Control of photoinduced energy- and electron-transfer steps in zinc porphyrin-oligothiophene-fullerene linked triads with solvent polarity

The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB.     

Sustainable domino Michael reaction catalyzed by a Brønsted base on silica gel: synthesis of bicyclo[2.2.2]octane-2,5-dione derivatives

Domino Michael reactions of oxophorone and its derivatives 4 with Michael partners 3 have been effected to give bicyclo[2.2.2]octane-2,5-dione derivatives 7 by a catalytic amount of a Brønsted base (NMAP-Li) generated from N-methylaminopropylated silica gel (NMAP) and n-BuLi. The NMAP pellets were efficiently reused up to six times in 86% average yield.     

Strange giant resonance in (K −,π−) reaction

We point out a possibility of strange giant resonances that can be excited by the (K ^?,π^?) reaction on nuclear targets. Recent experimental data on⁴⁰Ca are analyzed from this point of view.     

Page usage in a quadtree index

This paper provides a characterization of the storage needs of a quadtree when used as an index to access large volumes of 2-dimensional data. It is shown that the page occupancy for data in random order approaches 33%. A precise mathematical analysis that involves a modicum of hypergeometric functions and dilogarithms, together with some computer algebra is presented.A brief survey of the analysis of storage usage in tree structures is included. The 33% ratio for quadtrees is to be compared to the figures for binary search trees (50%), tries (69%), and quadtries (46%).The research of this author was done while visiting INRIA, Rocquencourt, France under support from the Ministry of Education of Japanese Government.Work of this author was supported in part by the Basic Research Action of the E.C. under contract No. 3075 (Project ALCOM).     

Total synthesis of (+)-obtusenyne

The stereoselective total synthesis of (+)-obtusenyne is described. The oxonene skeleton possessing trans-orientated alkyl substituents at the α,α′-positions was stereoselectively constructed via cyclization of the corresponding hydroxy epoxide promoted by Eu(fod)₃.     

Reversed-phase partition high-pressure liquid chromatography of trace amounts of inorganic and organic mercury with silver diethyldithiocarbamate

Inorganic and organic mercury diethyldithiocarbamates have been separated by reversedphase partition high-pressure liquid chromatography. The mercury chelates were formed by an exchange reaction with silver diethyldithiocarbamate in chloroform, in the presence of acetate buffer (pH 5.0). The inorganic and organic mercury chelates in the extract were separated within 30 min on a 3.9 x 300 mm mu-Bondapak C(18) column. EDTA (10(-4)M) in methanol-water mixture (78:22 v v ) was used as eluent at a flow-rate of 0.5 ml min .     

Effect of Non‐Specifically Adsorbed Ions on the Surface Oxidation of Pt(111)

The oxidation processes of a Pt(111) electrode in alkaline electrolytes depend on non‐specifically adsorbed ions according to in situ X‐ray diffraction and infrared spectroscopic measurements. In an aqueous solution of LiOH, an OH_ad adlayer is formed in the first oxidation step of the Pt(111) electrode as a result of the strong interaction between Li⁺ and OH_ad, whereas Pt oxidation proceeds without OH_ad formation in CsOH solution. Structural analysis by X‐ray diffraction indicates that Li⁺ is strongly protective against surface roughening caused by subsurface oxidation. Although Cs⁺ is situated near the Pt surface, the weak protective effect of Cs⁺ results in irreversible surface roughening due to subsurface oxidation.     

Electrolytic reduction of Tc(VII) in nitric acid solution using glassy carbon electrode

Electroreduction of Tc(VII) was studied in nitric acid solution using glassy carbon electrode. The electroreduction was conducted at a constant potential –300 mV (vs. Ag/AgCl) with a potentiostat. It was found that the difference of the Tc concentration in the solutions before and after the electrolysis was negligibly small. This means that there were almost no TcO₂ or Tc deposited on the carbon fiber electrode during the electroreduction. Absorption spectra and distribution coefficients obtained by ion-exchange analysis indicated that Tc(VII) was reduced to Tc(IV).This work was financed by the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) under the framework of The Development of Innovative Nuclear Technologies.