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Structure Elucidation of Polyene Macrolide Antibiotic Lucensomycin by 2D NMR
LI Ning Wen Li Jian-yong He Qi-hua Jiang Xian Li
Chinese Journal of Magnetic Resonance, 2003, 20(4): 0-.
Polyene macrolide antibiotic is composed of 25 to 37 carbons with conjugated polyene fragment, substituted by hydroxyl and glycosidation of aminopolysaccharide. It has the characteristics of light unstability, wide antifungal spectrum, low toxicity by intravenous injection, high toxicity by oral administration. In this paper, it was reported that the idntification and detailed assignment of Lucensomycin, antifungal active substance produced from actinomycetes-1356, by means of UV, IR, MS, 1D and 2D NMR technology. Furthermore, the deficiency of 13C NMR data for olefinic carbons reported in literature was also corrected and the regularity for NMR data of polyene macrolide was summarized.
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DETERMINATION OF ROTATIONAL REORIENTATION CORRELATION TIME AND 59 Co NUCLEAR QUADRUPOLAR COUPLING CONSTANT OF POLYAMMONIUM MACROCYCLIC COBALTICYANIDE SUPERCOMPLEXES IN DILUTE AQUEOUS SOLUTIONS——An Application of Dynamic Laser Light Scattering Method
ZHOU Ping1*, AU-YEUNG Steve C. F.2
Chinese Journal of Magnetic Resonance, 2003, 20(4): 319-328.
The correlation time, τc , and the nuclear quadrupolar coupling constant (NQCC) of I >1/2 nuclei are important parameters for characterizing local and microdynamic structures of molecules. However, it is often difficult to determine those constants in solution. In this study, τc and NQCC of the 59 Co nuclei were determined for a series of supercomplexes [12] aneN4 [Co(CN)6 ], [18]aneN6 [Co(CN)6 ], [24]aneN8 [Co(CN)6 ], [16]aneN4 [CoCN)6 ], [24]aneN6 [Co(CN)6 ] and [32]aneN8 [Co(CN)6 ] in dilute solution. The Dynamic Laser Light Scattering (DLLS) method, which is now widely used in macromolecule research, was first applied to determine the hydrodynamic radii (0.4~0.6 nm) of these molecules. Based on the Stokes-Einstein-Debye equation and the measured hydrodynamic radii, the rotational reorientation correlation times τc were calculated. τc obtained in this study had a range of 3.8~9.5×10-11 s, which arefairly reasonable for molecules with molecular weights of about 300~500. Finally, NQCC of the 59 Co nuclei in the supercomplexes were determined by combining the τc values calculated and the experimentally measured longitudinal relaxation times, T 1 , of the 59 Co nuclei. The NQCC values obtained ranged from 0.5 to 2.2 MHz, which are considerably lower than those extracted from solid static NMR lineshape (5 to 7 MHz). The difference is probabl
y due to the structural effects originating from the anisotropy of local electric gradient around 59 Co nucleus in solid.
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DYNAMICS OF SODIUM 4-DECYL NAPHTHALENE SULFONATE MOLECULES IN MICELLES STUDIED BY 1 H NMR RELAXATION
YANG Xiao-yan1, TAN Xiao-li2, YUAN Han-zhen1, MAO Shi-zhen1, ZHAO Sui2, ZHANG Lu2, AN Jing-yi2, YU Jia-yong2, DU You-ru1*
Chinese Journal of Magnetic Resonance, 2003, 20(4): 329-333.
1 H spin-spin (T 2 ) relaxation times of sodium 4-decyl naphthalene sulfonate (SDNS) protons at different concentrations of 0.82 and 2.59 mmol/L were meas
ured at 298, 303 and 313 K. These T 2 values give the information about the dynamic characteristic of SDNS molecules in their monomeric and micellar states. The decrease in the T 2 values of a part of SDNS micellar protons, which participate in the formation of the palisade layer, with the increase in temperature suggests that the palisade layer becomes more tightly compact with the increase in temperature in order to prevent water penetration into the hydrophobic micellar core. While the reverse effect of the other protons in the T 2 values with the temperature up to 313 K shows that their motion of those protons is enhanced.
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RADICALS GENERATED FROM THERMALLY -TREATED POLY(ARYL-ETHER-KETONE) COPOLYMERS CONTAINING 1,5-NAPHTHALENE MOIETIES STUDIED BY ESR SPECTROSCOPY
DONG Feng-xia, ZHENG Ying-guang*,NIU Ya-ming, WANG Gui-bin, JIANG Zhen-hua*
Chinese Journal of Magnetic Resonance, 2003, 20(4): 343-348.
Poly(aryl-ether-ether-ketone)copolymers containing 1,5-Naphthalene moieties have been heated at 340 ℃ in air for different time, and it has been sho
wn that crosslinks are formed under oxidative condition, causing a reduction in the crystallizability of the material. Using ESR spectroscopy, we investigated t
he radicals generated from P(EEK-co-20 mol% ENEK) random copolymers heated at 340 ℃ in air and in nitrogen in this study. The ESR spectra obtained in the process of thermal treatment were originated from two species of free radicals, namely the RO[KG-*2]\5free radicals (R\-1) and the naphthalene free radicals (R\-2). Based on the above experimental observations, it can be concluded that both free radical species take part in the crosslinking reaction, but R\-1 plays a more important role.
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STRUCTURES OF 4,6,1′,6′-TETRACHLORO-4,6,1′,6′-TETRADEOXYGALACTOSUCROSE AND ITS DERIVATIVES DETERMINED BY 1 H AND 13 C NMR
Department of Chemistry, Zhengzhou University, Zhengzhou 450052, China
Chinese Journal of Magnetic Resonance, 2003, 20(4): 357-361.
4,6,1′,6′-tetrachloro-4,6,1′,6′-tetradeoxygalactosucrose and its two monoacetyl derivatives were synthesized. The structures of the compounds were elucidated by using 1 H NMR, 13 C NMR, MS and 2D NMR.
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MICROSTRUCTURE OF STYRENE-MALEIC ANHYDRIDE COPOLYMERS STUDIED BY 13 C NMR
DU Ding-zhun, WU De-cheng, PAN Cai-yuan
Chinese Journal of Magnetic Resonance, 2003, 20(4): 363-372.
Two styrene/maleic anhydride copolymers (St/MAh), H10 and UV4, were prepared by controlled polymerization at 110 ℃, using 1-(ethoxycarbonyl)-prop-1-yl dithiobenzoate (EPDTB) as a chain transfer agent and AIBN as an initiator, and by copolymerization in THF with EPDTB as an initiator under UV irradiation at
room temperature respectively. Normal 13 C NMR spectra and DEPT135 spectra were measured for both copolymers. All carbon chemical shifts in St/MAh copolymers were assigned. As a comparison, chemical shifts of the main chain carbons were calculated based on the substitution constants for phenyl group of St unit: α =16, β=6, γ=-2, and for anhydride group of MAh: α =13.5, β=2.5, γ=-2. The molar ratio of St to MAh, (FS /FM ), alternation degree, number-average sequence length of St block, molar ratio of cis- to trans-configuration of MAh ring and numberaverage molecular weight for the samples H10 and UV4 were calculated using integral values of the corresponding peaks. The copolymer UV4 had much higher alternating degree than that of H10, indicating a big influence of polymerization temperature on the formation of alternating structure in the copolymerization of St and MAh.
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DYNAMIC EQUILIBRIUM BETWEEN THE TAUTOMERS OF GOSSYPOL STUDIED BY 2D NMR
SHEN Ying-lin, YANG Sheng-hua, YING Wei, YAN Xiao-hua, MA Xue-yi*
Chinese Journal of Magnetic Resonance, 2003, 20(4): 373-378.
Three tautomers of gossypol, aldehyde (I), lacto (II) and ketal (III), exist in CDCl\-3, and are in equilibrium. 1 H NMR spectra of the three tautomers were assigned by means of 1D and 2D NMR techniques including 1 H-1 H COSY, DEPT, HMQC (1 H Detected Heteronuclear Multiple Quantum Coherence) and HMBC (1 H Detected Heteronuclear Multiple Bond Connectivity) experiments.
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CHEMICAL STRUCTURE OF REALOXIFEN HYDROCHLORIDE DETERMINED BY NMR TECHNIQUES
HAN Hai1, LI Zhang-wan2, ZHANG Qiang2, ZHENG Hu2, WENG Ling-ling2
Chinese Journal of Magnetic Resonance, 2003, 20(4): 403-408.
Realoxifen hydrochloride is a new drug that can be used for the prevention and treatment of osteoporosis and other diseases caused by osteoporosis. In
this study, NMR techniques, including DEPT, two-dimensional 1 H-1 H COSY, HMQC and HMBC, were used for the elucidation of its structure.
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A SPECTROSCOPIC STUDY ON INCLUSION COMPLEX OF β-CYCLODEXTRIN WITH GARDENIA YELLOW
LIU Shu-ling, TONG Jian-bo, LIU Yun, Qiao-hua, ZHANG Sheng-wan*
Chinese Journal of Magnetic Resonance, 2003, 20(4): 409-413.
Gardenia yellow is a physiologically active and edible nature pigment. Its usage, however, is limited due to its instable property. An inclusion complex of Gardenia yellow pigment with β-cyclodextrin was synthesized. UV, IR, fluorescence and NMR spectroscopy was used to confirm the formation of the inclusion complex and to determine the composition and the formation constant of the inclusion complex. The results show that β-cyclodextrin and Gardenia yellow pigment form a 1∶1 inclusion complex. This experiment will provide reference frame for the application of Gardenia yellow pigment.
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AN IMPROVED METHOD FOR CALCULATING 17 O NMR CHEMICAL SHIFT OF HYDROXYL GROUP IN CARBOXYLIC ACIDS
YU Zhi-li, GAO Li-mei, LIU Zong-ying, LI Yan-ping, YANG Peng
Chinese Journal of Magnetic Resonance, 2003, 20(4): 415-419.
In this paper an improved method for calculating the 17 O NMR chemical shift of hydroxyl group in carboxylic acids, including saturated and unsaturated fatty acids, benzyl acids, benzyl acetic acids, benzyl propenoic acids and amino acids, was discussed. A new parameter, Δα, was proposed for calculation.
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COMMON MALFUNCTIONS OF A BRUKER AC-80 SPECTROMETER, DIAGNOSIS AND SOLUTIONS
ZHOU Xin, SUN Xian-ping, LOU Jun, ZENG Xi-zhi, TIAN Ming-xian, LIU Mai-li
Chinese Journal of Magnetic Resonance, 2003, 20(4): 421-428.
Some common malfunctions found on a Bruker AC-80 NMR spectrometer are analyzed and summarized, and for which the possible solutions are proposed. On one hand, one can save valuable time for research if the malfunctions are repaired rapidly. On the other hand, it's important for researchers to grasp the frequently used techniques in dealing with and preventing malfunctions, and in designing and modifying commercial NMR spectrometers in order to meet the needs of the innovated experiments.