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A POWERFUL METHOD OF STUDYING METABOLISM IN BRAIN——High Resolution Nuclear Magnetic Resonance Spectroscopy
WANG Ke-qiang1, WANG Li-min1, XIA Wei2, YU Yi-hua2, GU Xing-hua1, JIA Jian-guo1, GE Jun-bo1
Chinese Journal of Magnetic Resonance, 2001, 18(2): 99-104.
In this paper, a howerful method was introduced to study the metabolism in brain. Adult rats were frozen with liquid-N\-2 through a self-command funnel. A
fter perchloric acid (PCA) extracts were prepared and lyophilized, the residual substance were dissolved in D2 O and investigated with 1 H and 31 P nuclear magnetic resonance spectroscopy (MRS). Result:High-resolution nuclear magnetic resonance spectroscopy of brain tissue was achieved. 31 P MRS reveals ATP, ADP, phosphocreatine, inorganic orthophosphate and manifold aliphatic phosphates and sugar phosphates; 1 H MRS shows many resonance peaks, including lactate, N-acetylaspartate, choline, creatine, GABA, myo-inositol, succinate and manifold amino acids. The peaks were integrated and the relative values might be used to express the metabolism or damnification of brain.
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STUDY OF 31 P NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY IN ACUTE HYPOXIC BRAIN OF RAT
GU Xing-hua1, WANG Li-min1, JIA Jian-guo1, WANG Yang1, XIA Wei2, YU Yi-hua2, WANG Ke-qiang1, GE Jun-bo1
Chinese Journal of Magnetic Resonance, 2001, 18(2): 105-112.
Nuclear magnetic resonance spectroscopy (MRS) is a unique scatheless noninvasively method to detect the metabolism of brain in cell level on living body.
31 P MRS is used to check and measure the content varieties of manifold metabolites in brain.; Purpose:Study of 31 P MRS in acute hypoxic brain of rat.;
Materials and methods:(1) Twentyl adult male SD rats suffered from hypoxic experiments were divided into four groups -0min(control), 5min,10min,15min. Then the brains were quickly frozen with liquid N\-2 and the whole brains were removed and restored in liquid N\-2. (2) The frozen brains were pulverized to a fine powder with a stainless steel mortar and pestle chilled with liquid N2 . Then perchloric acid (PCA) were added into the tissue powder, and the extract were lyophilized. (3) The extracts were dissolved in 0.5mL D\-2O for MRS analysis.; Results:(1) Hypoxia reduced the densities of high-energy phosphates (ATP, PCr) and increased content of Pi. The ratio of PCr/Pi and ATP/Pi lowered and ADP/ATP raised. In exchangeable phosphate pool(EPP), the normal value of PCr was 42.4%, after 5min hypoxia episode, it decreased to 28.9%, ATP decreased from 33.8% to 19.2%, and Pi increased from 17.7% to 42.0%. (2) Hypoxia increased the content of GPC and GPE, which were metabolites of phospholipid resolved.; Conclusion: 31 P MRS of PCA extracts suit the study of energy metabolism and phospholipid metabolism of brain. Acute hypoxia lead to some obvious varieties of the spectroscopy, and the notable varieties were PCr/Pi and ATP/Pi. This may be used to diagnose the disease of hypoxia or ischemia.
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THE ESR RESEARCH ON THE STABILITY OF NITROXIDE FREERADICAL IN PLANT
LIU Li-hui, CAO Yuan-lin, ZHANG De-liang, ZHAO Bao-lu*
Chinese Journal of Magnetic Resonance, 2001, 18(2): 123-128.
In order to reasonably use nitroxides in plant, We compared the stability of several nitroxide compounds in plant. Under the same condition, the compound was lead into plant though soaking in the diluted solution. At different time, the ESR spectra of different parts of plant were measured and the growth
status of plant were observed. The characters of spin probes, which can exist steadily in plant with high signal and less toxicity are found. Usually they are
derivatives of pyrrolidine with small molecular weight. From the kinetic curves and growth states of the plant, it was found that the concentration of 10-4 mol/L of spin probe was proper for using. The results are helpful for the development of plant ESR imaging and may be developed to a new method for me
asuring plant physiology.
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INVESTIGATION ON PHOTO-INDUCED HYDROGEN ABSTRACTION IN PORPHYRIN/QUINONE SYSTEM
WANG Ying1,2, SUN Jian1, WANG Peng1, TIAN Qiu1, YAN Baozhen2, Xu Guozheng1, WANG Yuzhen1, LIU Yang1*
Chinese Journal of Magnetic Resonance, 2001, 18(2): 129-134.
A photo-induced hydrogen abstraction reaction have been proved in the porphyrin/quinone solution containing protic solvent by means of CIDNP and ESR methods.
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13 C HIGH-RESOLUTION SPECTRUM OF POLY(N-ISOPROPYLACRYLAMIDE) AS ASSIGNED WITH THE AID OF GAUSSIAN98 QUANTUM CHEMICAL CALCULATION
LIU Song-bai1, CHEN Qun1*, YANG Guang1, YAN Xiao-hu2
Chinese Journal of Magnetic Resonance, 2001, 18(2): 135-141.
The quantitative 13 C high resolution NMR spectrum of poly(N-isopropylacrylamide) (PNIPAAM) was assigned with the aid of Gaussian98 calculation. Two methods, γ-gauche effect and ab initio calculation, have been applied to calculate the 13 C NMR chemical shifts of stereosequences of PNIPAAM. The parameters for γ-gaucheeffect were developed from the ab initio calculations of diads. The basis set used was 6-31G*, and the method was GIAO-CHF. For ab initio calculation, all geometries were optimized via AM1 method and the 13 C NMR chemical shifts were calculated via GIAO-CHF method with STO-3G basis set. Stereosequences to triad level were considered for the methine carbon of main chain, while for the methylene and methyl carbons, stereosequences to tetrad and pentad level were considered respectively. It was found that the ab initio calculation can well reproduce the obse
rved 13 C NMR spectrum, while the γ-gauche effect method failed to give satisfactory result. Thus, based on the result of ab initio calculation, the signals of m
ethine carbons, methylene carbon and methyl carbon were assigned and the tacticity of PNIPAAM was turn out to be random. As a result, the ab initio calculation was proved to be an effective method to investigate the tacticities of macromolecules.
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NMR RESEARCH ON TRITERPENOID SAPONINS LATIFOLOSIDE I AND KUDINOSIDE K
OUYANG Ming-an1, TENG Rong-wei2, WANG De-zu2, YANG Chong-ren2
Chinese Journal of Magnetic Resonance, 2001, 18(2): 155-160.
This paper discussed the structure elucidation of two saponins, Latifoloside I isolated from Ilex latifolia Thunb and Kudinoside K isolated from Ilex
kudincha C. J. Tseng. On the basis of chemical and spectroscopic evidences, mainly modern 2D NMR technique, their structures were determined to be 3-O-β-D-glucopyranosyl-(1→3)-α-L-arabinopyranosyl-30(S)-3,19,23-trihydro-xyurs-12-en-28-oic- acid 28-O-β-D-glucopyranoside and 3-O-[α-L-rhamnopyranosyl-(1→2)]-[β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→3)]-α-L-arabinopyranoyl-3β,19α,20β-trihydr-oxyurs-12-en-28-oic acid 28-O-[α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside, respectively.
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STUDY OF THE DYNAMIC STRUCTURES AND EQUILIBRIA OF β-CYCLODEXTRIN WITH CYANINE DYES
TANG Ya-Lin1, FENG Juan1, XIANG Jun-Feng2, CHEN Ci-Ping2, YAN Wen-peng2, XU Guang-Zhi1
Chinese Journal of Magnetic Resonance, 2001, 18(2): 161-167.
The results of 1 H NMR investigation of β-Cyclodextrin inclusion complexes with three cyanine dyes in D2 O and DMSO solution are reported in this paper, It was found that there is difference in chemical shift of some protons both of β-Cyclodextrin cavity and of cyanine dyes between after and before complexing,the position of which is dependent upon the inclusive degree. Fluorescence spectroscopy of cyanine dyes showed that the fluorescence intensity of these dyes is obviously quenched due to the forming of inclusions with β-Cyclodextrin, calculation results based on fluorescence spectroscopy indicated that β-Cyclodextrin formed 1∶1 inclusion with three cyanine dyes respectively. Information about hydrogen bond was induced from the study of temperature dependence of chemical shift of hydroxyl protons in β-Cyclodextrin cavity, OH-3 and OH-6. Their equilibrium constants of inclusion complexes were obtained from NMR chemical shift titration. The structure model of three inclusion complexes and dynamic process entering β-Cyclodextrin cavity has been described in this paper.
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SPECTRAL SPECIFICITY OF A NEW FLAVONOID FROM SCUTELLARIA PLANIPES
ZHANG Yong-yu, SONG Aihua, BABA Masaki, OKADA Yoshihito, OKUYAMA Toru, HASHIMOTO Kadsunori, IKEYA Yukinobu, OKADA Minoru
Chinese Journal of Magnetic Resonance, 2001, 18(2): 169-173.
A new compound was isolated from the roots Scutellaria planipes (L.) and identified to be 5,7,3′,6′-tetrahydroxy-6,8,2′-trimethoxyflavone. It shows strong inhibitory effect for 5-lipoxygenase. All of the carbon signals were recognized and some assignment errors of similar compounds in the literature were corrected.
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ON PRELIMINARY APPROACH TO ESTIMATION AND PREDICTION OF CHEMICAL SHIFT OF CARBON-13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY IN ALKANES BASED ON A NOVEL ATOMIC DISTANCE-EDGE VECTOR (MDE OR ν )
OA
CHEN Qi-ting, YUAN Xiao-yan, CAO Chen-zhong, LIU Shu-shen, LIU Hailing, LI Zhi-liang
Chinese Journal of Magnetic Resonance, 2001, 18(2): 175-185.
Systematic studies were made on carbon-13 nuclear magnetic resonance (13 C NMR) and its regularity of chemical shift (CS). In the present paper, A novel atomic distance-edge (ADE ) vector or ν vector expressed in the form of energy was developed and found to be correlated excellently with the chemical shift (CSC ) for carbon-13 nuclear magnetic resonance (13 C NMR). The multiple linear regression (MLR) equations, CSC =aν +ap 3 =∑m j =0 aj νj +a 10 p 3 =a 0 (ν 0=1 )+a 1 ν 1 +a 2 ν 2 +a 3 ν 3 +a 4 ν 4 +bP 3 , of atomic modelling were established by the atomic distance-edge vector together with the path count of three bonding segment (C-C-C) It gives very good results for the modelled estimation and quantitative prediction with cross validation (CV ) of leave-one-out (LOO) procedure.