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.     

Polyhydroxy pregnanes from Dregea volubilis

Three new polyhydroxy pregnanes named dregealol (1), volubilogenone (2) and volubilol (3) were isolated from the flowers of Dregea volubilis, and their structures elucidated from extensive 2D NMR analysis. The structure of volubilol (3) was confirmed by X-ray crystallographic studies. The known pregnane derivatives drevogenin D, iso-drevogenin P and 17α-marsdenin were also isolated.     

Quantum fluctuation of electronic wave-packet dynamics coupled with classical nuclear motions

An ab initio electronic wave-packet dynamics coupled with the simultaneous classical dynamics of nuclear motions in a molecule is studied. We first survey the dynamical equations of motion for the individual components. Reflecting the nonadiabatic dynamics that electrons can respond to nuclear motions only with a finite speed, the equations of motion for nuclei include a force arising from the kinematic (nuclear momentum) coupling from electron cloud. To materialize these quantum effects in the actual ab initio calculations, we study practical implementation of relevant electronic matrix elements that are related to the derivatives with respect to the nuclear coordinates. Applications of the present scheme are performed in terms of the configuration state functions (CSF) using the canonical molecular orbitals as basis functions without transformation to particular diabatic basis. In the CSF representation, the nonadiabatic interaction due to the kinematic coupling is anticipated to be rather small, and instead it should be well taken into account through the off-diagonal elements of the electronic Hamiltonian matrix. Therefore it is expected that the nonadiabatic dynamics based on this CSF basis neglecting the kinematic coupling may work. To verify this anticipation and to quantify the actual effects of the kinematic coupling, we compare the dynamics with and without the kinematic-coupling terms using the same CSF set. Applications up to the fifth electronically excited states in a nonadiabatic collision between H(2) and B(+) shows that the overall behaviors of these two calculations are surprisingly similar to each other in an average sense except for a fast fluctuation reflecting the electronic time scale. However, at the same time, qualitative differences in the collision events are sometimes observed. Therefore it turns out after all that the kinematic-coupling terms cannot be neglected in the CSF-basis representation. The present applications also demonstrate that the nonadiabatic electronic wave-packet dynamics within ab initio quantum chemical calculation is feasible.     

Isolation, characterization, and theoretical study of La2@C78

A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5).     

Direct UHV-TEM observation of palladium clusters on a silicon surface.

About 1 monolayer of palladium was deposited onto a silicon (111) 7 x 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 x 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 x 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 x 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 x 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 x 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described.     

A facile synthesis of aliphatic polybenzoxazoles from a bis(o-aminophenol) or its hydrochloride and aliphatic dinitriles

A facile one-step method for the synthesis of aliphatic polybenzoxazoles has been developed. Thus, a series of aliphatic polybenzoxazoles having inherent viscosities of 0.2–0.7 dL/g in concentrated sulfuric acid were successfully synthesized by the melt polycondensation of alipatic dinitriles with 4,4′-diamino-3,3′-dihydroxybiphenyl (AHB) or its hydrochloride (AHB–HCl) with the elimination of ammonia or ammonium chloride, respectively. Monomer AHB–HCl was more reactive than the parent AHB, thereby affording higher molecular weight polybenzoxazoles in a shorter reaction time. The aliphatic polybenzoxazoles having 6–10 methylene units were highly crystalline with melting temperatures in the range of 187–308°C, which were stable up to 400°C in a melt state in nitrogen. © 1994 John Wiley & Sons, Inc.     

SPECTROSCOPY AND FLUORESCENCE QUENCHING OF TYROSINE IN LIMA BEAN TRYPSIN/CHYMOTRYPSIN INHIBITOR AND MODEL PEPTIDES

The effects of citrate ion concentration and pH on the optical spectra and fluorescence decay have been measured for several tyrosine model compounds and lima bean trypsin/chymotrypsin inhibitor, a protein containing one tyrosine at position 69 and seven disulfides but no tryptophan, in order to determine the location and environment of Tyr 69. Tyrosine in the protein is protected from citrate collisional quenching, as indicated by the dynamic quenching constant 9 to 15 times smaller than those for the model peptides. Static quenching remains, with a Stern-Volmer constant of about 1.0 M-1, somewhat smaller than those of L-tyrosine, tyrosine-glutamate, and leucine-tyrosine-leucine. The elevated pKa of Tyr 69, greater than or equal to 11.6, also indicates protein protection from solvent ions. Though Coulomb repulsion of the Glu 70/citrate pair may play a role in the shielding of Tyr 69 from citrate, our measurements indicate that steric effects of the protein structure are more important. Tyrosinate emission in the protein at neutral pH is minimal.     

Room Temperature Solid State Reaction Involving Structural Transformation of Covalent Oxide Network

An interesting structural transformation from a two dimensional (2d) covalent oxide network with a layered structure to a three-dimensional (3d) network with a tunnel structure was found at room temperature in the mixture of hydrated alkali-metal molybdenum bronze and amorphous alkali-metal molybdate. From various experimental results it was concluded that the transformation was due to a room temperature solid state reaction.