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.     

Polarized near-edge x-ray-absorption fine structure spectroscopy of C60-functionalized 11-amino-1-undecane thiol self-assembled monolayer: molecular orientation and evidence for C60 aggregation

Near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy was adopted to probe the unoccupied electronic states of C60 anchored onto an organized assembly of 11-amino-1-undecane thiol on Au(111). The polarization dependence of the intensity of pi* resonance associated with C60 pi network revealed the self-assembled monolayer (SAM) system to be oriented with an average molecular tilt angle of 57 degrees with respect to the surface normal. Invoking the absence of solid-state band dispersion effects and in comparison to solid C60 and /or 1-ML C60/Au(111), the electronic structure of the resulting assembly was found dominated by spectral position shift and linewidth and intensity changes of the lowest unoccupied molecular orbital (LUMO), LUMO+1, and LUMO+2 orbitals. The latter implied hybridization between N Pz of -NH2 group of thiolate SAM and pi levels of C60, resulting in a nucleophilic addition with a change in the symmetry of C60 from Ih to C1 in the SAM. Occurrence of a new feature at 285.3 eV in the NEXAFS spectrum, assigned previously to pi* graphitic LUMO, signified the formation of aggregated clusters, (C60)n of C60 monomer. Low tunneling current scanning tunneling microscopy confirmed them to be spherical and stable aggregates with n approximately 5.     

Molecule-Responsive Fluorescent Sensors of α-Helix Peptides Bearing α-Cyclodextrin, Pyrene and Nitrobenzene Units in Their Side Chains

-Helix peptides bearing one unit of -cyclodextrin (-CD), one unit of pyrene and one unit of nitrobenzene (NB) in their side chains have been designed and synthesized as novel molecule-responsive devices.In both the CD-peptides, -PR17 and -PL17, the NB unit is separated from the CD unit by two turns of the helix. Two reference peptides (PL17, and -P17,) have also been synthesized. The circular dichroism studies in the peptide absorption region (200–250 nm)of -PR17 and -PL17 suggestthat the CD-peptides form stable-helixstructures (83–77%), which was destabilized by accommodating guest molecules (e.g., n-pentanol) into the CD cavity. It suggests that formation of intramolecular host–guest(CD–NB) complex stabilized thehelical structure and exogenous guest molecule excluded the appending NB moiety from inside to outside of the CD cavity, thereby causing destabilization of the helical structure and increasing the random coil content. The ICD spectra of the peptides in the pyrene and nitrobenzene absorption region (250–40 nm) suggest that NB forms inclusion complex with CD. The fluorescence studies revealed that the fluorescence of the pyrene unit is quenched by the NB unit in -PR17 and -PL17. The fluorescence intensity increases with increasing guest concentration for the CD-peptides.This guest-responsiveenhancement in the fluorescence intensity can be explained in terms of increased distance between the pyrene and NB moieties, which is caused by exclusion of the NB moiety from the CD cavity by guest accommodation. Using the guest-responsive fluorescence quenching properties of the CD-peptides, we have obtained binding constants for various short chain alkanols. -PL17 has higher binding affinity to the guest molecules than its isomer, -PR17, indicating that the location of functional groups on the peptide scaffold is important in molecule detection.     

Structure elucidation of AK-toxins,host-specific phytotoxic metabolites produced by alternaria kikuchiana tanaka

The structures of two host-specific phytotoxic metabolites, AK-toxin I and II, isolated from culture broth of Alternaria kikuchiana Tanaka (the fungus causing black spot disease of Japanese pear) were determined to be the ester consisting of N-acetyl-β-methyl-phenylalanine and 9,10-epoxy-8-hydroxy-9-methyl-2E, 4Z, 6E-decatrienoic acid ($\text{1}$) and its β-demethyl derivative ($\text{2}$).     

New chemosensor for larger guests based on modified cyclodextrin bearing seven hydrophobic chains each with a hydrophilic end group

A new chemosensor for larger guests was prepared. The new chemosensor bears hydrophobic units at the primary hydroxy side and a dansyl unit at the secondary hydroxy side of β-cyclodextrin. Due to the hydrophobic units, the new chemosensor is sensitive to large or slender guests such as SDS and insensitive to 1-adamantanol, which is a good guest for the natural β-CD.     

Study of enzyme inhibitory activities by dipyridamole

Inhibitory activities of Dipyridamole (DPM, 2,6-bis(diethanolamino)-4,8-dipiperidinopyrimido(5,4-d)py rim idine) against xanthine oxidase (XO), carbonic anhydorase (CA) and monoamine oxidase (MAO) were studied, in vitro. DPM did not inhibit XO and CA, but it strongly inhibited MAO. The type of inhibition by DPM against MAO with respect to benzylamine as a substrate was uncompetitive.     

Effect of labile hydrogens on measurement of tritium preserved in hydrogens of cellulose

Various f-elements are separated as anionic complexes from both acidic and alkaline solutions by precipitation with alkylpyridinium salts. The precipitates are also cationic surfactants where the simple counter-ion (e.g. nitrate or chloride) is replaced by the negatively charged complex anion of an actinide or lanthanide. The low solubility of these precipitates is explained by a strong affinity of divalent complex counter-ions of f-elements to the quaternary nitrogen. Precipitations in solutions of nitric acid allow to separate tetravalent f-elements from other metals, in alkaline carbonate solutions tetravalent and hexavalent actinides are precipitated simultaneously. The last procedure yields precipitates, which are very intimate mixtures of hexavalent and tetravalent actinides. This allows to prepare mixed oxides in a simple way.     

Facile S-alkyl thiocarbamate synthesis by a novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur

A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of S-alkyl thiocarbamate is observed. The present DBU-assisted carbonylation can also be applied to new synthetic methods for benthiocarb and orthobencarb (herbicides) and carbamoyl chlorides.