Hydrogen atom abstraction by methyl radicals in methanol glasses at 15–100 K: evidence for a limiting rate constant below 40 K by quantum-mechanical tunneling

Rate constants for hydrogen atom abstraction by methyl radicals in methanol glasses have been measured from 100 to 15 K. The Arrhenius plot is nonlinear and the reaction rate constant appears to reach a limiting value below 40 K. The results are discussed in terms of simple models for quantum-mechanical tunneling in the solid state at low temperatures. Assuming that the methyl group rotation in methanol brings about a merging of the energy level distribution at the potential barrier, the observation of temperature-independent rate constants below 40 K may be attributable to a freezing out of this rotation such that tunneling occurs only from the zero-point vibrational level.     

2-methyl tetrahydrofuran radicals formed by γ-radiolysis in the liquid phase

Identification of the radical species formed by γ-radiolysis of MTHF in the liquid phase was made by analysis of the ESR spectra observed from the spin-adducts of the radicals. A new secondary MTHF radical was found in addition to the tertiary radical.     

Extra coupling with sodium of an amino radical adsorbed on the zeolite

ESR spectra were observed from amino radicals adsorbed on the pre-heat-treated zeolite sorbing ammonia molecules. The extra coupling with the sodium ²³Na in the zeolite was observed in the spectrum from the amino-radicals.     

Structures of the hexafluorocyclopropane, octafluorocyclobutane, and decafluorocyclopentane radical anions probed by experimental and computational studies of anisotropic electron spin resonance (ESR) spectra

Anisotropic electron spin resonance (ESR) spectra are reported for the radical anions of hexafluorocyclopropane (c-C(3)F(6)(-)), octafluorocyclobutane (c-C(4)F(8)(-)), and decafluorocyclopentane (c-C(5)F(10)(-)) generated via gamma-irradiation in plastically crystalline tetramethylsilane (TMS) and rigid 2-methyltetrahydrofuran (MTHF) matrices. By combining the analysis of these experimental ESR spectra involving anisotropic hyperfine (hf) couplings with a series of quantum chemical computations, the geometrical and electronic structure of these unusual perfluorocycloalkane radical anions have been characterized more fully than in previous studies that considered only the isotropic couplings. Unrestricted Hartree-Fock (UHF) computations with the 6-311+G(d,p) basis set predict planar ring structures for all three radical anions, the ground electronic states being (2)A(2)(") for c-C(3)F(6)(-) (D(3h) symmetry), (2)A(2u) for c-C(4)F(8)(-) (D(4h)), and (2)A(2)(") for c-C(5)F(10)(-) (D(5h)), in which the respective six, eight, and ten 19F-atoms are equivalent by symmetry. A successful test of the theoretical computation is indicated by the fact that the isotropic 19F hf couplings computed by the B3LYP method with the 6-311+G(2df,p) basis set for the optimized geometries are in almost perfect agreement with the experimental values: viz., 19.8 mT (exp) vs 19.78 mT (calc) for c-C(3)F(6)(-); 14.85 mT (exp) vs 14.84 mT (calc) for c-C(4)F(8)(-); 11.6 mT (exp) vs 11.65 mT (calc) for c-C(5)F(10)(-). Consequently, the same computation method has been applied to calculate the almost axially symmetric anisotropic 19F hf couplings for the magnetically equivalent 19F atoms: (-4.90 mT, -4.84 mT, 9.75 mT) for c-C(3)F(6), (-3.54 mT, -3.48 mT, 7.02 mT) for c-C(4)F(8)(-), and (-2.62 mT, -2.56 mT, 5.18 mT) for c-C(5)F(10)(-). ESR spectral simulations performed using the computed principal values of the hf couplings and the spatial orientations of the 19F nuclei as input parameters reveal an excellent fit to the experimental anisotropic ESR spectra of c-C(3)F(6)(-), c-C(4)F(8)(-), and c-C(5)F(10)(-), thereby providing a convincing proof of the highly symmetric D(nh) structures that are predicted for these negative ions. Furthermore, using the computed 19F principal values and their orientations, the effective 19F anisotropic hf couplings along the molecular symmetry axes were evaluated for c-C(3)F(6)(-) and c-C(4)F(8)(-) and successfully correlated with the positions of the characteristic outermost features in both the experimental and calculated anisotropic spectra. In addition, the electronic excitation energies and oscillator strengths for the c-C(3)F(6)(-) , c-C(4)F(8)(-), and c-C(5)F(10)(-) radical anions were computed for the first time using time-dependent density functional theory (TD-DFT) methods.     

Furopyridines. XXXI. Birch reduction of furopyridines

Birch reduction of four furopyridines 1a‐d effected the characteristic cleavage of the furan ring, giving ethnylpyridinols 2a‐d , vinylpyridinols 3b,d , and ethylpyridinols 4a‐d , and the reduction of the furan ring, giving dihydrofuropyridine 5c,d.     

Observation of electrostatically released DNA from gold electrodes with controlled threshold voltages

DNA oligo-nucleotides, localized at Au metal electrodes in aqueous solution, are found to be released when applying a negative bias voltage to the electrode. The release was confirmed by monitoring the intensity of the fluorescence of cyanine dyes (Cy3) linked to the 5' end of the DNA. The threshold voltage of the release changes depending on the kind of linker added to the DNA 3'-terminal. The amount of released DNA depends on the duration of the voltage pulse. Using this technique, we can retain DNA at Au electrodes or Au needles, and release the desired amount of DNA at a precise location in a target. The results suggest that DNA injection into living cells is possible with this method.     

Transformation of peptide nanotubes into a vesicle via fusion driven by stereo-complex formation

Two types of peptide nanotubes, one is prepared from an amphiphilic peptide having a right-handed helix segment and the other from that having a left-handed helix segment, are shown to transform the morphology into a vesicle by membrane fusion due to stereo-complex formation between these helical segments.     

Stable incorporation of gold nanorods into N-isopropylacrylamide hydrogels and their rapid shrinkage induced by near-infrared laser irradiation

In this study, we prepared gold nanorod (NR)-embedded N-isopropylacrylamide (NIPAM) hydrogels and studied their volume phase transition behavior induced by near-infrared (near-IR) laser irradiation utilizing the photothermal conversion characteristics of the NRs. When poly(ethylene glycol)-modified NRs were used for the preparation of composite gels, the NRs showed marked dispersion stability in the gel. Near-IR laser irradiation of the gel (cylindrical shape, diameter = 140 microm) under the following conditions, NR concentrations in the gel > or =100 microM and laser irradiation power > or =490 mW, resulted in shrinkage of the gel in the following manner: (1) waist formation around the irradiation spot and (2) growth of the waist along the axial directions of the gel. The gel shrinking induced by near-IR irradiation occurred much more rapidly than that afforded by a temperature jump, because the former was not accompanied by the skin layer formation, which disturbs the rapid shrinking of the gels. When a composite gel containing the model drug (rhodamine-labeled dextran) was irradiated with a near-IR laser, the rapid release of the drug was observed. Taking advantage of the high spatial resolution of the irradiation point, we further achieved the irradiation-point-specific release of the drug from one such gel.