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241.
For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and 1H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (Mn = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386  相似文献   
242.
Using a mass-loss method, we investigated the solubility change of gallium nitride (GaN) in supercritical ammonia with mixed mineralizers [ammonium chloride (NH4Cl)?+?ammonium bromide (NH4Br) and NH4Cl?+?ammonium iodide (NH4I)]. The solubilities were measured over the temperature range 450–550 °C, at 100 MPa. The solubility increased with NH4Cl mole fraction at 450 °C and 100 MPa. The temperature dependence of the solubility curve was then measured at an equal mole ratio of the two mineralizers. The slope of the solubility–temperature relationship in the mixed mineralizer was between those of the individual mineralizers. These results show that the temperature dependence of the solubility of GaN can be controlled by the mineralizer mixture ratio. The results of the van’t Hoff plot suggest that the solubility species were unchanged over the investigated temperature range. Our approach might pave the way to realizing large, high-quality GaN crystals for future gallium-nitride electronic devices, which are increasingly on demand in the information-based age.  相似文献   
243.
We have designed and synthesized two room‐temperature‐fluorescent π‐conjugated liquids based on the N‐heteroacene framework ( 1 and 2 ). These two π‐conjugated liquids, which contained one and two thiophene rings, respectively, exhibited different electronic properties and rheology behaviors. Single‐crystal X‐ray analysis of dithiophene‐appended compound 4 revealed that two thiophene rings hindered the interactions of the imino N atoms with acids through the formation of interactions between the S atoms of the thiophene rings and the imino N atoms of the pyrazine group. On the other hand, monothiophene‐appended molecules 1 and 3 each contained an unhindered imino N atom on the opposite site to the thiophene ring. Upon dissolving various acids with different pKa values in compounds 1 and 2 , these slight structural differences gave rise to marked differences in their acid‐response behaviors, thereby resulting in the emission of variously colored fluorescence in the liquid state. Furthermore, when acids with lower pKa values was dissolved in compounds 1 and 2 , phase transition occurred from an isotropic liquid state to a self‐organized liquid‐crystalline phase.  相似文献   
244.
The synthesis and structural analysis of a quintuple [6]helicene with a corannulene core is reported. The compound was synthesized from corannulene in three steps including a five‐fold intramolecular direct arylation. X‐ray crystallographic analysis revealed a C5‐symmetric propeller‐shaped structure and one‐dimensional alignment in the solid state. The enantiomers of the quintuple [6]helicene were successfully separated by HPLC, and the chirality of the two fractions was identified by CD spectroscopy. A kinetic study yielded a racemization barrier of 34.2 kcal mol?1, which is slightly lower than that of pristine [6]helicene. DFT calculations indicate a rapid bowl‐to‐bowl inversion of the corannulene moiety and a step‐by‐step chiral inversion pathway for the five [6]helicene moieties.  相似文献   
245.
The Michael addition of a chiral amine [(-)- 6] to alpha,beta-unsaturated esters ( 4) was attained and the stereoselectivity was inverted by changing the solvent from diethyl ether to tetrahydrofuran when alpha,beta-unsaturated esters having an aromatic ring at the beta-position were employed. In addition, the chiral auxiliary in the Michael adducts ( 9A) was facilely removed with N-iodosuccinimide to afford beta-amino esters ( 10A) and 2-methoxy- d-bornylaldehyde ( 11), which can be reclaimed to the chiral amine ( 6) by reductive amination.  相似文献   
246.
Iron triflate, in situ-formed from FeCl3 and triflic acid, or FeCl3 and silver triflate efficiently catalyse the intermolecular addition of carboxylic acids to various alkenes to yield carboxylic esters; the reaction is applicable to the synthesis of unstable esters, such as acrylates.  相似文献   
247.
To identify the correlation between the phosphorylation ratios by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-ToF MS) analysis and enzyme kinetics (K(m), V(max), and V(max)/K(m)) is important to understand whether MALDI-TOF MS can be applied for monitoring the properties of peptides that are substrates of protein kinases. The correlation between phosphorylation ratios and enzyme kinetics was examined using peptides for protein kinase C (PKC) and for 60 kDa phosphoprotein, encoded by the cellular sarcoma gene (c-Src). Phosphorylation ratios, analyzed by MALDI-ToF MS, showed higher correlation coefficient (r = > +0.7) for V(max)/K(m) compared with that (r = < -/+0.6) for K(m) or V(max). For ion modes, a higher correlation coefficient between phosphorylation ratios and V(max)/K(m) was identified in the positive mode (r = > +0.7) compared to that in the negative mode (r = < +0.5). These results suggest that MALDI-ToF MS is a useful tool to evaluate V(max)/K(m) of peptides for protein kinases.  相似文献   
248.
An efficient synthesis of (-)-ternatin derivatives directed toward their SAR at the beta-OH-D-Leu(7) moiety and their biological activities against 3T3-L1 murine adipocytes are described.  相似文献   
249.
The complexes [NaphAu(PPh(3))], and [mu-Naph{Au(PPh(3))}(2)]ClO(4), having the Au-C (aromatic) bond have been synthesized and characterized. The unique structure of with two gold atoms bridged by a naphthyl group has been determined by X-ray crystallography. The intramolecular Au-Au separation in is 2.7731(4) A. Upon excitation at 266 nm, both complexes display intraligand phosphorescence at room temperature in solution and in solid state.  相似文献   
250.
The marine fireworm, Eurythoe complanata, is known as a dangerous animal for humans because it induces skin inflammation through its small setae. Here, the inflammation-inducing substance was successfully isolated from the whole body using a methanolic extraction, and the inflammatory activity was determined using a bioassay. The structure was spectroscopically revealed to be a trimethylammonium with an unsaturated carbon chain and was named complanine. Complanine enhanced PKC activity in combination with TPA in vitro. This may explain the molecular mechanism behind its inflammation-inducing activity.  相似文献   
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