Isolation and structure determination of a new lasso peptide subterisin from Sphingomonas subterranea

A new lasso peptide named subterisin was isolated from the culture broth of Sphingomonas subterranea NBRC 16086^T. The molecular formula of subterisin was established as C₇₈H₁₂₁O₂₂N₂₁ based on accurate mass analysis. The chemical structure of subterisin was determined by 2D NMR experiments. The presence of macrolactam ring of Gly1–Glu8 was indicated by NOESY experiment and MS/MS analysis. The three-dimensional structure of subterisin in solution was established by calculation based on NMR data. The proposed biosynthetic gene cluster of subterisin was found on the genome of S. subterranea.     

Multiple Mechanism of NCA Polymerization: Effect of N-Acetylglycine NCA and Related Additives

Polymerization of α-aminoisobutyric acid NCA by alkaline salts of various basicity as well as amines has been investigated. The study was focused on the effect on the initial polymerization rate of additives such as N-acetylglycine NCA and some other less electrophilic additives (l-acetyl-2-pyrrolidone, 3-acetyl-2-oxazolidone, 1-acetyl-3-methylhydantoin) which are all models of the growing chain end produced by the NCA anion pathway. The acetyl endgroup was detected by 250 MHz ¹H-NMR in all the polymers of α-aminoisobutyric acid NCA obtained in the presence of l-acetyl-3-methylhydantoin and triethyl amine or sodium methoxide initiators, whereas the additives influenced variously the kinetics of polymerization according to the nature of the initiator used. The results were interpreted in the light of a multiple mechanism supposing the simultaneous presence of the initiator anion, its conjugate acid, and NCA anion for basic salt initiation. Thus, the observed effect has to be considered as the sum of an elementary acceleration due to NCA anion and of an elementary deceleration due to the initiator anion. Predominance of the pathways involving NCA anion could be shown this way. This conclusion could be extended to γ-benxyl-L-glutamate NCA which is a more reactive NCA. However, the deceleration observed with some additives led us to believe that a nonnegligible participation of initiator anion during initiation cannot be excluded.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).     

Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State

Femtosecond time-resolved absorption and picosecond time-resolved emission measurements were carried out for highly concentrated aqueous solutions of K₂[Pt(CN)₄] to investigate excited-state dynamics of the [Pt(CN)₄²⁻] oligomers formed with metallophilic interactions. Time-resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90-ps and 400-ps dynamics were assigned to the S₁ → T₁ intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency-detected-wavelength 2D analysis revealed that the 135-cm⁻¹ and 65-cm⁻¹ oscillations arise from the Pt–Pt stretch motions of the S₁ trimer and S₁ tetramer, respectively. The obtained time-resolved spectroscopic data provide a clear view of the excited-state dynamics of the [Pt(CN)₄²⁻] oligomers in the femto-/picosecond time region.     

Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time-resolved absorption spectroscopies in the visible to near-infrared and mid-infrared regions. The time-domain vibrational data in the visible region show that the initially formed Franck-Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low-frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time-resolved mid-infrared spectroscopy directly detected the formation of the open-ring isomer with the same time constant as the decrease of the closed-ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed-ring isomer and the open-ring isomer in the ground state.     

Flapping Peryleneimide as a Fluorogenic Dye with High Photostability and Strong Visible‐Light Absorption

Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S₁ excited state. The S₁ planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM).