Synthesis of new photoresponsive polyesters containing norbornadiene moieties by the ring‐opening copolymerization of donor–acceptor norbornadiene dicarboxylic acid anhydride with donor–acceptor norbornadiene dicarboxylic acid monoglycidyl ester derivatives

The ring‐opening copolymerization of donor–acceptor norbornadiene (D–A NBD) dicarboxylic acid monoglycidyl ester derivatives with D–A NBD dicarboxylic acid anhydride was performed with tetraphenylphosphonium bromide as a catalyst in toluene to produce new norbornadiene (NBD) polyesters containing D–A NBD moieties in the main chain and in the side chain in one step in good yields. The photoisomerization of the D–A NBD moieties in these polyesters proceeded very smoothly to give the corresponding quadricyclane groups. Because these NBD polyesters contained many NBD moieties in the polymer chain, they had the highest capacity for heat storage in the D–A NBD polymers reported so far. The stored thermal energy of the irradiated polyesters was evaluated by differential scanning calorimetry analysis to be approximately 150–190 J/g. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4412–4421, 2005     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

Convenient green preparation of dipeptides using unprotected α-amino acids

Dipeptides and amides were obtained in high yields from N-carbobenzyloxy α-amino acids and 3-phenylpropanoic acid with unprotected α-amino acids via the corresponding mixed carbonic carboxylic anhydrides using ethyl chloroformate and triethylamine by an ecological and convenient method in which the protection of C-terminals is not needed.     

Multiple reflections of Lamb waves at a delamination

Wave propagation in laminated plates with delaminations was calculated using the semi-analytical finite element method. The visualization results and deeper numerical analyses revealed the following phenomena on the fundamental Lamb modes at delamination regions of laminated plates. First, Lamb wave propagates toward the delamination, and then splits into two independent waves at the "Entrance" of the delamination with no significant reflections. These two waves reach the "Exit" of the delamination with the different phases and arrival time. Thus reflected and transmitted waves are excited at the Exit. The repetition of such reflections at the Exit causes the multiple reflections at regular intervals corresponding to the delamination size.     

Flow characteristics of pressure reducing valve with radial slit structure for low noise

Pressure reducing valves are widely used to maintain the pressure of gas reservoirs to specific values. In a normal valve, supply pressure is decompressed with an orifice structure. When compressed air passes through the orifice structure, considerable noise occurs at the downstream side. In this paper, we have developed a radial slit structure that can reduce pressure without noise. The noise is reduced by changing the orifice structure into the radial slit structure. The radial slit structure valve reduces pressure without noise by suppressing the generation of turbulence and shock wave at the downstream. The analysis of the flow in radial slit structure was achieved by CFD2000 software. The flow rate and pressure distribution were simulated and compared with the experimental result. To confirm the generation of shock wave, the flow of orifice and radial slit structure at the downstream was visualized by Schlieren photography method. A shock wave was generated in the orifice structure, but no shock wave was generated in the radial slit structure. Noise reduction efficiency was investigated by the experiment. The experiment apparatus was set up to JIS standards. The experimental results indicated that the noise level decreased by approximately 40 dB in the slit structure. It is confirmed that the radial slit structure has effectiveness for low noise in the pressure reducing flow. And, it is expected that it can be applied to various kinds of industrial fields.     

207Pb chemical shift thermometer at high temperature for magic angle spinning experiments

The temperature dependence of 207Pb chemical shift in magic angle spinning (MAS) NMR spectrum of Pb(NO3)2 provides a sensitive method to calibrate sample temperatures in MAS NMR. The temperature dependence is uniform in the temperature range between 30 degrees C and 400 degrees C. The NMR sensitivity and the line width are also favorable.     

Photodynamic Therapy for Cancer Cells Using a Flash Wave Light Xenon Lamp

We determined photodynamic therapy (PDT) efficacy using a flash wave (FW) and a continuous wave (CW) light, of which the fluence rate was 70 W/cm², for murine thymic lymphoma cells (EL-4) cultivated in vitro. The irradiation frequency and the pulse width of the FW light were in the range of 1–32 Hz and less than one millisecond, respectively. 5-Aminolevulinic acid-induced protoporphyrin IX (ALA-PpIX) was used as a photosensitizer. When EL-4 with ALA administration was irradiated by the light for 4 h (irradiation fluence: 1.0J/cm²), the survival rate of EL-4 by the FW light was lower than that by the CW light, except for the FW light with irradiation frequency of 32 Hz, and decreased gradually with decreasing irradiation frequency. Moreover, the FW light, especially at lower irradiation frequency, was superior to the CW light for the generation of singlet oxygen in an aqueous PpIX solution. Therefore, thehigher PDT efficacy for EL-4 of the FW light would be caused by the greater generation of singlet oxygen in the cells.     

Observation of nonlinear coupling between small-poloidal wave-number potential fluctuations and turbulent potential fluctuations in Ohmically heated plasmas in the JFT-2M tokamak

Two types of electrostatic modes with small-poloidal wave numbers (approximately 1 and 10-15 kHz) are observed in the edge region of Ohmically heated plasmas in the JFT-2M tokamak. The envelope of the higher frequency coherent mode is modulated at the frequency of the lower frequency mode. A bispectral analysis revealed that a significant nonlinear coupling among the two types of fluctuations and the broadband background turbulent potential fluctuations occurs inside the last closed magnetic flux surface, suggesting that a nonlinear process such as the parametric-modulational instability is involved.     

Carbonyl orientation determines regio- and enantioselectivity in 1,2-/1,4-reduction of an NAD model compound

An optically active, axially chiral NAD model compound(1) with a quinoline ring system was reduced by the chiral NADH model compound (4), affording a mixture of 1,2- and 1,4-dihydroquinolines. The carbonyl orientation governs the molecular arrangement in the transition state of the reaction and determines the regio- and enantioselectivity of the product.