Reactivity of (2,4-cycloheptadiene-1,6-dione)Fe(CO)3: synthesis of hinokitiol and (7,8-diphenylheptatriafulvalene-1,6-quinone)Fe(CO)3

The reactivities of tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron toward several kinds of nucleophiles and electrophiles were investigated. As a result, it was found that tricarbonyl(2,4-cycloheptadiene-1,6-dione)iron has several reaction sites and undergoes several types of reactions. A new synthetic route to hinokitiol and tricarbonyl-(7,8-diphenylheptariafulvalene-1,6-quinone)iron from (2,4-cycloheptadiene-1,6-dione)iron was explored.     

CP/MAS (13)C NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the CP/MAS (13)C NMR spectrum of the native cellulose

The precise assignments of cross polarization/magic angle spinning (CP/MAS) (13)C NMR spectra of cellulose I(alpha) and I(beta) were performed by using (13)C labeled cellulose biosynthesized by Acetobacter xylinum (A. xylinum) ATCC10245 strain from culture medium containing D-[1,3-(13)C]glycerol or D-[2-(13)C]glucose as a carbon source. On the CP/MAS (13)C NMR spectrum of cellulose from D-[1,3-(13)C]glycerol, the introduced (13)C labeling were observed at C1, C3, C4, and C6 of the biosynthesized cellulose. In the case of cellulose biosynthesized from D-[2-(13)C]glucose, the transitions of (13)C labeling to C1, C3, and C5 from C2 were observed. With the quantitative analysis of the (13)C transition ratio and comparing the CP/MAS (13)C NMR spectrum of the Cladophora cellulose with those of the (13)C labeled celluloses, the assignments of the cluster of resonances which belong to C2, C3, and C5 of cellulose, which have not been assigned before, were performed. As a result, all carbons of cellulose I(alpha) and I(beta) except for C1 and C6 of cellulose I(alpha) and C2 of cellulose I(beta) were shown in equal intensity of doublet in the CP/MAS spectrum of the native cellulose, which suggests that two inequivalent glucopyranose residues were contained in the unit cells of both cellulose I(alpha) and I(beta) allomorphs.     

Doppler-free two-photon excitation spectroscopy and the Zeeman effects of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) band of naphthalene-d8

Doppler-free two-photon excitation spectrum and the Zeeman effect of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) transition of naphthalene-d8 have been measured. 908 lines of Q(Ka)Q(J)KaKc transition of J=0-41, Ka=0-20 were assigned, and the molecular constants of the S1 1B1u(v21=1) state were determined. Perturbations were observed, and those were identified as originating from Coriolis interaction. No perturbation originating from an interaction with triplet state was observed. The Zeeman splittings from lines of a given J were observed to increase with Kc, and those of the Kc=J levels increased linearly with J. The Zeeman effects are shown to be originating from the magnetic moment of the S1 1B1u state, which is along the c axis and is induced by mixing of the S2 1B3u state to the S1 1B1u state by J-L coupling. Rotationally resolved levels were found not to be mixed with a triplet state from the Zeeman spectra. Accordingly, it is concluded that nonradiative decay of an isolated naphthalene excited to low rovibronic levels in the S1 1B1u state does not occur through the intersystem mixing. This is at variance with generally accepted understanding of the pathways of the nonradiative decay.     

End-cap effects on vibrational structures of finite-length carbon nanotubes

Vibrational structures of C60-related finite-length nanotubes, C(40+20n) and C(42+18n) (1 < or = n < or = 4), in which n is, respectively, the number of cyclic cis- and trans-polyene chains inserted between fullerene hemispheres, are analyzed from density functional theory (DFT) calculations. To illuminate the end-cap effects on their vibrational structures, the corresponding tubes terminated by H atoms C(20n)H20 and C(18n)H18 (1 < or = n < or = 5) are also investigated. DFT calculations show a broad range of vibrational frequencies for the finite-size nanotubes: high-frequency modes (1100-1600 cm(-1)) containing oscillations along tangential directions (tangential modes), medium-frequency modes (700-850 cm(-1)) whose oscillations are located on the edges or end caps, and low-frequency modes (300-600 cm(-1)) involving oscillations along the radial directions (radial modes). Broadening of the calculated frequencies is due to the number of nodes in the standing waves of normal modes in the finite-size tubes. In the capped tubes, calculated vibrational frequencies are insensitive to the number of chains (n), whereas in the uncapped tubes, most vibrational frequencies change significantly with an increase in tube length. The discrepancy in the size dependency is reasonably understood by their C-C bonding networks; the capped tubes have similar bond-length alternation patterns within the polyene chains irrespective of n, whereas the uncapped tubes have various bond-deformation patterns. Thus, DFT calculations illuminate that the edge effects have strong impacts on the vibrational frequencies in the finite-size nanotubes.     

Doppler-free two-photon excitation spectroscopy and the Zeeman effects. Perturbations in the 14(0)1 and 1(0)(1)14(0)1 bands of the S1 <-- S0 transition of C6D6

Doppler-free two-photon excitation spectra and the Zeeman effects for the 1 band of the S1 1B2u <-- S0 1A1g transition in gaseous benzene-d6 were measured. Although the spectral lines were strongly perturbed, almost all of the lines near the band origin could be assigned. From a deperturbation analysis, the perturbation near the band origin was identified as originating from an anharmonic resonance interaction. Perturbation centered at K = 28-29 in the 14(0)1 band was analyzed, and it was identified as originating from a perpendicular Coriolis interaction. The symmetry and the assignment of the perturbing state proposed by Schubert et al. (Schubert, U.; Riedle, E.; Neusser, H. J. J. Chem. Phys. 1989, 90, 5994.) were confirmed. No perturbation originating from an interaction with a triplet state was observed in both bands. From the Zeeman spectra and the analysis, it is demonstrated that rotationally resolved levels are not mixed with a triplet state. The intersystem mixing is not likely to occur at levels of low excess energy in the S1 state of an isolated benzene. Nonradiative decay of an isolated benzene in the low vibronic levels of the S1 state will occur through the internal mixing followed by the rotational and vibrational relaxation in the S0 state.     

Azulene-substituted aromatic amines. synthesis and amphoteric redox behavior of N,N-Di(6-azulenyl)-p-toluidine and N,N,N',N'-tetra(6-azulenyl)-p-phenylenediamine and their derivatives

[reaction: see text] N,N-Di(6-azulenyl)-p-toluidine (1a) and N,N,N',N'-tetra(6-azulenyl)-p-phenylenediamine (2a) and their derivatives with 1,3-bis(ethoxycarbonyl) substituents on each 6-azulenyl group (1b and 2b) were prepared by Pd-catalyzed amine azulenylation and characterized as a study into new aromatic amines for multistage amphoteric redox materials. The redox behavior of each compound was characterized by cyclic voltammetry. These compounds undergo facile reduction to stable anion radicals and dianion diradicals owing to the resonance stabilization between the 6-azulenyl groups and exhibit electrochemical oxidation depending on the amine subunits. The ESR measurement of anion radicals and a dianion diradical generated by the electrochemical reduction of amine 1b and diamine 2b revealed that the unpaired electron of these radicals delocalizes over the entire azulene ring including the central nitrogen atoms. UV-vis spectral analysis of amines 1a,b and diamines 2a,b, taken during the electrochemical reduction, exhibited a gradual decrease of the absorption bands of the neutral species along with an increase of the new absorption maxima at 625, 605, 640, and 610 nm, respectively, with the development of well-defined isosbestic points at 502, 562, 478, and 545 nm, respectively. As indicated by a combined ESR and UV-vis spectral study, the species giving rise to the new absorption maxima are concluded to be the generation of anion radicals and dianion diradicals of aromatic amines and diamines with high thermodynamic stability.     

不同爆炸载荷下TA2钛合金圆管膨胀破坏过程

金属柱壳破坏过程与材料、结构及载荷等相关,断裂结果呈现多种形式,采用有限元结合实验对不同爆炸载荷作用下,TA2钛合金圆管的破坏机制开展研究。有限元结果显示:对于理想均质柱壳,由于冲击波传播使壁厚中间形成二次塑性区,圆管壁厚中部的等效塑性应变总是大于内、外壁。在较高爆压下,裂纹在加载阶段从试样壁厚中部起始,沿45°或135°向内外壁剪切扩展;而在较低爆压下,破坏发生在自由膨胀阶段,断裂从内壁起始向外壁剪切扩展,两者破坏过程和机制不同,总体来说,与实验现象符合较好。相关实验中出现的一些外壁拉伸断裂现象,可能与试样的几何、材料缺陷等因素相关,其对金属圆管爆炸破坏的影响值得进一步关注。     

Laser induced memory bits in photorefractive LiNbO3 and LiTaO3

We study experimentally the formation of refractive index voxels (volume elements) in photorefractive LiNbO₃ and LiTaO₃ crystals illuminated with high irradiance femtosecond laser pulses. We used 150 fs pulses at 800 nm wavelength (energy 6–50 nJ) tightly focused inside the crystals in a single shot regime. This resulted in a formation of a micrometer size region of elevated refractive index, which may be used as memory bits in information storage/retrieval application. The maximum refractive index change of 5×10⁻⁴ was recorded in undoped LiNbO₃ at an average light intensity of ∼TW/cm² that is close to the breakdown threshold. A simple setup for photorefractive recording and in situ monitoring of the refractive index changes has been proposed. M. Sūdžius leaves from: the Institute of Materials Science and Applied Research of Vilnius University, Lithuania.     

Preparation of Aqueous Polyurethane Dispersions Using Aromatic Diisocyanate

Aqueous polyurethane dispersions were prepared by the reaction of hydroxyl-terminated poly(ethylene adipate), ethylene glycol, dimethylol propionic acid and aromaic diisocyante, 4,4′-diphenylmethane diisocyanate. The influence of molecular weight of oligoester and molar ratio between isocyanate and hydroxyl groups (NCO/OH) in the prepolymerization step were investigated. Molecular weight, particle size and particle size distribution were measured and compared. It was verified that the molecular weight increases with increasing in NCO/OH molar ratio. The results suggest that the hard segment content plays an important role in particle size and particle size distribution of the dispersions.     

Atomic surfaces, tilings and coincidence I. irreducible case

An irreducible Pisot substitution defines a graph-directed iterated function system. The invariant sets of this iterated function system are called the atomic surfaces. In this paper, a new tiling of atomic surfaces, which contains Thurston’sβ-tiling as a subclass, is constructed. Related tiling and dynamical properties are studied. Based on the coincidence condition defined by Dekking [Dek], we introduce thesuper-coincidence condition. It is shown that the super-coincidence condition governs the tiling and dynamical properties of atomic surfaces. We conjecture that every Pisot substitution satisfies the super-coincidence condition. The second author is supported by a JSPS Postdoc Fellowship.