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THE VALIDITY OF HIGH TEMPERATURE APPROXIMATION IN NMR SPECTROSCOPY AND ITS RELATED PROBLEMS
DING Shang-wu, YE Chao-hui, CHEN Cheng-Lung, CHOU Chin-Hsin
Chinese Journal of Magnetic Resonance, 2002, 19(2): 107-114.
A large body of conspicuous publications in recent years asserts that the high t emperature approximation (HTA), a mostly tested and most widely used assumption in NMR spectroscopy and MRI technology, is invalid for concentrated samples in h igh magnetic fields such as for a proton COSY spectrum of water. A by-product o f the alleged collapse of HTA, which is equally surprising, is the existence of i ntermolecular multi-quantum-coherences (MQC) in low viscosity liquids such as wa ter. In this work, both HTA and intermolecular MQCs in liquids will be criticall y examined in light of our theoretical analysis and experimental results. Our co nclusions are: (1) There are no macroscopic quantum systems in conventional NMR samples such as water at room temperature. (2) At room temperature, high tempera ture approximation is still one of the most trustworthy approximations applicabl e to NMR and (3) The MQCs observed in proton COSY spectrum in, e.g., water, have nothing to do with quantum mechanical intermolecular spin interactions.
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STUDY OF 17 O-NMR CHEMICAL SHIFTS OF HYDROXY-CONT AINED COMPOUNDS
LI Li-dong, LI Lin-sheng*
Chinese Journal of Magnetic Resonance, 2002, 19(2): 115-123.
Based on systematical induction and summarization of data o f 17 O-NMR chemical shifts of hydroxy-contained compounds already reported, the article provides the equation(1): δ cal =δ 0n +Δα+Δβ+Δγ for primary, secondary, tertiary alcohol and i -R—OH(em -R refers to substituents whose atom directly connected with hydroxy not telong ed to chain alkane) and equation(2): δ cal =δ 0 +Δo +Δm +Δp for substituted hydroxybenzenes. 15 substituent parameters for calculating the 17 O-NMR chemical shifts of alcoho ls and carboxylic acids and 23 substituent parameters for substituted hydroxybenze nes are gained with regression analysis in connection with least square. Equatio n(1) is checked regressively by the 17 O-NMR chemical shifts of 140 compounds of primary, secondary, tertiary alcohol and i -R—OH, and equati on(2) is checked regressively by 17 O-NMR chemical shifts of 60 compounds of substituted hydroxybenzenes. Consequently, their confidence limits both are 99. 5% and calculating errors(4δ ) for over 90% compounds are less than (relatio nerrors 0.5%).
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STRUCTURAL DETERMINATION OF PETROVIIN FROM SAUSSUREA PETROVII BY 2D NMR
DAI Jing-qiu, LIU Zhong-li, YANG Li*
Chinese Journal of Magnetic Resonance, 2002, 19(2): 133-136.
From the Inner Mongolia medicinal plant, Saussurea petrovii , which was coll ecte d in the suburb of Lanzhou city, Gansu province of China, a colourless gum compo und was isolated. The compound was identified as a new eudesmane type sesquiterp ene ester, petroviin, by MS and NMR. The structure of petroviin was determined b y two-dimensional NMR spectroscopy for the first time. All the 1 H and 13 C NMR resonances were assigned unambiguously. The relative configuration of petroviin was also evaluated.
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1 H NMR SPECTROSCOPY OF AMNIOTIC FLUID OF CHICK EMBRYO
FENG Yue1,2, CHANG Jian-hua1, ZHANG Xu2, LIU Mai-li2*
Chinese Journal of Magnetic Resonance, 2002, 19(2): 137-142.
1 H NMR spectroscopy of amniotic fluid of chick embryo was reported for the f irst time. 29 compounds, including amino acids, organic acids, carbohydrates and lipids, were observed and their 1 H NMR resonances were assigned using one- and two-dimensional NMR methods.
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PREPARATION AND NEGATIVE MRI SPIN-SPIN RELAXATION ENHANCEMENT OF SUPERPARAMAGNETIC IRON OXIDES
YU Kai-chao1,2, ZHANG Yan1, YANG Yun-huang2, LU Guang2, LIU Ma i-li1,2, YE Chao-hui1,2
Chinese Journal of Magnetic Resonance, 2002, 19(2): 143-148.
Superparamagnetic iron oxides (SPIO) are known for their fast T 2 (T *2 ) relaxation properties which result in a strong decrease in signal intensity (negative enhancement) of such reticuloendothelial system as the liver, the spleen, and et al where they accumulate. For its low solubility in water, SPIO usually are colloidally coated and stabilized with a matrix such as dextran or liposomes . In this work, a series of micelle coated and stabilized SPIO colloids were pre pared and the T 2 values of these SPIO micells were measured, aiming to in vestig ate the effect of properties of different micelles on SPIO solution. The experim ental data showed that both different kind of charge which the micelle has and t he molecular weight of surfactant have distinct effect on the T 2 relaxation of SPIO colloid. The SPIO colloid coated by PEG-400 was selected for the acute toxi city and MR imaging contrast test. The results indicated that there was no obviou s toxicity for this polymeric micelle coated SPIO colloid, and mini dose (20 μm o l/kg) of SPIO exhibits the obvious negative enhanced MRI signal intensity in the rat liver tissue.
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NMR STUDIES OF COMPLEXES [Co(TREN)(AMINO ACIDATO-N, O)]X2 ·n H2 O IN S OLUTION
SHAO Wei-yan, ZHONG Shi-zhou, HU Xiao-peng, CAI Ji-wen
Chinese Journal of Magnetic Resonance, 2002, 19(2): 149-157.
NMR experiments at various temperature or with different solvents were used to characterize the nature of hydrogen bonds and conformation of several c omplexes in solution, namely the trans(N, t-N) isomer of [Co(tren)(DL-phen ylalaninato)](ClO4 )2 (Ⅰ), Co(tren)(L-pro-linato)]I2 ·H2 O(Ⅱ), [Co(tren)(L-valinato)]I2 ·1/3H2 O(Ⅲ), Co(tren)(L-isoleucinato)]I2 (Ⅳ), [Co(tren)(L-leucinato)]I2 (Ⅴ). Compared with their crystal structures in whi ch inte rmolecular double or single hydrogen bonds were observed. Intramolecular double or single hydrogen bonds formed by the carbonyl oxygen of the amino acidato li gand and the amino hydrogen of the tren ligand were observed in Ⅲ, Ⅳ, Ⅴ. Whil e the situations in Ⅰand Ⅱ need more investigations. The 1 H and 13 C NMR assignments were achieved by 2D NMR(COSY and HMQC ).
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FOUR CAFFEOYLQUINIC ACIDS FROM MORINA NEPALENSIS VAR. ALBA HAND.-MAZZ.
TENG Rong-wei1, ZHOU Zhi-hong2, WANG De-zu1, YANG Chon g-ren1*
Chinese Journal of Magnetic Resonance, 2002, 19(2): 167-174.
Four compounds were isolated from water-soluble part of whole plant of Morina nepalensis var. alba Hand.-Mazz.by CC on Si gel, RP-8, Sephadex LH-20. Based on spectroscopic evidences, their structures were elucidated as 3-O-caffeoyl-quinic acid (1 ), 3, 5-O-dicaffeoyl-quinic acid (2 ), 3, 4-O- dicaffeoyl-quinic acid (3 ] ) and 4, 5-O- dicaffeoyl-quinic acid (4 ), respectively. Complet e assignments of 1 H and 13 C spectra of these four compounds were obtained by 2D NMR spe ctra. Furtherm ore, 1 H and 13 C Chemical shifts of compound 1 and 2 were determined with both in CD3 OD and DMSO-d6 solvent. All four compounds were firstly isolated from the Morin a plants.
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PHOTO-CIDNP INVESTIGATION OF HYDROGEN TRANSFER REACTIONS OF 1-ACETYLINDOLE-2, 3-DIDONE
WANG Xin-yan1, WANG Ting1, YAN Bao-zhen1*, ZHANG Yan
Chinese Journal of Magnetic Resonance, 2002, 19(2): 187-194.
The photoreactions of 1-acetylindole-2, 3-didone (AID) with several hydrogen don ors in benzene-d6 and acetonitrile-d3 at room temperature were investigate d by m easurement of the chemically induced dynamic nuclear polarization (CIDNP). The polarization pattern of AID indicates an intermediate with spin density distribut ion of a σ π radical, in this case, aneutral radical AIDH· was formed.; A hydrogen attraction interaction between 3AID+* and the donors result ed in the formation of stable neutral radical pairs, which have triplet multiplicity and can diffuse apart to make the pair loose enough for the nuclear polarization to b e developed. The radical pairs could undergo back hydrogen transfer or separate and diffuse and meet again to lead to the observed products.
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STUDY OF MAGNETIC PROPERTIES OF A SUPERFINE MANGANESE COMPLEX OF DITHIOLATE AND PHENANTHROLINE-5, 6-DIONE
PAN Qing-cai1, PENG Zheng-he2
Chinese Journal of Magnetic Resonance, 2002, 19(2): 195-202.
The magnetic properties of the complex MnLL′ (L: mnt2- , maleonitriledithiolate: L′=phen-5, 6-dione, 1, 10-phenanthroline-5, 6-dio ne) were characterized by variable-temperature susceptibility and EPR of solid powder, EPR in DMSO, DMF and acetone solutions. The title complex MnLL′is hi gh spin tetracoordinate complex. The complex MnLL′possess remarkable paramagnet ism. Experiment fact of EPR of MnLL′is explained by theory.
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METHODS TO DETERMINE THE ABSOLUTE STEREOCHEMISTRY OF ORGANIC COMPOUNDS BY NMR SPECTROSCOPY
TENG Rong-wei1, SHEN Ping2, WANG De-zu1, YANG Chong-ren1*
Chinese Journal of Magnetic Resonance, 2002, 19(2): 203-223.
This paper reviews the NMR methods to determine the absolute stereoche mistry of organic compounds.The methods are classified into two types in terms o f the principle in this paper. One applies magnetic anisotropy effect of phenyl orother aryl groups, such as Mosher method, methods utilizing MPA or other AM As chiral reagents. The other type applies glycosylation shift effects due to glyco sylate reactions, such as tetra-O-benzoyl glucosylation method and fucofurano side method. This review deals with the principle, the determining process, the advantages and disadvantages of each mothod.