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21.
《Magnetic resonance in chemistry : MRC》2003,41(8):599-602
Gradient‐enhanced pulse schemes are presented for the detection of quaternary and methylene carbons. The new pulse schemes permit the detection of quaternary and methylene (—CH2) carbons or CH2 carbons alone from a single experiment. Efficient suppression of CH and CH3 carbons in all the pulse schemes is achieved by creating their antiphase magnetization and then dephasing using gradients. In the pulse schemes for detection of only CH2 carbons, the quaternary carbons are also suppressed either by dephasing using gradients or by rendering them unobservable by retaining in longitudinal order. The experimental results of the gradient pulse schemes are demonstrated on cholesteryl acetate and cyclosporin A. These one‐dimensional techniques, because of their simplicity and the ease of performing the experiments, can be important for routine chemical applications. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
22.
《Magnetic resonance in chemistry : MRC》2003,41(8):626-628
15N isotopic enrichment was necessary for the unequivocal assignment of the 1H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C6H5CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, 1J(15N,1H) = 102.2 Hz, 2J(15N,1H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the 29Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
23.
《Magnetic resonance in chemistry : MRC》2003,41(1):61-64
Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C15H20N5)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C15H20N5)]Cl compound. NMR studies allowed an unambiguous assignment of all 1H and 13C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C15H20N5)](CH3COO)H2O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C15H20N5)]+ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
24.
Multiwalled carbon nanotubes were modified by carboxy groups. Four independent methods for the determination of the degree
of functionalization of the surface were proposed: 13C NMR spectroscopy, thermogravimetry, titrimetry, and fluorimetry. The first two methods show the total content of carboxy
groups in the sample, and the latter two methods give information about the content of the surface groups only.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 291–295, February, 2008. 相似文献
25.
《Magnetic resonance in chemistry : MRC》2003,41(1):77-79
The complete assignment of the 1H and 13C NMR spectra of the title enediones, bearing as substituents N‐aziridinyl (a novel compound), methoxy, chloro and methylsulfanyl, is reported. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
26.
Jacquelyn A. Carioscia Lauren Schneidewind Casey O'Brien Robert Ely Caitlin Feeser Neil Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2007,45(23):5686-5696
The ability to prepare high Tg low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (Tg) for several thiol–norbornene materials. Results indicate that Tgs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high Tg materials. In particular, as much as a 70 °C increase in Tg was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007 相似文献
27.
28.
Feng-Yu Wang 《Probability Theory and Related Fields》1994,98(3):299-306
Summary By using coupling methods, some lower bounds are obtained for the first Neumann eigenvalue on Riemannian manifolds. This method is new and the results improve some known estimates. An example shows that our estimates can be sharp.Research supported in part by the Foundation of Beijing Normal University 相似文献
29.
Raushan Z. Buzyakova 《Topology and its Applications》2007,154(4):917-924
We describe the structure of spaces of continuous step functions over GO-spaces. We establish a relation between the Dedekind completion of a GO-space L and properties of the space of continuous functions from L to 2 with finitely many steps. We use the established relation to prove that a countably compact GO-space L has Lindelöf Cp(L) iff the Dedekind remainder of L is Lindelöf and every compact subspace of L is metrizable. Or equivalently, a countably compact GO-space L has Lindelöf Cp(L) iff every compact subspace of L is metrizable and a Gδ-set in L. Other results are obtained. 相似文献
30.
Sridevi Kaiti Eric Fossum 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):2099-2106
A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via 1H, 13C, and 31P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, Mn, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using 31P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with Td (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006 相似文献