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921.
C. L. Crofcheck E. W. Nelson J. L. Jacobs A. B. Scranton 《Journal of polymer science. Part A, Polymer chemistry》1995,33(10):1735-1744
The temperature-dependent luminescence of tris (β-diketone) chelates of europium was used for in situ temperature measurements during cationic photopolymerizations of vinyl ethers. These molecular-level luminescent probes provided a real-time, noninvasive method for monitoring temperature during these high-speed polymerizations. Two specific probes, tris (benzoyl-1, 1, 1-trifluoroacetone) europium and tris (1,1,1,5,5,5,-hexafluoroacetylacetone) europium, met several stringent spectral and performance requirements for application in our system. The luminescence from these probes exhibits a reproducible temperature dependence over a wide temperature range and is not sensitive to changes in viscosity. In situ temperature profiles obtained using this novel technique verified the importance of thermal effects during these highly exothermic photopolymerizations. These studies have demonstrated the utility of the tris(β-diketone) europium chelates for characterizing the temperature during high-speed photopolymerizations that cannot be monitored using conventional techniques. © 1995 John Wiley & Sons, Inc. 相似文献
922.
Thio-substituted dienes bearing an enone moiety were readily prepared from 3-sulfolenes, and their intramolecular Diels-Alder (IMDA) reactions were studied. Octahydronaphthalenones were produced in good yield with high stereoselectivity. Hexahydroindenones were also obtained, but the stereoselectivity was lower. 相似文献
923.
A systematic investigation in isolated 5-hydroxyisoxazole–water complexes (5-HIO · (H2O)nn = 1–3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K2 is the most stable isomer in the gas phase, and the tautomer K1 to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WEcis ↔ 3WK1 and 2WEtrans ↔ 2WK2 is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between Ecis and K1 cannot happen without solvent-assisted. 相似文献
924.
Shinsaku Fujita 《Theoretical chemistry accounts》2007,117(3):353-370
Planted three-dimensional (3D) trees, which are defined as a 3D version of planted trees, are enumerated by means of Fujita’s
proligand method formulated in Parts 1–3 of this series [Fujita in Theor Chem Acc 113:73–79, 80–86, 2005; Fujita in Theor
Chem Acc 115:37–53, 2006]. By starting from the concepts of proligand and promolecule introduced previously [Fujita in Tetrahedron
47:31–46, 1991], a planted promolecule is defined as a 3D object in which the substitution positions of a given 3D skeleton are occupied by a root and proligands.
Then, such planted promolecules are introduced as models of planted 3D-trees. Because each of the proligands in a given planted
promolecule is regarded as another intermediate planted promolecule in a nested fashion, the given planted promolecule is
recursively constructed by a set of such intermediates planted promolecules. The recursive nature of such intermediate planted
promolecules is used to derive generating functions for enumerating planted promolecules or planted 3D-trees. The generating
functions are based on cycle indices with chirality fittingness (CI-CFs), which are composed of three kinds of sphericity
indices (SIs), i.e., a
d
for homospheric cycles, c
d
for enantiospheric cycles, and b
d
for hemispheric cycles. For the purpose of evaluating c
d
recursively, the concept of diploid is proposed, where the nested nature of c
d
is demonstrated clearly. The SIs are applied to derive functional equations for recursive calculations, i.e., a(x), c(x
2), and b(x). Thereby, planted 3D-trees or equivalently monosubstituted alkanes as stereoisomers are enumerated recursively by counting
planted promolecules. The resulting values are collected up to 20 carbon content in a tabular form. Now, the enumeration problem
initiated by mathematician Cayley [Philos Mag 47(4):444–446, 1874] has been solved in such a systematic and integrated manner
as satisfying both mathematical and chemical requirements. 相似文献
925.
926.
The molecular structures and vibrational spectra of the three isomers of pyridinecarboxamide (picolinamide, nicotinamide, isonicotinamide) were calculated with the Density Functional Theory (DFT) method using the B3LYP function and the 6-31++G(d,p), Z2PolX, Z3PolX basis sets. The calculations were performed by using the Gaussian98W packet program set. The total energy distributions (TED) of the vibrational modes of these molecules were calculated by using the Scale 2.0 program and the vibrational modes of the molecules were determined. The Scaled Quantum Mechanical (SQM) method was used in the scaling procedure. In the experimental part of the study, the solid phase FT-IR and Micro Raman spectra of the three isomers of pyridinecarboxamide have been recorded in the range of 4000-650 and 1200-100 cm−1, respectively. The calculated wavenumbers were compared to the corresponding experimental values. As a result, the observed bands of the three isomers of pyridinecarboxamide were assigned with good accuracy. 相似文献
927.
Solvent effects in a carbenoid N-H insertion route to triarylamines via 2-diazo-1,3-cyclohexanedione
Peter Livant 《Tetrahedron letters》2005,46(12):2113-2116
The Rh-carbenoid derived from 2-diazo-1,3-cyclohexanedione inserts into the N-H bond of arylalkylamines and diarylamines. A solvent for this reactive carbenoid is suggested. The insertion products undergo a Pd-mediated aromatization to afford alkyldiarylamines and triarylamines. 相似文献
928.
Robert?WeisEmail author Armin?Presser Werner?Seebacher 《Monatshefte für Chemie / Chemical Monthly》2003,134(8):1129-1136
Summary. 3-Carboxamides and 3-carboxanilides of 6-alkyl and 6-aryldihydropyridin-2(1H)-ones have been prepared via different reaction pathways. All synthesized amides show hydrogen bonds in their NMR spectra. The 4-hydroxy compounds were obtained as a mixture of tautomers. Their configurations were elucidated by NMR experiments.Received December 16, 2002; accepted December 20, 2002
Published online June 2, 2003 相似文献
929.
研究了BiTaO4∶Pr3+, BiTaO4的光致发光性质, 测量了BiTaO4的红外透射和漫反射光谱. BiTaO4的光致发光光谱发射峰位于约420, 440, 465 nm; 其激发谱在约330~370 nm范围有明显的激发. BiTaO4∶Pr3+的光致发光光谱为Pr3+的特征发射, 主峰为606 nm, 来自Pr3+的3P0→3H6跃迁; 其激发谱由来自于基质的峰值为325 nm和范围在375~430 nm的宽激发带以及Pr3+的特征激发组成, 325 nm, 375~430 nm的激发带可能分别来自钽酸根团的电荷迁移跃迁和基质的带间缺陷能级的吸收; 在BiTaO4∶Pr3+中存在着基质→Pr3+的能量传递. 由于BiTaO4∶Pr3+基质的密度和Pr3+的发光强度均超过PbWO4, 因此BiTaO4∶Pr3+可能是潜在的重闪烁体. 相似文献
930.