Intramolecular excimer emission of triply bridged [3.3.N](3,6,9)carbazolophanes

The photophysical properties of a series of triply bridged [3.3.n](3,6,9)carbazolophanes ([3.3.n]Cz, n = 3, 4, 5, 6) were studied as a model compound for a fully overlapped carbazole excimer. In these [3.3.n]Cz molecules, a plane angle of the two carbazole moieties changed systematically from nearly parallel to oblique, with increases in the length of the methylene chain n bridging at the 9-position of each carbazole ring. Absorption bands of [3.3.n]Cz showed the blue-shift and the splitting for (1)L(a) <-- (1)A and (1)L(b) <-- (1)A transition bands of the reference carbazole monomer, respectively. These spectral changes in [3.3.n]Cz were explained by Kasha's molecular exciton theory with the distance r and dihedral angle theta between the carbazole moieties in the ground state. In both liquid and glass matrixes, [3.3.n]Cz showed intramolecular excimer emission. The emission peak wavelength changed from 409 nm (n = 6) to 480 nm (n = 3) depending on r in the ground state. The dependence of the peak wavelength on r clearly showed that relative configurations of carbazole moieties in the ground state were preserved even in the excimer states. The smaller radiative rate of the excimer emission than the reference monomer was explained by the dimer symmetry of [3.3.n]Cz.     

Rapid analysis of hydrocarbons and inert gases by a multidimensional gas chromatograph

A combination of a pressure switching system with multiple columns and photoionization detectors makes possible rapid analysis of a mixture of inorganic gases and hydrocarbons. Hydrocarbons are separated by a narrow bore capillary column. An alumina PLOT column is used for the separation of lower molecular weight hydrocarbons, especially C4 isomers, while a combination of a micro-packed column with Porapak N and a PLOT capillary column with Molecular Sieve 5A is used for the fast separation of inorganic gases. A photoionization detector is a powerful additional tool for organic gas analysis.     

Flow-through micro sensor using immobilized peroxidase with chemiluminometric FIA system for determining hydrogen peroxide.

A micromachined flow cell (overall size; 25 x 25 x 1 mm3) was designed for the fast determination of hydrogen peroxide, based on a luminol-H2O2 chemiluminescence reaction catalyzed by immobilized peroxidase (POD). The flow cell consisted of a sandwich of anisotropically etched silicon and glass chips and contained a spiral channel (20 turns, 50 cm long, 150 microm wide, 20 microm depth, channel volume 1.4 microl) and two holes (1 mm diameter). POD was covalently immobilized with 3-(trimethoxysilyl)propyldietylenetriamine and glutaraldehyde on the inner surface of the channel. The chip was placed in front of a window of a photomultiplier tube and used as a flow cell in a single-line flow-injection analysis system using a luminol solution as a carrier solution. The sample volume for one measurement was 0.2 microl. The maximal sampling rate was 315 h(-1) at a carrier solution flow rate of 10 microl min(-1). A calibration graph for H2O2 was linear for 5 nM - 5 microM; the detection limit (signal-to-noise = 3) was 1 nM (7 fg in 0.2 microl injection). The H2O2 concentration in rainwater was determined using this sensor system.     

Polymerization of five-, six-, and seven-membered ring lactams by using metallic potassium or metallic aluminum alkylate as catalyst and certain N-acyl lactams or diphenyl ketene as initiator

Polymerization of five-, six-, and seven-membered lactams by metallic potassium or MAlEt₄ (where M is Li, Na, or K) as a catalyst and N-acyl lactam or diphenylketene as an initiator was carried out at temperatures below 80°C. By using MAlEt₄ instead of a metallic potassium catalyst in the polymerization of α-piperidone the propagation was continued until the reduced viscosity of polymer reached a value of 0.9. The polymer obtained has a film-forming ability. The experimental results obtained in the gasometry suggest that MAlEt₄ reacts with lactam to form such a complex of the type (where M is Li, Na, or K and X is an ethyl or 2-oxo-alkylene-imine group). The resulting complexes are considered to increase the solubility of catalyst and also to protect the polymer endgroups from side reactions by stabilizing the alkali metal as the complex. In addition, the mode of action of diphenylketene as an initiator was revealed by the facts that the corresponding N-diphenylacetyl lactam was obtained from the reaction of diphenyl ketene with lactam and N-diphenylacetyl lactam itself was useful for the polymerization of α-piperidone.     

Metal cation extraction properties of linear all-ortho phenolic oligomers

A series of ethyl acetate (nBP-Es) and trioxyethylene ether (nBP-OE) derivatives of linear all-ortho methylene-linked oligomers of p-tert-butylphenol (n = 1–7) were prepared, and cation extraction properties were determined. For alkali metal cations, nBP-Es showed the affinity, and especially 5BP-Es showed the selectivity for Na⁺. On the other hand, nBP-OE also showed sufficient affinity; however, the extraction behavior was completely different from that of nBP-Es, that is, the affinity of even membered BP-OE was higher than that of the odd membered. nBP-Es extracted cations by forming a cavity winding around them, while nBP-OE extracted with two trioxyethylene chain picking up cations. For alkaline earth metal cations, nBP-Es extracted more than that for alkali cations. Particularly, 7BP-Es showed the highest affinity for larger cations, Sr²⁺ and Ba²⁺, among phenolic oligomers and 18-crown-6 compound. On the other hand, nBP-OE showed a lower affinity than that for alkali cations. It was concluded that the linear phenolic oligomers extracted alkali and alkaline earth metal cations and the kind of ion ligand introduced influenced the affinity and the selectivity. © 1996 John Wiley & Sons, Inc.     

Dynamic instability of truncated conical shells under periodic axial load

Based on the Dynamic version of Donnell type basic equations neglecting bending deformations before instability, the parametric instability of truncated conical shells subjected to periodic axial load is studied under four different boundary conditions. Applying Galerkin's method, the basic equations are reduced to a system of coupled Mathieu equations, from which the instability regions are determined by using Hsu's results. As a numerical example, instability regions for a completely clamped shell are determined for relatively wide range of frequencies. The effects of static axial load as well as damping force on the instability regions are also examined.     

Optically stimulated luminescence (OSL) study of synthetic stishovite

Optically stimulated luminescence (OSL) of synthetic stishovite was investigated for a future dating technique of meteor impact craters. Luminescence around 330 nm was measured on the γ-ray irradiated stishovite under two stimulating light sources of infrared laser (830 nm) and blue light emitting diode set (470 nm). Thermoluminescence (TL) studies before and after the OSL measurements showed the intensities around 100–200°C and 220–350°C to increase and those around 350–450°C to decrease. This indicates that a part of deep-trapped charges excited during the OSL measurements were retrapped by shallower traps. The infrared stimulated luminescence (IRSL) after the TL measurement up to 450°C could not be detected, while the blue light stimulated luminescence (BLSL) after TL had about one-tenth of the intensity before TL. This indicates that a part of the charges in shallower traps were detrapped thermally and returned to the deeper traps which were related to BLSL. The result implies that some of the BLSL-related traps are quite stable at room temperature and could be used for geological dating. In addition, two paramagnetic centers produced by sudden release of high pressure in synthesis process were found in the unirradiated stishovite by electron spin resonance (ESR). Their g-factors are g=2.00181 and g=2.00062 for an axial signal and g=2.00305 for the other isotropic signal. These signals could be used for an evidence of impacts if those signals could be stored in geological time.     

Aromatization of enamines promoted by a stoichiometric amount of palladium(II) salts: a novel method for the synthesis of aromatic amines.

Enamines (1a-r) prepared from cyclohexanones, cyclohexane-1,3-diones, or tetralones led to arylamines (2a-r) in one pot when treated with a stoichiometric amount of palladium salts [PdCl2-(MeCN)2] in acetonitrile in the presence of triethylamine at room temperature or at elevated temperature, in some cases for 5 min to 2 h. The initial electrophilic attack of palladium chloride on the beta-carbon of the enamines led to a sigma-palladium species (8) which triggered a series of reactions (-->9-->10-->11-->12) destined for aromatization to give 2a-r in good yields. The intervention of such a sigma-palladium species has been attested by a trapping experiment. On the basis of this reaction mechanism, we have developed another new process capable of transforming acyclic compounds having 6-en-2-one frameworks (16, 23, 25) to arylamines (2s-u) when their enamines were treated under the similar conditions as above, featuring again the formation of sigma-palladium species such as 8 as the initial key intermediate.     

彩色胶片与数字照相的成像效率分析及对其未来的预测

本文作者曾经通过评估成像效率的当前状态和理论极限之间的差距以及分析产生此差距的原因预测过卤化银照相材料的未来发展.本文描述了采用上述的方法来评估和分析彩色胶片与数字照相的现状.经预测在未来前者成像效率的改进余地会远大于后者.