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1.
Jiri Brus Hana Petříčková Jiri Dybal 《Monatshefte für Chemie / Chemical Monthly》2002,133(12):1587-1612
Summary. A brief overview of our recent results concerning the application of 2D CRAMPS experiments to investigate a wide range of
materials is presented. The abilities of the 2D 1H–1H spin-exchange technique to characterize the structure of organic solids as well as the limitations resulting from segmental
mobility and from undesired coherence transfer are discussed. Basic principles of 1H NMR line-narrowing and procedures for analysis of the spin-exchange process are introduced. We focused to the qualitative
and quantitative analysis of complex spin-exchange process leading to the determination of domain sizes and morphology in
heterogeneous multicomponent systems as well as the characterization of clustering of surface hydroxyl groups in polysiloxane
networks. Particular attention is devoted to the determination of the 1H–1H interatomic distances in the presence of local molecular motion. Finally we discuss limitations of the 13C–13C correlation mediated by 1H–1H spin exchange to obtain structural constraints. The application of Lee-Goldburg cross-polarization to suppress undesired coherence transfer is proposed.
Corresponding author. E-mail: brus@imc.cas.cz
Received May 28, 2002; accepted (revised) July 1, 2002 相似文献
2.
L. A. Baltina O. Kunert A. A. Fatykhov R. M. Kondratenko L. V. Spirikhin L. A. BaltinaJr. F. Z. Galin G. A. Tolstikov E. Haslinger 《Chemistry of Natural Compounds》2005,41(4):432-435
Resonances for protons and C atoms in the 1H and 13C NMR spectra of glycyrrhizic acid and its esters were assigned using high-resolution 1H (600 MHz) and 13C (150 MHz) NMR methods.
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Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 347–350, July–August, 2005. 相似文献
3.
T. V. Tyumkina I. F. Nuriev L. M. Khalilov V. R. Akhmetova U. M. Dzhemilev 《Chemistry of Natural Compounds》2009,45(1):61-65
The structure of a new compound was determined using PMR and 13C NMR spectroscopy (HHCOSY, HSBC, HMBC, ROESY) as 2-[3′-methoxy,4-O-β-D-galactopyranos-1-yl)benzyl]-3-(3″,4″-dimethoxybenzyl)-4hydroxybutyric acid, which was isolated for the first time from
seeds of Scotch thistle Onopordum acanthium L.
*For No. XII, see [1].
Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–55, January–February, 2009. 相似文献
4.
Comparative quantum chemical calculations of structural parameters, chemical shifts of 11B NMR spectra, and atomic charges in 10-vertex boron hydride anions [1-CB9H10]− and [1-B10H9N2]− were performed using the restricted Hartree-Fock method with the 6-31++G(D,P) basis set.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1853–1855, September, 2007. 相似文献
5.
Nizam M. El-Ashgar Issa M. El-Nahhal Mohamed M. Chehimi Michel Delamar Florence Babonneau Jacques Livage 《Journal of Sol-Gel Science and Technology》2007,41(1):3-10
A new insoluble solid functionalized ligand system bearing chelating ligand group of the general formula P-(CH2)3-N[CH2CONH(C6H4)NH2]2, where P represents [Si–O]
n
polysiloxane network, was prepared by the reaction of the immobilized diethyliminodiacetate polysiloxane ligand system, P-(CH2)3N(CH2CO2Et)2 with 1,2-diaminobenzene in toluene. 13C CP-MAS NMR, XPS and FTIR results showed that most ethylacetate groups (–COOEt) were converted into the amide groups (–N–C=O).
The new functionalized ligand system exhibits high capacity for extraction and removal of the metal ions (Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with efficiency of 95–97% after recovery from its primary metal complexes. This functionalized ligand system formed 1:1
metal to ligand complexes. 相似文献
6.
Yu. K. Grishin I. P. Gloriozov S. M. Gerdov V. A. Roznyatovsky L. L. Frolova A. V. Kuchin Yu. A. Ustynyuk 《Russian Chemical Bulletin》2008,57(8):1689-1696
The selectivity of deuterium distribution between the nonequivalent positions in 3-carene (1), 4-α-acetyl-2-carene (2), and 4-(1-hydroxyethyl)-2-carene (3) has been measured by 2H-{1H} NMR spectroscopy at the natural abundance of deuterium. These “H/D-isotope portraits” were shown to be typical of terpenes
and terpenoids produced in plants via the biosynthetic DXP pathway. The mechanism of acylation of 1 was studied by the density functional theory method (PBE functional, TZ2p basis set). The six-membered ring in compound 1 is planar. However, the endo attack of electrophiles on this ring is more favorable both kinetically and thermodynamically. It was shown both experimentally
and theoretically that the elimination of a hydrogen atom in the second reaction step proceeds stereoselectively at the C(2)
atom from the anti position with respect to the three-membered ring and occurs with pronounced nucleophilic assistance from the carbonyl group.
For Part 2, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1657–1664, August, 2008. 相似文献
7.
1H NMR spectra in CDCl3 of poly(N-vinylpyrrolidone), epoxidized poly(N-vinyl-pyrrolidone), and products derived from the latter by modification with amino acids (glycine, β-alanine, γ-aminobutyric
acid, and ε-aminocaproic acid) were examined. The 1H NMR spectra of the modified polymers contain signals for water protons due to different centers of water sorption. These
signals differ in chemical shift and integral intensity and indicate a changed spatial packing of the polymer as the result
of its modification.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2377–2380, October, 2005. 相似文献
8.
Zal U’yun Wan Mahmood Che Abd Rahim Mohamed Mei Wo Yii Zaharudin Ahmad Kamaruzzaman Ishak Abdul Kadir Ishak 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(1):107-113
Inventories and fluxes of 210Pb, 228Ra and 226Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits
with the thickness of water column between 42 and 83 m depth. The inventories of 210Pb, 228Ra and 226Ra were calculated range from 0.15–2.55 Bq cm−2, 0.05–0.40 Bq cm−2 and 6.83–83.63 Bq cm−2, meanwhile the fluxes ranged from 0.005–0.079 Bq cm−2 yr−1, 0.009–0.048 Bq cm−2 yr−1 and 0.003–0.037 Bq cm−2 yr−1, respectively. The results show that the highest inventories and fluxes for 210Pb, 228Ra and 226Ra were found at station WC 01 and EC 05. Because there are additional sources of 210Pb, 228Ra and 226Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended
particles, fast rate of regeneration and greater production of those radionuclides and others. 相似文献
9.
A. S. Volk I. N. Krasikova S. D. Anastyuk P. S. Dmitrenok T. F. Solov’eva 《Chemistry of Natural Compounds》2007,43(5):519-524
The structure of lipid A from the marine γ-proteobacterium Pseudoalteromonas nigrifaciens IAM 13010T that was prepared by hydrolysis of the corresponding lipopolysaccharide by acetic acid (1%) was determined by chemical analysis,
13C NMR spectroscopy, and MALDI/TOF and LSIMS mass spectrometry. It was shown that lipid A is a β-1,6-bonded disaccharide of glucosamine that is substituted by two phosphoric acids (in the C1 and C4′ positions), two (R)-3-hydroxyalkanoic
(normal and branched) acids with ester bonding (at the C3 and C3′-positions), and (R)-3-hydroxydodecanoic and (R)-3-dodecanoyloxydodecanoic
acids (both with amide bonding at C2′ and C2, respectively). It was hypothesized that this type of structure is typical of
lipid A from bacteria of the genus Pseudoalteromonas in general.
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Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 425–429, September–October, 2007. 相似文献
10.
Lenoble V Garnier C Masion A Ziarelli F Garnier JM 《Analytical and bioanalytical chemistry》2008,390(2):749-757
This work allowed the characterization of the Cd-binding sites of two compounds taken as models for exudates, the main components
of soil organic matter (SOM). The studied compounds were exopolysaccharides (EPS), specifically exudates of roots (polygalacturonic
acid) and of soil bacteria (Phytagel). Potentiometric acid–base titrations were performed and fitting of the obtained results
indicated the presence of two main classes of acidic sites, defined by their pK
a values, for both EPS but of a different nature when comparing the two compounds. The two studied exopolysaccharides presented
different acidic/basic site ratios: 0.15 for Phytagel and 0.76 for polygalacturonic acid. Spectroscopic techniques (13C/113Cd NMR, FTIR) distinguished different Cd surroundings for each of the studied EPS, which is in agreement with the titration
results. Furthermore, these analyses indicated the presence of –COOH and –OH groups in various proportions for each exopolysaccharide,
which should be linked to their reactivity towards cadmium. Cadmium titrations (voltammetric measurements) also differentiated
different binding sites for each compound and allowed the determination of the strength of the Cd-binding site of the EPS.
Fitting of the results of such voltammetric measurements was performed using PROSECE (Programme d’Optimisation et de Speciation Chimique dans l’Environnement), a software coupling chemical speciation calculation and binding parameter optimization. The fitting, taking into account
the Cd2+/H+ competition towards exopolysaccharides, confirmed the acid-base titrations and spectroscopic analyses by revealing two classes
of binding sites: (i) one defined as a strong complexant regarding its Cd2+–EPS association (logK = 9–10.4) and with basic functionality regarding H+–EPS association (pK
a = 11.3–11.7), and (ii) one defined as a weak complexant (logK = 7.1–8.2) and with acidic functionality (pK
a = 3.7–4.0). Therefore the combination of spectroscopic analyses, voltammetry, and fitting allowed the precise characterization
of the binding sites of the studied exopolysaccharides, mimicking the main SOM components. Furthermore, the binding parameters
obtained by fitting can be used in biogeochemical models to better define the role of key SOM compounds like exudates of roots
and of soil bacteria on trace metal transport or assimilation. 相似文献
11.
Evaluation of <Superscript>137</Superscript>Cs soil-to-plant transfer: Natural and model experiments
D. Butkus B. Lukšienė M. Konstantinova 《Journal of Radioanalytical and Nuclear Chemistry》2009,279(2):411-416
Soil and meadow grass were sampled in the whole territory of Lithuania in 1992–2000. For the laboratory experiment, spring
wheat Triticum aestivum L. “Nandu” was used because its root system type is similar to that of perennial meadow grass. The 137Cs soil-to-plant transfer factor of spring wheat was determined and the results were compared with the predicted values using
a compartment model of soil-to-plant transfer and with the results of the field experiment. The results of comparing the measured
and calculated transfer factor using the model show rather good coincidence, however, the calculated values were overestimated.
The reason for overestimation can be that the uptake rate is not influenced only by the soil-to-plant transfer. The results
of the model experiment (from 0.005 m2·kg−1 to 0.053 m2·kg−1) are close to those of the field measurements for grass (from 0.013 m2·kg−1 in 1992–1995 to 0.10 m2·kg−1 in 1999–2000). 相似文献
12.
D. Desideri M. A. Meli C. Roselli L. Feduzi 《Journal of Radioanalytical and Nuclear Chemistry》2009,279(2):591-600
In various samples of Mytilus galloprovincialis, 210Po was determined by alpha-spectrometry while Mn, Fe, Ni, Cu, Zn, Cd, Sn, Hg and Pb by energy dispersive, polarised X-ray
fluorescence spectrometry (EDPXRF). The mussels of different sizes were taken from 7 sites in the central Adriatic Sea along
the Marche coastal region during the four seasons of the year. 210Po activity concentration ranged between 57 and 343 Bq·kg−1 dry weight. The concentration ranges of heavy metals (μg·g−1 dry weight) were as follows: Mn: 72.9–83.1; Fe: 45.1–754; Ni: 1.3–7.6; Cu: 17.9–156; Zn: 60.9–189; Cd: 0.6–1.0; Sn: 0.6–3.9;
Hg always <0.5; Pb: 2.0–9.0. The data obtained depend upon the site and the period of the sampling and they are also compared
with those obtained by other authors for the same organism in the Mediterranean and other Italian seas. 相似文献
13.
Ricardo O. Silva Ricardo A. W. Neves Filho Rodrigo Azevedo Rajendra M. Srivastava Hugo Gallardo 《Structural chemistry》2010,21(3):485-494
In this article, we describe the complete 1H and 13C NMR signal assignments of four 1,2,4-oxadiazoles possessing light-emitting liquid crystal properties. These results were
obtained by using one- and two-dimensional NMR techniques as well as GIAO (PCM) calculations at B3LYP/6-311++G(d,p) level
for compounds 1 and 2a–d. The computed values are in good agreement with the ones obtained experimentally. In addition, some previously unexplained
thermotropic features of compounds 2a–d could be clarified with the help of the geometry optimization calculations carried out by us. 相似文献
14.
Determination of the structure of heparin-derived oligosaccharides by 1H NMR is challenging because resonances for all but the anomeric protons cover less than 2 ppm. By taking advantage of increased
dispersion of resonances for the anomeric H1 protons at low pD and the superior resolution of band-selective, homonuclear-decoupled (BASHD) two-dimensional 1H NMR, the primary structure of the heparin-derived octasaccharide ∆UA(2S)-[(1 → 4)-GlcNS(6S)-(1 → 4)-IdoA(2S)-]3-(1 → 4)-GlcNS(6S) has been determined, where ∆UA(2S) is 2-O-sulfated ∆4,5-unsaturated uronic acid, GlcNS(6S) is 6-O-sulfated, N-sulfated β-d-glucosamine and IdoA(2S) is 2-O-sulfated α-l-iduronic acid. The spectrum was assigned, and the sites of N- and O-sulfation and the conformation of each uronic acid residue were established, with chemical shift data obtained from BASHD-TOCSY
spectra, while the sequence of the monosaccharide residues in the octasaccharide was determined from inter-residue NOEs in
BASHD-NOESY spectra. Acid dissociation constants were determined for each carboxylic acid group of the octasaccharide, as
well as for related tetra- and hexasaccharides, from chemical shift–pD titration curves. Chemical shift–pD titration curves
were obtained for each carboxylic acid group from sub-spectra taken from BASHD-TOCSY spectra that were measured as a function
of pD. The pK
As of the carboxylic acid groups of the ∆UA(2S) residues are less than those of the IdoA(2S) residues, and the pK
As of the carboxylic acid groups of the IdoA(2S) residues for a given oligosaccharide are similar in magnitude. Relative acidities
of the carboxylic acid groups of each oligosaccharide were calculated from chemical shift data by a pH-independent method. 相似文献
15.
J. J. LaBrecque P. R. Cordoves M. A. Cordoves K. Perez D. Palacios J. A. Alfonso 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(3):669-674
This work presents the results of 137Cs, 40K, 232Th and 238U concentration (Bq kg−1) values in coastal marine sediments collected from 38 sites along the coastline of the island of Margarita, Venezuela. The
purpose was to determine baseline values for these radionuclides in surface marine sediments and to detect if there were any
anomalously high concentration values. Only three of the 38 sediments analyzed had measurable values above the detection limit
of 0.9 Bq kg−1 for 137Cs and the highest only being 1.4 Bq kg−1. While, the concentration (Bq kg−1) ranges for the primordial radionuclides, 40K, 232Th and 238U were as follows: 12.2–211.7, <1.5–9.8 and <4.4–20.7, respectively. These concentration ranges for the primordial radionuclides
can be considered as baseline values for surface marine sediments for areas that are considered not polluted by man or contaminated
by nature. Finally, the concentration range of 137Cs can also be employed as baseline values, which only seem to have been the result of the atmospheric testing of nuclear
weapons in the past. 相似文献
16.
I. M. Chung Mohd Ali A. Ahmad C. Y. Yu K. H. Ma J. G. Gwag Y. J. Park 《Chemistry of Natural Compounds》2005,41(6):650-653
One new compound 3,7,11,15,19-pentamethyl-9α,10α,11α,17α,18α-pentahydroxy-n-tetracosan-1-oxy-p-hydroxycaffeoate (oryzaterpenyl
caffeoate) (1), together with three known fatty acids linoleic acid, stearic acid and myristic acid were isolated and identified from the
rice grain of Oryza sativa. The structure of the new compound was elucidated by 1D and 2D NMR spectroscopic techniques (1H-1HCOSY, 1H-13C HETCOR) aided by EI-MS, and IR spectra.
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Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 535–537, November–December, 2005. 相似文献
17.
Zang Q Keire DA Wood RD Buhse LF Moore CM Nasr M Al-Hakim A Trehy ML Welsh WJ 《Analytical and bioanalytical chemistry》2011,399(2):635-649
Heparin, a widely used anticoagulant primarily extracted from animal sources, contains varying amounts of galactosamine impurities.
Currently, the United States Pharmacopeia (USP) monograph for heparin purity specifies that the weight percent of galactosamine
(%Gal) may not exceed 1%. In the present study, multivariate regression (MVR) analysis of 1H NMR spectral data obtained from heparin samples was employed to build quantitative models for the prediction of %Gal. MVR
analysis was conducted using four separate methods: multiple linear regression, ridge regression, partial least squares regression,
and support vector regression (SVR). Genetic algorithms and stepwise selection methods were applied for variable selection.
In each case, two separate prediction models were constructed: a global model based on dataset A which contained the full range (0–10%) of galactosamine in the samples and a local model based on the subset dataset B for which the galactosamine level (0–2%) spanned the 1% USP limit. All four regression
methods performed equally well for dataset A with low prediction errors under optimal conditions, whereas SVR was clearly
superior among the four methods for dataset B. The results from this study show that 1H NMR spectroscopy, already a USP requirement for the screening of contaminants in heparin, may offer utility as a rapid method
for quantitative determination of %Gal in heparin samples when used in conjunction with MVR approaches. 相似文献
18.
H. N. Altshuler L. P. Abramova N. V. Malyshenko G. Yu. Shkurenko E. V. Ostapova 《Russian Chemical Bulletin》2005,54(8):1978-1981
The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na+, K+, and Ba2+ as matrices was studied. The selectivity coefficients of ion exchanges Ba2+-H+, Na+-H+, K+-H+, Na+-K+, and Na+-NH4
+ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol−1.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005. 相似文献
19.
V. Ya. Kavun I. A. Tkachenko N. A. Didenko A. B. Slobodyuk V. I. Sergienko 《Russian Journal of Inorganic Chemistry》2010,55(8):1179-1183
The ionic mobility in heptafluorozirconates (NH4)2.7Rb0.3ZrF7 and (NH4)2.75Cs0.25ZrF7 has been studied by 1H and 19F NMR in the temperature range 150–430 K. The types of ion motion were determined and their activation energies were estimated.
A phase transition results in a modification in which diffusion in the ammonium sublattice and orientational disorder of ZrF73− anions are observed. Owing to diffusion of ammonium ions, the compounds have relatively high ionic conductivity (σ ≥ 5 ×
10−5 S/cm at 420 K). 相似文献
20.
Nicolas Dargère Véronique Bounor-Legaré Fernande Boisson Philippe Cassagnau Grégory Martin Phillipe Sonntag Nicolas Garois 《Journal of Sol-Gel Science and Technology》2012,62(3):389-396
Hydridosilazane compounds containing Si–N and Si–H bonds can be used as precursors of SiOx materials. The hydrolysis-condensation reactions of tetramethyldisilazane, as a polyhydridosilazane model compound, were
investigated by 1H and 29Si liquid NMR spectroscopy. These reactions were carried out at room temperature for up to 120 min in presence of water. The
identified products are short linear siloxane species (hydride terminated polydimethylsiloxanes MHDxMH) and cyclosiloxanes. Silicon hydride persistence in the reactional mixture suggested that silazane group is more sensitive
to hydrolysis reaction than silicon hydride group. Moreover, additional experiments evidenced that the low steric hindrance
of the silicon hydride influences the silazane hydrolysis kinetic. Hence the presence of ammonia released during silazane
hydrolysis reaction was demonstrated to be a catalyst of the silicon hydride hydrolysis reaction. 相似文献