Fine Substituent Effects in Sandwich Complexes: A Threshold Ionization Study of Monosubstituted Chromium Bisarene Compounds

Mass‐analyzed threshold ionization spectra of jet‐cooled [(η⁶‐PhMe)(η⁶‐PhH)Cr] and [(η⁶‐Ph₂)(η⁶‐PhH)Cr] reveal with unprecedented accuracy the effects of methyl and phenyl groups on the electronic structure of bis(η⁶‐benzene)chromium. These “pure” substituent effects allow quantitative experimental determination of the ionization energy changes caused by the mutual substituent influence in bisarene systems. Two types of such influence have been revealed for the first time in bis(η⁶‐toluene)chromium.     

Radical copolymerization of vinylidene cyanide with 2,2,2‐trifluoroethyl methacrylate: Structure and characterization

A novel copolymer of vinylidene cyanide (VCN) and 2,2,2‐trifluoroethyl methacrylate (MATRIF) was synthesized by bulk free radical process in a 52% yield from an equimolar comonomer feed. The copolymer's composition and microstructure were analyzed by FTIR, ¹H‐ and ¹³C‐NMR spectroscopy, SEC, and elemental analysis. The reactivity ratios calculated from both the Q‐e Alfrey‐Price parameters and the Jenkins' Patterns Scheme indicate a tendency to alternation in the copolymerization, the latter method suggesting that MATRIF homopropagation be slightly favoured (r_V = r₁₂ = 0.1, r_M = r₂₁ = 0.3). The molar incorporation of VCN in the copolymer was only 42 mol % according to the 9.0 wt % nitrogen content determined by elemental analysis, in good agreement with the value obtained by ¹H‐NMR. High‐resolution ¹H and ¹³C‐NMR spectra were used to study the microstructure of the copolymer. As an example, the three well‐resolved carbonyl resonances in the ¹³C‐NMR spectrum were assigned to the MATRIF‐centered triads VMV, VMM, and MMM, respectively, (V and M stand for VCN and MATRIF, respectively). The presence of VCN dyads (e.g., in VVM and VVV sequences) was shown to be marginal or absent altogether. Thermogravimetric analysis of poly(VCN‐co‐MATRIF) copolymer showed good thermal stability, and its main pyrolytic degradation taking place only above 368 °C. A 4% weight loss at about 222 °C suggested the presence of a few VCN homodyads, possibly inducing thermal depolymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Simple and robust digital holography for high-resolution imaging

Based on the point spread function of holographic system,the lateral resolution of digital holographic imaging system without any pre-magnification is studied.The expression of resolution limitation of holographic imaging system is thus presented.We investigate the possibilities to improve the lateral resolution.The simple experimental setup with an off-axis arrangement is built.By using a U.S.Air Force(USAF)test target as microscopic object,the recorded holograms are reconstructed digitally based on the principle of Fresnel diffraction.The lateral resolution of 2.76 μm without any pre-magnification is demonstrated experimentally,which matches the theoretical prediction well.     

Characterization and Spatial Matching of Laser Diode Beams

It is shown that the type of lateral waveguide of a laser diode cannot be determined uniquely based on just the measured magnitude of astigmatism. For a unique determination, the K-factor of Petermann, which characterizes the wavefront curvature at the laser output facet, must be measured as well. In order to determine the type of lateral waveguide, a setup for measuring astigmatic distances in the range 0–200 m with an error of ±2 m and a K-factor with an error of 20% was developed. Operational features of the setup were analyzed, and a technique that allows one to minimize the effect of beam ellipticity on the measurement results was found. Using the technique, the optimization of spatial matching of a laser diode with a ring interferometer of the butterfly type was accomplished. For transformation of the astigmatic elliptical beam into the axially symmetric mode of the interferometer, we have used an optical system that consists of two cylindrical and one spherical lenses. The algorithm for designing the matching system was developed, and the 85% injection of radiation of a AlGaAs laser diode into the principal mode of a ring interferometer was experimentally demonstrated.     

Electronic effects of heterocyclic ring systems as evaluated with the aid of 13C and 15N NMR chemical shifts and NBO analysis

The electronic effects of the 5‐ and 6‐membered heterocyclic rings on the C?N? N unit of five different hydrazone derivatives of pyridine‐2‐, ‐3‐ and ‐4‐carbaldehydes, pyrrole‐2‐carbaldehyde, furan‐2‐ and ‐3‐carbaldehydes and thiophene‐2‐ and ‐3‐carbaldehydes have been studied with the aid of ¹³C and ¹⁵N NMR measurements together with the natural bond orbital (NBO) analysis. As model compounds are used the corresponding substituted benzaldehyde derivatives. The polarization of the C?N unit of the hydrazone functionality of the heteroaryl derivatives occurs in an analogous manner with that of phenyl derivatives. The electron‐withdrawing heteroaryl groups destabilize and the electron‐donating groups stabilize the positive charge development at the C?N carbon while the effect on the negative charge development is opposite. The ¹⁵N NMR chemical shift of the C?N and C?N? N nitrogens and the NBO charges at C?N? N unit can be correlated with the replacement substituent constants σ of the heteroaryl groups. ¹³C NMR shifts of the C?N carbon of N,N‐dialkylhydrazones of the heteroarenecarbaldehydes can be correlated with a dual parameter equation possessing the polar substituent constant σ* of the heteroaryl group and the electronegativity of the heteroatom as variables. Copyright © 2008 John Wiley & Sons, Ltd.     

Indirect carbon–carbon spin–spin couplings across one,two and three bonds in pyridine and diazine systems: experiment and theory

An excellent linear correlation is found between a large body of experimental spin–spin carbon–carbon couplings, J(CC), across one, two and three bonds in pyridine and diazine ring systems and the corresponding B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) computations. The correlation does not differ significantly from the simplest relationship possible, J(CC)_exp. = J(CC)_calcd., within a small and random spread of about 1 Hz. There are 276 experimental values considered, and 124 out of these are new and come from the present work. The aromatic carbon–carbon couplings vary from ?7.6 through +78.5 Hz. It is shown that the correlation provides a reliable tool for predictions of the signs of aromatic J(CC)'s even if the magnitudes of the latter are of the order of 1 Hz. It is demonstrated, for the first time, that the relatively weak ² J(CC) couplings, in the heteroaromatic systems studied, can bear either sign and span a considerable range of about 11 Hz. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in analogous benzene ring system. Substituent effects on the aromatic J(CC)'s turn out to be significant not only for ¹J(CC)'s but also for most of ³J(CC)'s and ² J(CC)'s, and the computation neatly reciprocates these trends. Copyright © 2008 John Wiley & Sons, Ltd.     

Diastereofacial selectivity in some 4‐substituted (X) 2‐adamantyl derivatives: electronic versus steric effects

π‐Facial selectivity data for the reduction and methylation of some 4^ax‐substituted (X) 2‐adamantanones ( 3 , Y = O) as well as the nucleophilic trapping of secondary and tertiary 4^ax‐substituted (X)‐2‐adamantyl cations ( 4 ; R = H and CH₃, respectively) and the 4‐methylene‐2‐adamantyl radical ( 8 ) are presented. The pronounced anti‐face selectivities observed for ( 3 , Y = O and 4 , R = CH₃) emphasize the importance of the steric factor as expected for systems with a strong steric bias. However, the dominant syn‐face capture of 4 (R = H) was completely unexpected and highlights a subtle interplay between steric and electronic effects. Finally, the very high anti‐face stereoselectivity for the trapping of ( 8 ) with the trimethylstannyl anion (Me₃Sn^?) is rationalized in terms of an electrostatic effect overwhelming the steric factor. Copyright © 2007 John Wiley & Sons, Ltd.     

Substituent Effects on Hyperfine Coupling Constants Analyzed in Terms of π-Bound Electron Perturbation Theory

Substituent effects on the hyperfine interaction (hfi) constants of hydrocarbon, quinone, aza-, and hydroazaaromatic radicals are analyzed in terms of -bound electron perturbation theory. For odd alternant radicals, substituent effects are described in terms of second-order perturbation theory using a quadratic dependence on the constants of the substituents. The results of the calculation agree well with the available experimental data.     

Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes

Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.     

腰椎间盘纤维环膨隆症站立位动态脊髓造影的临床意义

目的:在MRI或CT检查的腰腿痛病人中,通过站立位动态脊髓造影,了解椎间盘纤维环在腰椎中立、过屈、过伸三位置下的变化,并探讨其临床意义,筛选出具有手术指征的LDH病人,决定手术方式.方法:对86例LDH患者,行站立或平卧中立、过屈、过伸脊髓造影,对比分析两组动态变化.鉴别出LDB,选择性行有限椎板减压,或保留其椎间盘.结果:脊髓造影侧位像“拿破仑帽”状影,站立三位置均明显大于平卧位,差异非常显著(P＜0.01),在动态变化中平卧位者改成由中至屈曲位时,硬膜囊受压影较站立位者明显缩小,差异非常显著(P＜0.01),站立由中至伸时,压迫影较平卧位增大,差异显著(P＜0.05).其中28例,行有限椎板切除或保留其椎间盘,效果优良.结论:站立位会使LDB加重、临床症状加重,因站立过伸位使腰椎管狭窄病人症状加重.而平卧位造影时因重力负荷减轻,(拿破仑帽)影像不明显或消失,而出现假阴性.