High pressure FTIR study of intramolecular hydrogen bonding and conformation of a small peptide in solution

Effect of pressure on conformational equilibria of a small peptide N-acetyl-l-Pro-l-Leu-Gly-NH₂ in a chloroform solution has been studied by FTIR spectroscopy. Absorption in the NH stretching region was measured at pressures in the 1–1080 bar range and at 296 K, and decomposed into component bands by least-squares fitting. Intensity ratios of bands which were assigned to a hydrogen-bond-free conformer and intramolecularly hydrogen-bonded conformers with 10- and 13-membered hydrogen bonded rings, respectively, were examined as a function of pressure. It was found that the conformer with the 13-membered ring has definitely smaller partial molar volume than the other two conformers which have nearly the same volume with each other. On the basis of a simple dielectric model, we have shown that the conformer with the 13-membered hydrogen-bonded ring has a considerably large dipole moment which is consistent with the α-helical structure suggested by the previous variable-temperature FTIR study.     

AMPHIPHILIC COPOLYMERS AS MEDIA FOR LIGHT-INDUCED ELECTRON TRANSFER-II. ELECTROSTATIC EFFECT ON THE BACK ELECTRON TRANSFER

Abstract— Photosensitized reduction of zwitterionic viologen (SPV) and methyl viologen (MV²⁺) was investigated using an amphiliphilic copolymer having phenanthryl and sulfonate groups (APh) as photosensitizer in aqueous solutions. In the presence of triethanolamine the accumulation of SPV * (photoproduct) was found to be faster than that of MV⁺. This attributed to the electrostatic repulsion between SPV. and anionic segments of APh. Such difference between SPV and MV²⁺ was minimized in the case of the related monomer model. Retardation of the back reaction for the APh-SPV system was also demonstrated by laser photolysis, k _b= 8.7 × 10⁷ M ^-1 s^-1 for the polymer system as compared to k _b= 2.8 × 10⁹ M ^-1 s^-1 for the monomer model system. Strong salt-effects on the yield of the photoreduction and the rate of back reaction confirm the strong electrostatic interaction between the photoproducts and polyanions. This remarkable electrostatic effect of the polyanions was simulated by electrochemical redox reactions by using a graphite electrode coated with APh.     

2-Pyridone and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives: a new class of hydrogen bond equivalents of uracil

Hydrogen bond complex stability between adenine (A) and hydrogen bond equivalents of uracil: 2-pyridone derivatives (U^X _X2O) and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives (U^X _SO2) was studied, and as the result, the hydrogen bond energy of U^X _X2O-A and a complex of UX^X _SO2-A, was about 1.5 kcal/mol more stable than that of the corresponding adenine-uracil derivatives complex, respectively. The energy difference between the imide tautomer and enol tautomer was smaller than those of uracil derivatives. U^F _SO2 can form a stable complex with A, and its imide tautomer is stable.     

Synthesis of poly (ether-sulfone-amide)s by palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structure,aromatic diamines,and carbon monoxide

A general method for the preparation of aromatic poly (ether-sulfone-amide)s has been developed. Polymerization is based on the palladium-catalyzed polycondensation of aromatic dibromides containing ether sulfone structural units, aromatic diamines, and carbon monoxide. Reactions were carried out in N, N-dimethylacetamide (DMAc) in the presence of palladium catalyst, triphenylphosphine, and 1,8-diazabicyclo [5,4,0]–7–undecene (DBU), and gave a series of poly (ether-sulfone-amide)s with inherent viscosities up to 0.86 dL/g under mild conditions. The polymers were quite soluble in strong acids, dipolar aprotic solvents, and pyridine. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight losses of the polymers were observed in the range above 470°C in air. The glass transition temperatures of the polymers were around 230°C, which are higher than those of poly (ether-sulfone) analogues. These polymers also showed the good tensile strengths and tensile modulus. © 1994 John Wiley & Sons, Inc.     

Revisiting the Rate-Limiting Step of the ANS–Protein Binding at the Protein Surface and Inside the Hydrophobic Cavity

8-Anilino-1-naphthalenesulfonic acid (ANS) is used as a hydrophobic fluorescence probe due to its high intensity in hydrophobic environments, and also as a microenvironment probe because of its unique ability to exhibit peak shift and intensity change depending on the surrounding solvent environment. The difference in fluorescence can not only be caused by the microenvironment but can also be affected by the binding affinity, which is represented by the binding constant (K). However, the overall binding process considering the binding constant is not fully understood, which requires the ANS fluorescence binding mechanism to be examined. In this study, to reveal the rate-limiting step of the ANS–protein binding process, protein concentration-dependent measurements of the ANS fluorescence of lysozyme and bovine serum albumin were performed, and the binding constants were analyzed. The results suggest that the main factor of the binding process is the microenvironment at the binding site, which restricts the attached ANS molecule, rather than the attractive diffusion-limited association. The molecular mechanism of ANS–protein binding will help us to interpret the molecular motions of ANS molecules at the binding site in detail, especially with respect to an equilibrium perspective.     

Surgical effects on soft tissue produced by a 405-nm violet diode laser in vivo

This study evaluated the surgical performance of a 405-nm diode laser in vivo, using living rat liver tissue. Tissue was incised by irradiation with the laser at low output power ranging from 1 W (722 W/cm²) to 3 W (2165 W/cm²) on a manual control at a rate of 1 mm/s. As a control, incisions using a stainless scalpel were compared. Immediately after operation, the surface of the incisions was macroscopically observed and histopathologically evaluated by microscopy. Laser-ablated liver tissue was smooth with observable signs of remnant carbonization and easily acquired hemostasis. The thickness of the denatured layer increased in proportion to the output power; the coagulation layer did not thicken accordingly. Bleeding could not be stopped for tissues incised with the stainless scalpel. The 405-nm diode laser thus proved to be effective for ablating soft tissue with high hemostatic ability at low power.     

Measurement of the spectral distribution of a multi-mode dye laser light by using speckle patterns

A simple method of measuring the wavelength γ₁ and the spectral line spacing Δγ of a multi-mode dye laser light by using the correlated speckle patterns produced at the far-field of a diffuser is proposed. Examples of the obtained values of γ₁ and Δγ are 6.0 × 10³ Å and 3.0 × 10¹ Å, respectively.     

Photodecarbonylation of ruthenium carbonyl octaethylporphyrin via stepwise two-photon absorption of visible light

The photoinduced decarbonylation of a ruthenium(II) carbonyl octaethylporphyrin (RuOEP(CO)(Py)) complex has been shown to occur upon nanosecond pulse laser irradiation as a visible light excitation source, which is reasonably interpreted by a stepwise two-photon absorption process.