Emission from charge recombination during the pulse radiolysis of 9-cyano-10-phenylethynylanthracenes with donor and acceptor substituents

Emission from 9-cyano-10-phenylanthracene and 9-cyano-10-phenylethynylanthracenes having donor and acceptor substituents (RA = PA, PEA, OEA, NEA, and DEA) was studied with the time-resolved fluorescence measurement during the pulse radiolysis of RAs in benzene (Bz). PA and DEA showed only monomer emission, while other RAs (PEA, OEA, and NEA) showed both monomer and excimer emissions with much lower intensities. On the basis of the steady-state and transient absorption and emission measurements, the formation of RA in the singlet excited state ((1)RA*) can be attributed to the charge recombination between RA radical cation and anion (RA*+ and RA*-, respectively) which are initially generated from the radiolytic reaction in Bz. It is expected that for PA with a twisted geometry, the charge recombination between PA*+ and PA*- occurs to give (1)PA* during the pulse radiolysis in Bz. For PEA and OEA, pi-stacking interaction is possible for the formation of an encounter complex during the charge recombination between RA*+ and RA*-. For NEA, it is expected that NEA*+ and NEA*- collide neck-to-neck to generate the excimer due to the twisted geometry. For DEA, a considerably twisted structure is assumed to give (1)DEA* with strong ICT character but not (1)(DEA)2* because of the bulky donor substituent.     

Folding dynamics of cytochrome C using pulse radiolysis

Pulse radiolysis is a powerful method to realize real-time observation of various redox processes, which induces various structural and functional changes occurring in biological systems. However, its application has been mainly limited to studies of the redox reactions of rather smaller biological systems such as DNA because of an undesired reaction due to various free radicals generated by pulse radiolysis. For application of pulse radiolysis to generate plenty of redox reactions of biological systems, selective redox reactions induced by electron pulses have to be developed. In this study, we report that in the presence of the high concentration of the denaturant, guanidine HCl (GdHCl), the selective reduction of the oxidized cytochrome c (Cyt c) takes place in time scales of a few microseconds by the electron transfer from the guanidine radical that is formed by the fast reaction of e(aq)(-) with GdHCl, consequently leading to folding kinetics of Cyt c. By providing insight into the folding dynamics of Cyt c, we show that the pulse radiolysis technique can be used to track the folding dynamics of various biomolecules in the presence of a denaturant including GdHCl.     

Dehydration from conserved stem regions is fundamental for ligand-dependent conformational transition of the adenine-specific riboswitch

Conformational dynamics and observed equilibrium constants for ligand binding of the adenine-specific riboswitch (add-A riboswitch) in the absence of Mg(2+) and presence of various concentrations of poly-ethylene glycol having an average molecular weight of 200 indicated that 54.2 water molecules were released from P2 and P3 stem regions of the add-A riboswitch during conformational transition upon the binding of 2-aminopurine, an analog of the natural ligand adenine.     

Preparation of (Z)-1-fluoro-1-alkenyl carboxylates,carbonates and carbamates through chromium mediated transformation of dibromofluoromethylcarbinyl esters and the reactivity as double acyl group donors

CrCl₂/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl₂/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.     

Improvement in quantitative correction in SIMS using Saha-Eggert equation

Summary Improvement in Quantitative Correction in SIMS Using Saha-Eggert Equation A quantitative conversion of the secondary-ion current intensities into the elemental concentrations using the Saha-Eggert ionization equation was tried with a 78Ni-18Cr-1Ti-1Fe-1Cu-1Zr (each in at %) alloy. Improvements were made on the best-fit search of fitting parameters (T andN _e). It proved to be important for the success in the conversion (1) to use the secondary-ion intensities from the sample in oxygen gas of >1.5×10^–3 Pa, (2) to add the molecularion intensities to those of mother atomic ions even when the former are small and (3) to search for the fitting parameters considering the relative errors of concentrations not only for the internal standards but for as many elements as possible. With these procedures the largest error of elemental concentration could be reduced to 22% (Ar⁺ bombardment), 31% (O₂ ⁺ bombardment) and 19% (N₂ ⁺bombardment).A part of this paper was presented at the 4th International Conference on Secondary Ion Mass Spectrometry, Osaka, November 1983.     

(+)-4-Hydroxysarcocapnine: Structure and stereochemical considerations

(+)-4-Hydroxysarcocapnine obtained from Sarcocapnos enneaphylla (L.) DC. has been shown by spectral studies and synthesis to possess the new 4-hydroxyisocularine structure (1a). Straightforward assignment of the configuration of a 4-hydroxycularine by NMR is also-discussed.     

Spanning Trees Crossing Few Barriers

We consider the problem of finding low-cost spanning trees for sets of $n$ points in the plane, where the cost of a spanning tree is defined as the total number of intersections of tree edges with a given set of $m$ barriers. We obtain the following results: (i) if the barriers are possibly intersecting line segments, then there is always a spanning tree of cost $O(\min(m^2,m\sqrt{n}))$; (ii) if the barriers are disjoint line segments, then there is always a spanning tree of cost $O(m)$; (iii) ] if the barriers are disjoint convex objects, then there is always a spanning tree of cost $O(n+m)$. All our bounds are worst-case optimal, up to multiplicative constants.     

Mössbauer study on Fe0.068Ni0.932Cl2 with competing spin anisotropies

Mössbauer measurements on Fe_0.068Ni_0.932Cl₂ were done at temperatures between 55K and 4.2K. We have found that below T_N-50K an observed spectrum is composed of two kinds of spectra and that the composition ratio changes gradually with temperature. The average angle of Fe²⁺ spins, \(\overline {\theta _{Fe} } \) , with the c-axis is smaller than \(\overline {\theta _c } \) by ?15° at each temperature below T_N, where \(\overline {\theta _c } \) is the average angle of total spins with the c-axis in this system obtained from the neutron scattering measurements. This is reasonably understood if we take into account that Fe²⁺ spins have the strong uniaxial anisotropy along the c-axis. We discuss the coexistence of the two kinds of spectra by considering the exchange energy of Fe²⁺ spins and the local magnetic anisotropy.     

Ultrafast photoinduced intramolecular charge separation and recombination processes in the oligothiophene-substituted benzene dyads with an amide spacer

Photoinduced intramolecular charge separation (CS) and recombination (CR) processes of the tetrathiophene-substituted benzene dyads with an amide spacer (4T-PhR, R = 4-H (1), 4-CN (2), 3,4-(CN)2 (3), 4-NO2 (4), 3,5-(NO2)2 (5)) in solvents of different polarities were investigated using various fast spectroscopies. It was revealed that the CS rates depend on the ability of the acceptor and solvent polarity. Ultrafast CS with the rate of 5 x 10(12) s(-1) was revealed for 5 in PhCN and MeCN. The ultrafast CS can be attributed to the large electronic coupling matrix element between the donor and the acceptor despite the relative long donor-acceptor distance. The existence of the state with large electron density on the spacer between 14T*-PhR and LUMO should facilitate the CS process in the present dyad system. It was also revealed that the CR rates in these dyads were rather fast because of the enhanced superexchange interaction through the amide spacer.