Unexpected electron transfer in cryptochrome identified by time-resolved EPR spectroscopy

Subtle differences in the local sequence and conformation of amino acids can result in diversity and specificity in electron transfer (ET) in proteins, despite structural conservation of the redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of the ET partners, and thus the stabilization of the charge-separated states, contribute substantially.     

Glucose concentration determination based on silica sol-gel encapsulated glucose oxidase optical biosensor arrays

Optical biosensor arrays for rapidly determining the glucose concentrations in a large number of beverage and blood samples were developed by immobilizing glucose oxidase (GOD) on oxygen sensor layer. Glucose oxidase was first encapsulated in silica based gels through sol-gel approach and then immobilized on 96-well microarrays integrated with oxygen sensing film at the bottom. The oxygen sensing film was made of an organically modified silica film (ORMOSIL) doped with tris(4,7-diphenyl-1,10-phenanthroline) ruthenium dichloride (Ru(dpp)₃Cl₂). The oxidation reaction of glucose by glucose oxidase could be monitored through fluorescence intensity enhancement due to the oxygen consumption in the reaction. The luminescence changing rate evaluated by the dynamic transient method (DTM) was correlated with the glucose concentration with the wide linear range from 0.1 to 5.0 mM (Y = 13.28X − 0.128, R = 0.9968) and low detection limit (0.06 mM). The effects of pH and coexisting ions were systemically studied. The results showed that the optical biosensor arrays worked under a wide range of pH value, and normal interfering species such as Na⁺, K⁺, Cl⁻, PO₄³⁻, and ascorbic acid did not cause apparent interference on the measurement. The activity of glucose oxidase was mostly retained even after 2-month storage, indicating their long-term stability.     

Spectral Mismatch Effect of Ultraviolet Radiometers in Actual UV-C Measurement

The management of radiant exposure to ultraviolet (UV) radiation, especially in the wavelength range from 100 nm to 280 nm (i.e. UV-C), is important for virus inactivation or photobiological safety. Recently, many commercial UV radiometers have been used to measure UV-C irradiance for industrial and public applications. The accuracy of the four types of commercial UV radiometers was investigated by comparing the reference irradiance values obtained from the spectral irradiance standard. It was found that the displayed values of the UV radiometers have discrepancies, such that the measured value can be more than twice the actual value in a certain case. The spectral mismatch between the calibration and test sources is a major factor in the discrepancies in the UV-C measurements. With spectral mismatch correction, most corrected values show a tendency to improve the result to approaching the reference values within 20%. Users need to provide spectral information about the source and radiometer used for UV-C measurement.     

Electrochemical synthesis of a polypyrrole thin film with supercritical carbon dioxide as a solvent

A conductive polypyrrole (PPy) film was successfully synthesized in a homogeneous supercritical carbon dioxide (scCO2)/acetonitrile (AN) system. The occurrence of a homogeneous supercritical state was confirmed by observations of the phase behavior of the system through a high-pressure cell with a viewing window. The concentration of a supporting electrolyte, tetrabutylammonium hexafluorophosphate (TBAPF6), significantly changed the phase behavior of the scCO2/AN system. The polymerization rate of the film in that system decreased with further addition of CO2. This result suggested that the low viscosity of scCO2 did not play an important role in improving the growth rate of the PPy film. The low polymerization rate might have been due to the electron-transfer resistance arising from the low dielectric constant of scCO2/AN mixture. The roughness of the film prepared in the homogeneous scCO2/AN system was 1/10 that synthesized in AN itself as a solvent. The slow growth of film and the high diffusion rate of the monomer seemed to account for the smooth flat film formation.     

FTIR studies of conformational energies of poly(acrylic acid) in cast films

Fourier transform infrared (FTIR) spectroscopic measurements have been undertaken to estimate the conformational energies of poly(acrylic acid) (PAA) cast films in the temperature range of 40–130°C. The temperature dependence of the IR spectra in the C=O stretching region has been analyzed to yield the side-chain and backbone conformational energies. The estimated energies are close to those previously obtained by polarized Raman spectroscopic measurements for PAA solutions. Combining the FTIR value of conformational energy with the simplified rotational isomeric state (RIS) model proposed in the Raman analysis provides a persistence length in accordance with earlier SAXS experiments. The data also agree with the Gibbs-DiMarzio predictions, further substantiating the validity of the analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 507–515, 1997     

The chemical synthesis of a cyclic oligosaccharide derivative with branching

A cyclic oligosaccharide derivative was synthesized by cationic ring-opening polymerization of an anhydrodisaccharide derivative under high vacuum in dichloromethane with 20 mol% of PF₅ as initiator. Analysis of the spectral results showed that the oligomer chain is composed of only 3 glucose units connected by -1,6 linkages with a glucopyranosyl branching unit at C-4 of each sugar residue in the main chain.     

Formal total synthesis of enigmazole A

A stereoselective formal total synthesis of enigmazole A, a marine macrolide isolated from Cinachyrella enigmatica, is described. Lewis acid mediated intramolecular allylation of an α-acetoxy ether, prepared from alcohol and carboxylic acid fragments was carried out to construct the methylene THP ring with high stereoselectivity. The late-stage macrolactonization of the corresponding seco-acid provided a known synthetic intermediate of enigmazole A.     

Fabrication of Compositional‐Gradient Biodegradable Polymeric Films Showing Self‐Bending Deformation

A compositional graded film of poly(ε‐caprolactone) (PCL) with 4,4′‐thiodiphenol (TDP), in the film thickness direction, was fabricated by self‐diffusing of TDP in the PCL melt. We found out the self‐bending deformation of the gradient film, which bent into a rolled‐up shape by itself. The initial shape of the film was flat when the sample was quenched from the melt. Upon the fast crystallization of PCL, the gradient film bent to the side with low TDP content. Then, after PCL crystallized the film bent to the opposite direction, that is, to the side with high TDP content. This bending to the TDP rich region was induced by not only the crystallization of PCL but also mass transfer due to the diffusion of TDP from TDP rich region to poor region.

     

Electron correlation study for two-electron atoms by a simple correlated wave function

The difference in the electron correlation between H^- and other two-electron atoms is clarified by the introduction of the r₁₂ term in the wave function. By using the expansion of r₁₂, a certain modification of the usual electron correlation factor 1 + Cr₁₂ is introduced and its effectiveness is examined. Calculations are carried out for the ground state and the three lowest excited states (2³S, 2³P and 2¹P). The peculiar electron correlation in the ground state of H^? is shown by looking at the Coulomb hole for closed- and open-shelf models in comparison with those for other two-electron atoms.     

Optical Phase Conjugation in Polyesters with Cyanoazobenzene Units in the Side Chain

Efficient optical phase-conjugate (PC) signals in four kinds of novel polyester films containing cyanoazobenzene units in the side chain are reported. One of them can efficiently generate only the photoinduced anisotropy (PA) component of PC signal, while the other three films can simultaneously generate two types of PC signals, PA and holographic components. These polymers have good potential not only as a phase conjugator but also as a polarization-sensitive hologram-recording material.Presented at the International Commission for Optics Topical Meeting, Kyoto, 1994