岩田 耕一

Conjugated polymers incorporated with cycloplatinated complexes (P1-Pt and P2-Pt) were used as dispersants for single-walled carbon nanotubes (SWCNTs). Significant changes in the UV-vis absorption spectra were observed after the formation of the polymer/SWCNT hybrids. Molecular dynamics (MD) simulations revealed the presence of a strong interaction between the cycloplatinated complex moieties and the SWCNT surface. The photoinduced electron transfer processes in these hybrids were strongly dependent on the type of the comonomer unit. Upon photoexcitation, the excited P1-Pt donates electrons to the SWCNT, while P2-Pt accepts electrons from the photoexcited SWCNT. These observations were supported by results from Raman and femtosecond time-resolved transient absorption spectroscopy experiments. The strong electronic interaction between the Pt complexes and the SWCNT gives rise to a new hybrid system that has a controllable photoinduced electron transfer flow, which are important in regulating the charge transport processes in SWCNT-based optoelectronic devices.

The excited-state dynamics of pyrene incorporated into poly(substituted methylene)s is investigated by picosecond time-resolved fluorescence spectroscopy and femtosecond time-resolved near-IR absorption spectroscopy in the 900-1400 nm region. The pyrene rings in poly (substituted methylene)s are photoexcited to the monomer excited state immediately after UV irradiation, followed by prompt excimer formation with time constants of a few picoseconds to a few hundred picoseconds. The excimer formation in poly(substituted methylene)s proceeds with much shorter time constants than that in pyrene-incorporated polyacrylates, vinyl polymer counterparts with the same side-chain structures, indicating the presence of stronger electronic interaction between the pyrene rings in poly(substituted methylene)s. The effects of every methylene substitution hold when each pyrene ring is connected to the polymer backbone with a monomethylene linker, while the effects are observed only weakly when a tetramethylene linker is employed. The results demonstrate the effectiveness of every methylene substitution in the prompt excimer formation of pyrene connected to the polymer backbone either directly or with the monomethylene linker.

Novel regioisomeric alkylated-naphthalene liquids were designed and synthesized. In the solvent-free liquid state, 1-alkyloxy regioisomers showed excimeric luminescence, whereas 2-alkyloxy analogues exhibited monomer-rich luminescence features. Correlations among the molecular structures and the photophysical, calorimetric, and rheological properties are presented, demonstrating the impact of regioisomerism on the alkylated-chromophore liquid systems.

Novel methodologies utilizing pulsed or intense CW irradiation obtained from lasers have a major impact on biological sciences. In this article, recent development in biophysical researches fully utilizing the laser irradiation is described for three topics, time-resolved fluorescence spectroscopy, time-resolved thermodynamics, and manipulation of the biological assemblies by intense laser irradiation. First, experimental techniques for time-resolved fluorescence spectroscopy are concisely explained in Section 2. As an example of the recent application of time-resolved fluorescence spectroscopy to biological systems, evaluation of the viscosity of lipid bilayer membranes is described. The results of the spectroscopic experiments strongly suggest the presence of heterogeneous membrane structure with two different viscosity values in liposomes formed by a single phospholipid. Section 3 covers the time-resolved thermodynamics. Thermodynamical properties are important to characterize biomolecules. However, measurement of these quantities for short-lived intermediate species has been impossible by traditional thermodynamical techniques. Recently, development of a spectroscopic method based on the transient grating method enables us to measure these quantities and also to elucidate reaction kinetics which cannot be detected by other spectroscopic methods. The principle of the measurements and applications to some protein reactions are reviewed. Manipulation and fabrication of supramolecues, amino acids, proteins, and living cells by intense laser irradiation are described in Section 4. Unconventional assembly, crystallization and growth, amyloid fibril formation, and living cell manipulation are achieved by CW laser trapping and femtosecond laser-induced cavitation bubbling. Their spatio-temporal controllability is opening a new avenue in the relevant molecular and bioscience research fields. This article is part of a Special Issue entitled “Biophysical Exploration of Dynamical Ordering of Biomolecular Systems” edited by Dr. Koichi Kato.

© 2018 the Owner Societies. The electronic and vibrational relaxation of carotenoids is one of the key processes in the protection of living cells as well as in the functions of proteins involved in photosynthesis. In this study, the electronic and vibrational relaxation dynamics of β-carotene and its derivatives with substituents on the terminal rings is investigated using femtosecond time-resolved absorption and stimulated Raman spectroscopy in the near-IR region. The carbonyl substituent induces low-frequency shifts of the steady-state and transient absorption bands, decreases of the excited-state lifetimes and the acceleration of vibrational relaxation of the conjugated main chain, whereas the hydroxyl substituent only slightly affects them. The effects of the carbonyl group in the electronic relaxation dynamics are explained well by the lengthening of effective conjugation by the carbonyl group through a partial conjugation between the main chain and the terminal ring. Time-resolved near-IR stimulated Raman spectroscopy demonstrates the significance of the peripheral substitution with the carbonyl group for the vibrational energy relaxation of β-carotene derivatives in the lowest excited singlet state.