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1.
Andrea Santagati Agostino Marrazzo Giuseppe Granata 《Journal of heterocyclic chemistry》2003,40(5):869-873
Derivatives containing the thieno[2,3‐d]pyrimidin‐4‐one system, potential selective COX‐2 inhibitors, were prepared starting from ethyl ester of 2‐isothiocyanato‐5‐phenyl‐3‐thiophenecarboxylic acid ( 2 ); their structural elucidation is also reported. 相似文献
2.
Michelina Soccio Lara Finelli Nadia Lotti Valentina Siracusa Tiberio A. Ezquerra Andrea Munari 《Journal of Polymer Science.Polymer Physics》2007,45(13):1694-1703
Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the Tg value, a decrement of Tm, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007 相似文献
3.
Spatio temporal dynamics of the positive column of a dc neon glow discharge is studied and investigated experimentally and theoretically. Spatio temporal analysis by means of biorthogonal decomposition method (BOD) gives insights into the mechanism of irregularity and can be employed for characterization of spatio‐ temporal complexity. In the weak nonlinear region, the wave dynamics is approximated by an amplitude equation of the Ginzburg‐Landau equation (CGLE) with complex coefficients and an additional integral term based on a fluid model. In the present work we deal with irregular spatio‐temporal data. A comparison between the numerical analysis of the experimental data and simulation results are studied. A good agreement between the dynamical behaviour for experimental space‐time data and theoretical simulation space‐time results was obtained. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
4.
Sk. Asrof Ali Yunusa Umar B. F. Abu‐Sharkh Hasan A. Al‐Muallem 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5480-5494
The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s−1 at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006 相似文献
5.
A micro-reactor system with continual spectrophotometric detection has been operated in Sequential Injection lab-on-valve (SI-LOV) mode and applied to enzyme kinetics and inhibition studies, using acetylcholinesterase (AChE) and angiotensin-converting enzyme (ACE) as model systems. With the advantages of automation, real-time kinetic measurement, and thorough mixing, the SI-LOV micro-reactor system allows for the monitoring of initial reaction rates and determination of reactant concentrations in the reaction mixture, both of which are essential for the determination of kinetic constants for enzymes and inhibitors. Enzyme, substrate, and inhibitor are precisely metered by the syringe pump and delivered to a stirred micro-reactor, followed by a reference scan that establishes the baseline for the following reaction rate measurement. Michaelis constants (Km) for AChE and ACE were determined to be 0.16 mM and 0.30 mM, respectively, which are consistent with literature values. The type of inhibition (competitive, uncompetitive, or mixed), the dissociation constants for the inhibitors, and the inhibitor dose-response curves were also determined. 相似文献
6.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
7.
8.
The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)). 相似文献
9.
A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ). 相似文献
10.
A two-step protocol for the first chemoselective cleavage of 2-hydroxy acid amides has been developed. Mesylation of the model substrate 2-(hydroxypropionylamino)-4-methylpentanoic acid methyl ester (11) followed by treatment with N-ethylthiourea (13) allows cleavage of 2-hydroxy acid amides under smooth conditions. Successful application of this methodology to the open-chain transesterification product 15 (methylester) of the cyclic heptadepsipeptide HUN-7293, a potent inhibitor of inducible cell adhesion molecule expression, delivered the corresponding hexapeptide 18 with unprotected N-terminus in 70-75% yield. This result demonstrates that the protocol developed even works in the presence of an ester and several methylated and unmethylated amide bonds. Finally, a sequence of ligation of methyl D-dehydroglutaminate (20) to the C-terminus of the saponification product 21, followed by the degradation protocol and ring closure, allowed chemical "point mutation" at the DGCN site affording the aza analogue of HUN-7293 (24) in 15% overall yield. To the best of our knowledge this is the first report on chemoselective cleavage of 2-hydroxy acid amides. 相似文献