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1.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
2.
锥形光纤间耦合特性的分析与检测 总被引:2,自引:0,他引:2
将通信光纤的末端拉制成锥形,利用光信号在光纤锥形区特有的传输和耦合特性,实现了光纤的耦合、连接和分束。用耦合模理论分析了锥形光纤间的传输和耦合性质,给出了光信号两锥形光纤间的耦合与两锥形光纤的距离和锥形区重叠长度等实验结果。 相似文献
3.
The influence of the electron-LO-phonon coupling on energy spectrum of the low-lying states ofan exciton inparabolic quantum dots is investigated as a function of dot size. Calculations are made by using the method of few-bodyphysics within the effective-mass approximation. A considerable decrease of the energy in the stronger confinement rangeis found for the low-lying states of an exciton in quantum dots, which results from the confinement of electron-phononcoupling. 相似文献
4.
Francisco‐Javier Sayas 《Numerical Methods for Partial Differential Equations》2003,19(5):555-570
This article presents and analyzes a simple method for the exterior Laplace equation through the coupling of finite and boundary element methods. The main novelty is the use of a smooth parametric artificial boundary where boundary elements fit without effort together with a straight approximate triangulation in the bounded area, with the coupling done only in nodes. A numerically integrated version of the algorithm is also analyzed. Finally, an isoparametric variant with higher order is proposed. © 2003 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 19: 555–570, 2003 相似文献
5.
《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
6.
7.
John A. Mikroyannidis Larysa Fenenko Masayuki Yahiro Chihaya Adachi 《Journal of polymer science. Part A, Polymer chemistry》2007,45(20):4661-4670
Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with ηEL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007 相似文献
8.
Demet Colak Ioan Cianga Ali Ekrem Muftuoglu Yusuf Yagci 《Journal of polymer science. Part A, Polymer chemistry》2006,44(2):727-743
Well‐defined polystyrene‐ (PSt) or poly(ε‐caprolactone) (PCL)‐based polymers containing mid‐ or end‐chain 2,5 or 3,5‐ dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). 1,4‐Dibromo‐2‐(bromomethyl)benzene, 1,3‐dibromo‐5‐(bromomethyl)benzene, and 1,4‐dibromo‐2,5‐di(bromomethyl)benzene were used as initiators in ATRP of styrene (St) in conjunction with CuBr/2,2′‐bipyridine as catalyst. 2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene initiated the ROP of ε‐caprolactone (CL) in the presence of stannous octoate (Sn(Oct)2) catalyst. The reaction of these polymers with amino‐ or aldehyde‐functionalized monoboronic acids, in Suzuki‐type couplings, afforded the corresponding telechelics. Further functionalization with oxidable groups such as 2‐pyrrolyl or 1‐naphthyl was attained by condensation reactions of the amino or aldehyde groups with low molecular weight aldehydes or amines, respectively, with the formation of azomethine linkages. Preliminary attempts for the synthesis of fully conjugated poly(Schiff base) with polymeric segments as substituents, by oxidative polymerization of the macromonomers, are presented. All the starting, intermediate, or final polymers were structurally analyzed by spectral methods (1H NMR, 13C NMR, and IR). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 727–743, 2006 相似文献
9.
John A. Mikroyannidis Helen A. Moshopoulou John A. Anastasopoulos Minas M. Stylianakis Larysa Fenenko Chihaya Adachi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(23):6790-6800
Poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐2,8‐vinylene) (PS) and poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐5,5‐dioxide‐2,8‐ vinylene) (PSO) as well as corresponding model compounds were synthesized by Heck coupling. Both the polymers and model compounds were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. The polymers showed a decomposition temperature at ~430 °C and a char yield of about 65% at 800 °C in N2. The glass‐transition temperatures of the polymers were almost identical (75–77 °C) and higher than those of the model compounds (26–45 °C). All samples absorbed around 390 nm, and their optical band gaps were 2.69–2.85 eV. They behaved as blue‐greenish light emitting materials in both solutions and thin films, with photoluminescence emission maxima at 450–483 nm and photoluminescence quantum yields of 0.52–0.72 in solution. Organic light‐emitting diodes with an indium tin oxide/poly(ethylene dioxythiophene):poly(styrene sulfonic acid)/polymer/Mg:Ag/Ag configuration with polymers PS and PSO as emitting layers showed green electroluminescence with maxima at 530 and 540 nm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6790–6800, 2006 相似文献
10.
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