想的信噪比,这个很重要!

由该图谱鉴定出10多种化学成分,多数成分可得到相对含量。

在此上载的1HNMR是全图,由于格式转换,不是很清晰,没有一并上载局部放大图,权作示意图谱吧。

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NMR波谱法直接分析有机混合物(3)-高聚物



作者:汪茂田


高聚物实际上也是混合物,早期(50-70年代)IR是分析高聚物的有力工具。随着NMR技术的发展和高场仪器的广泛使用,IR分析高聚物的功能远远低于NMR,NMR可以进行很多种实验得到多种不同的图谱,加之固体NMR的进步,也为溶剂不能溶解的高聚物提供了有力的分析技术。



本帖给出的例子是我为客户剖析的一种进口的高聚物(严格地说是寡聚物)。没经分离直接剖析混合物。只展示1HNMR,其它多种图谱和局部放大图谱省略。



它是4种二元酸(主成份二元酸是isophthalic acid)和2种多元醇的聚酯(恕我不能全部告诉成分组成),含少量稀释剂苯乙烯。并可求出各个单体相互间的摩尔比。
该寡聚物中还含有一定量的无机添加剂,通过分离而鉴定。

不难想象,像这样复杂的物质的详细分析,IR是不好办到的。多种MS技术结合也应该可以给出比较可信的结论,但可以说都不如NMR快速可靠。测定数种必要的NMR图谱的的时间花费并不多,但花费解析精力大些,解析图谱的快慢和分析结果的可靠性也与分析者的具体情况有关。

该例子为抛砖引玉,感兴趣的学者讨论。
只上载1HNMR,其它一系列图谱省略,见谅。

NMR波谱法直接分析有机混合物(4)-螯合剂混合物0

from:http://bbs.ok6ok.com/read.php?tid=232806

笔者剖析过很多种螯合剂混合物以及螯合剂与表面活性剂的混合物,基本上不经化学分离而直接用多种NMR技术和MS结合,综合分析,这些化学品多是进口产品。
这种产品含4种螯合剂,由于这些螯合剂混在一起,实际可看作“缓冲溶液”,在混合样品中的单个成分的NMR化学位移与单独成分的在相同溶剂中的NMR化学位移往往有一定差距,这个问题要解决好才能得到可靠数据。
下面是我近期分析的一种外国公司的产品,含有多于4个成分,除完成成分定性外,还可计算出各成分的近似摩尔比。请恕我不能公布具体成分,以此例说明NMR分析这类混合物的作用。
当然LC-MS也是有用的方法,但有时还要继续做MS-MS....,远不如NMR直观快捷。而EI-MS对这样的混合物则有一定局限性,因为有的成分在EI-MS中得不到分子峰,衍化后测定GC-MS也能得到可靠的结构鉴定信息,但由衍生化后的化合物的MS图谱倒推稍显麻烦,且仍然要有对照数据才能放心。

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NMR波谱法直接分析有机混合物(5)-庆大霉素

庆大霉素为一种多组分混合物抗生素,其主要成分是gentamicin C1, C1a, C2 and C2a.
过去国外药典规定要用1HNMR测定主要成分的相对含量,我国出口庆大霉素原药也必需按此法进行。

下面是庆大霉素600兆1HNMR图谱。选择每个成分的特征信号,必需不与其它成分信号重叠,积分,计算。


[ 本帖最后由 cc136520 于 2008-10-4 15:57 编辑 ]

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NMR波谱法直接分析有机混合物(6)-2D DOSY法测定西力士配方

from:http://bbs.ok6ok.com/read.php?tid=233932

西力士(Cialis)是礼来公司生产的治疗勃起障碍(ED)的药物,采用特殊的NMR技术(DOSY-Diffusion-ordered spectroscopy )可清晰辨认主成份Cialis以及配方中使用的多种辅料。图中有详细的归属。由此例不难看出NMR DOSY技术的威力是很强大的。

图谱来自文献。

[ 本帖最后由 cc136520 于 2008-10-4 16:03 编辑 ]

武汉磁共振中心正式挂牌

国家大型科学仪器中心——武汉磁共振中心正式挂牌
   参看:http://www.wipm.ac.cn/chinese/news/2008/080912.html
  2008年9月11日,国家科学技术部条件财务司在武汉组织专家对国家科学技术部、中国科学院、湖北省人民政府共建的国家大型科学仪器中心——武汉磁共振中心的建设进行了验收并举行揭牌仪式,同时任命叶朝辉院士为武汉磁共振中心主任、洪茂椿院士为中心技术委员会主任。科技部条件财务司巡视员吴波尔、湖北省科技厅副厅长郑春白、中科院基础局副局长刘鸣华、中科院武汉分院院长朱耀忠等领导出席了揭幕仪式。

  以陈霖院士为组长的专家组听取了中心依托单位中国科学院武汉物理与数学研究所的工作报告,审阅了有关技术文件,经实地检查、质询和充分讨论,认为:经过两年多的不懈努力和辛勤工作,依托单位圆满完成了“武汉磁共振中心”核心设备 — AVANCE III-800 型800MHz 核磁共振波谱仪的引进、安装、调试,实现了与原有谱仪资源的优化配置,相关仪器和配套设备运行正常,形成了以800 MHz为核心的一系列磁共振仪器共享平台。武汉磁共振中心建立了合理有效的管理运行机制,有力保证了大型科学仪器设备的开放共享。从2007年9月以来,核心设备800 MHz核磁共振波谱仪运行时间超过4000小时,共享率达47%。在核磁共振技术与方法、代谢组学和蛋白质结构生物学等相关研究领域发挥了支撑作用,取得了显著成效。极大地促进了武汉物理与数学研究所波谱学科的发展,并已形成一支结构合理、富有创新活力的科学研究和技术支撑队伍。专家组认为中心圆满完成了各项建设任务,一致同意通过验收。

  科技部条件财务司巡视员吴波尔指出,国家重点实验室和国家大型科学仪器中心是国家创新体系建设中的重要组成部分,前者以学科建设为中心,凝聚相关力量;后者以代表某领域最高水平或具有重大意义的仪器类型为中心,发挥相同领域的仪器作用,为各个领域的研究服务。中科院武汉物理与数学研究所作为波谱与原子分子物理国家重点实验室和武汉磁共振中心的共同依托单位,旨在将两者有机联系起来,充分发挥各自在研究领域和实验手段方面的优势,为国家创新发展作出贡献。

本帖最近评分记录
  • cc136520 在2008-10-4 15:56 评分: 金币 +5 原因: 多谢参与
引用:
原帖由 cc136520 于 2008-10-4 11:00 发表
庆大霉素为一种多组分混合物抗生素,其主要成分是gentamicin C1, C1a, C2 and C2a.
过去国外药典规定要用1HNMR测定主要成分的相对含量,我国出口庆大霉素原药也必需按此法进行。

下面是庆大霉素600兆1HNMR图谱。 ...
cc136520把庆大霉素的1HNMR图谱上载错了,请看下面是庆大霉素的1HNMR图谱:

附件

The 600MHz 1HNMRspectrumof a gentamicin batch.GIF (25.43 KB)

2008-10-4 15:31

The 600MHz 1HNMRspectrumof a gentamicin batch.GIF


本帖最近评分记录
  • cc136520 在2008-10-4 15:56 评分: 金币 +5 原因: 欢迎加盟化学吧,我赶紧改过来

“Pure by NMR”?

Timothy D. W. Claridge, Stephen G. Davies*, Mario E. C. Polywka, Paul M. Roberts, Angela J. Russell, Edward D. Savory and Andrew D. Smith
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, U.K.
Org. Lett., Article ASAP
DOI: 10.1021/ol802211p
Publication Date (Web): November 1, 2008
Integration of a 13C−1H satellite peak of a given 12C−1H parent resonance within a quantitative 1H NMR spectrum and comparison to the minor component represents a simple protocol for the accurate determination of diastereoisomeric ratios of up to 1000:1 (i.e., 99.8% de).

附件

ol802211p“Pure by NMR”.pdf (661.47 KB)

2008-11-21 11:44, 下载次数: 0


跳舞的原子:让原子自旋失控可以得到更好的MRI谱



the November 25 online issue of the Journal of Chemical Physics, they explain why scientists couldn't completely control the behavior of atomic nuclei during some nuclear magnetic resonance (NMR) experiments.
Some loss of control isn’t such a bad thing, explained Philip Grandinetti, professor of chemistry at Ohio State University. Now that he and his colleagues have derived a mathematical explanation of the strange atomic behavior, scientists can use it to make MRI images sharper.
The advance may one day help scientists to look inside people and objects without having to put them inside giant magnets -- an advance which could lead to portable MRIs.
NMR and its medical counterpart, MRI, reveal the inside of objects by detecting atoms that behave like tiny magnets. Inside the machine's strong magnetic field, atoms align according to north and south magnetic poles, spinning and precessing like tiny tops. Each type of atom broadcasts its identity by emitting a unique radio frequency, depending on its environment.
NMR can reveal the structure of individual molecules. But pictures of complex objects -- such as the human brain -- often lack detail, because whenever atoms happen to broadcast in opposite directions, they cancel each other out of the final image.
In a quest to boost NMR resolution, scientists routinely perform a certain type of experiment that keeps the spins of atoms under very strict control. They refer to such experiments as adiabatic.
The Ohio State scientist and his collaborators found that atoms in adiabatic experiments don't always behave as scientists intend them to.
They didn't set out to make such a fundamental discovery, Grandinetti explained. They'd only wanted to examine an earlier University of Alberta experiment which had been aimed at enhancing NMR signal strength.
"We originally wanted to work out a rigorous theoretical description of the Alberta experiment, but the more we tried to understand even the simplest adiabatic process in magnetic resonance, the more we realized that there was a disturbing discrepancy between theory and experiment," he said.
They uncovered the same contradiction in many other studies over decades of NMR research. Even though all these experiments seemed to run properly and yield good results, the atoms hadn't spun in a controlled way.
There was only the barest mention of the effect in the scientific literature over the years, and nobody had bothered to find the cause.
"To be fair, though, it wasn’t clear that this discrepancy posed a real problem, and most people thought the conventional theoretical approach was doing a fine job," he added. "It was only after we fully understood the reason for the discrepancy that we realized the conventional theoretical approach contained a flaw that might prevent better adiabatic processes from being discovered."
The scientists discovered that atoms were not spinning out of control, but rather were moving in a predictable way, according to a quantum mechanical concept called super-adiabaticity. The concept was first proposed in the late 1980s.
A super-adiabatic process is still adiabatic. That's why all those seemingly contradictory experiments ran properly -- the atoms were behaving in an adiabatic way, just not according to the commonly accepted adiabatic theory.
The idea is based on some very complex mathematics, but it can be visualized in three dimensions. If the trajectory of the atoms during an experiment were mapped on a globe, then the purpose of an adiabatic experiment is to move the atoms being studied from one point on the globe to another -- slowly, and following a very carefully designed path.
With super-adiabaticity, the atoms follow a different -- sometimes, wildly different -- path, but still end up at the right destination.
It's as if an airplane was scheduled to fly in a straight line from the North Pole to the South Pole, but instead veered way off course, spiraling southward until it eventually reached the other pole. The route was circuitous, but the end result was the same.
In the case of the NMR experiments, super-adiabaticity re-routed the atoms' flight plan.
Grandinetti hopes to incorporate the algorithm into software for controlling NMR and MRI measurements, where it might boost image resolution. One day, it might even help these instruments obtain signals from objects located outside of a magnet.
Scientists could also use super-adiabaticity to exert better control over atoms for quantum computing, and to make more precise structural studies of complex biological molecules, he said.
Collaborators on this research hailed from the Centre National de la Recherche Scientifique, the Université d'Orléans, and the Université de Lyon, France.
This research was funded by the National Science Foundation and the CNRS and Le Studium in France. (Sciencedaily.com)
Journal reference:
Michael Deschamps et al. Superadiabaticity in Magnetic Resonance. Journal of Chemical Physics, Volume 129, issue 20; Online November 25, 2008

模拟one hyperbolic secant adiabatic pulse (HS1-25-50-25) which was displayed in  "The Return of the Frequency Sweep: Designing Adiabatic Pulses for Contemporary NMR" (JMR, 2001,153,155).




from http://www.chinanmr.cn/bbs/viewt ... fromuid=204#pid4688

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