Stepwise solvatochromism of ketyl anions in the gas phase: photodetachment excitation spectroscopy of benzophenone and acetophenone radical anions microsolvated with methanol

Electronic absorption spectra of bare and methanol-solvated radical anions of benzophenone ((C6H5)2CO) and acetophenone ((C6H5)CH3CO) were measured by monitoring the photodetachment efficiency in the gas phase. Strong absorption bands due to autodetachment after transitions to bound excited states were observed. Stepwise spectral shifts approaching the limit of the condensed phase spectra were found to occur as the cluster size increases. In the case of benzophenone radical anion, the solvation of two methanol molecules exhibits the near convergence to the limit, representing the full coordination with the solvent molecules around the carbonyl group. For the acetophenone case, the coordination number was not apparently determined because of their relatively small shifts. Relationships between hydrogen bonding and electronic structure are analyzed for the spectral shifts with the aid of calculations based on density functional theory. The calculational results show that the coordination angle of the solvent molecule is affected mostly by steric hindrance around the carbonyl group, and that there is no evidence for reorientation due to specific hydrogen bonding interaction with the singly occupied orbital, which has been formerly persisted for an interpretation of the transient absorption following pulse radiolysis in alcoholic solutions. An alternative possibility involving deformation with respect to intramolecular coordinates is discussed.     

Effects of the DNA state fluctuation on single-cell dynamics of self-regulating gene

A dynamical mean-field theory is developed to analyze stochastic single-cell dynamics of gene expression. By explicitly taking account of nonequilibrium and nonadiabatic features of the DNA state fluctuation, two-time correlation functions and response functions of single-cell dynamics are derived. The method is applied to a self-regulating gene to predict a rich variety of dynamical phenomena such as an anomalous increase of relaxation time and oscillatory decay of correlations. The effective "temperature" defined as the ratio of the correlation to the response in the protein number is small when the DNA state change is frequent, while it grows large when the DNA state change is infrequent, indicating the strong enhancement of noise in the latter case.     

Metallo supramolecular assemblies of bis-squaraines by allosteric Ca2+ ion binding

Alkyl chain tethered bis-squaraines bind to Ca2+ ions through the participation of the negatively charged oxygen of the central cyclobutene moiety to form folded H-type aggregates. The initially formed Ca2+ complex is preorganized to facilitate cooperative allosteric binding of Ca2+, resulting in the formation of extended supramolecular arrays. The electronic absorption, IR, and ESI-MS studies support the formation of metallo supramolecular architectures of the folded H-type dimers of the bis-squaraines.     

Pressure-induced structural, magnetic, and transport transitions in the two-legged ladder Sr3Fe2O5

The layered compound SrFeO(2) with an FeO(4) square-planar motif exhibits an unprecedented pressure-induced spin state transition (S = 2 to 1), together with an insulator-to-metal (I-M) and an antiferromagnetic-to-ferromagnetic (AFM-FM) transition. In this work, we have studied the pressure effect on the structural, magnetic, and transport properties of the structurally related two-legged spin ladder Sr(3)Fe(2)O(5). When pressure was applied, this material first exhibited a structural transition from Immm to Ammm at P(s) = 30 ± 2 GPa. This transition involves a phase shift of the ladder blocks from (1/2,1/2,1/2) to (0,1/2,1/2), by which a rock-salt type SrO block with a 7-fold coordination around Sr changes into a CsCl-type block with 8-fold coordination, allowing a significant reduction of volume. However, the S = 2 antiferromagnetic state stays the same. Next, a spin state transition from S = 2 to S = 1, along with an AFM-FM transition, was observed at P(c) = 34 ± 2 GPa, similar to that of SrFeO(2). A sign of an I-M transition was also observed at pressure around P(c). These results suggest a generality of the spin state transition in square planar coordinated S = 2 irons of n-legged ladder series Sr(n+1)Fe(n)O(2n+1) (n = 1, 2, 3, ...). It appears that the structural transition independently occurs without respect to other transitions. The necessary conditions for a structural transition of this type and possible candidate materials are discussed.     

Highly active and tunable catalysts for O2 evolution from water based on mononuclear ruthenium(II) monoaquo complexes

The catalytic activity of [Ru(tpy)(bpy)OH(2)](2+) (tpy = 2,2':6',2'-terpyridine and bpy = 2,2'-bipyridine) increased by a 4'-substituted ethoxy group on the tpy ligand by more than one order of magnitude to give 1.1 × 10(-1) s(-1) of catalyst turnover frequency, which is comparable with the hitherto-reported champion data.     

Generation and amplification of magnetic islands by drift interchange turbulence

We investigate the multiscale nonlinear dynamics of a linearly stable or unstable tearing mode with small-scale interchange turbulence using 2D MHD numerical simulations. For a stable tearing mode, the nonlinear beating of the fastest growing small-scale interchange modes drives a magnetic island with an enhanced growth rate to a saturated size that is proportional to the turbulence generated anomalous diffusion. For a linearly unstable tearing mode the island saturation size scales inversely as one-fourth power of the linear tearing growth rate in accordance with weak turbulence theory predictions. Turbulence is also seen to introduce significant modifications in the flow patterns surrounding the magnetic island.     

Photoexcited States of UV Absorbers,Benzophenone Derivatives

The UV absorption, phosphorescence and phosphorescence‐excitation spectra of benzophenone (BP) derivatives used as organic UV absorbers have been observed in rigid solutions at 77 K. The triplet–triplet absorption spectra have been observed in acetonitrile at room temperature. The BP derivatives studied are 2,2′,4,4′‐tetrahydroxybenzophenone (BP‐2), 2‐hydroxy‐4‐methoxybenzophenone (BP‐3), 2,2′‐dihydroxy‐4,4′‐dimethoxybenzophenone (BP‐6), 5‐chloro‐2‐hydroxybenzophenone (BP‐7) and 2‐hydroxy‐4‐n‐octyloxybenzophenone (BP‐12). The energy levels and lifetimes of the lowest excited triplet (T₁) states of these BP derivatives were determined from the first peak of phosphorescence. The time‐resolved near‐IR emission spectrum of singlet oxygen generated by photosensitization with BP‐7 was observed in acetonitrile at room temperature. BP‐2, BP‐3, BP‐6 and BP‐12 show photoinduced phosphorescence enhancement in ethanol at 77 K. The possible mechanism of the observed phosphorescence enhancement is discussed. The T₁ states of 2‐hydroxy‐5‐methylbenzophenone, 4‐methoxybenzophenone and 2,4′‐dimethoxybenzophenone have been studied for comparison.     

Influencing factors on heterogeneous water oxidation catalysis by di-μ-oxo dimanganese complex on mica as a synthetic model of photosystem II

The influencing factors on heterogeneous water oxidation catalysis (WOC) were investigated in a synthetic photosystem II model developed by adsorbing [(OH₂)(terpy)Mn^III(μ-O)₂Mn^IV(terpy)(OH₂)]³⁺ (terpy = 2,2′:6′,2″-terpyridine) (1) as an oxygen evolving center onto mica. For chemical WOC using a Ce⁴⁺ oxidant, the catalytic activity of 1 on mica increased by a factor of 2.3 or 1.4 by co-adsorption (0.015 mmol g^?1) of redox-inactive trications of Al³⁺ or Ce³⁺ with 1 (0.15 mmol g^?1), respectively, whereas it decreased by co-adsorption (0.25 mmol g^?1) of excess Al³⁺ or Ce³⁺. The cooperative catalysis by two equivalents of the adsorbed 1 for water oxidation could be facilitated by enrichment of 1 by trications at their low co-adsorption conditions. The decreased catalytic activity at high trications co-adsorption conditions could be explained by impeded penetration of Ce⁴⁺ oxidant ions into a mica interlayer. For photochemical WOC containing a [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine) photoexcitation center in mica, the drying treatment at 65 °C under the vacuum after 1 adsorption was required in adsorbate preparation, possibly to maintain favorable arrangement of 1 and [Ru(bpy)₃]²⁺ in a mica interlayer. The drying treatment at 65 °C under the vacuum after [Ru(bpy)₃]²⁺ adsorption inactivated the photochemical WOC. The proton-coupled electron transport from interior [Ru(bpy)₃]²⁺ centers to ones near the surface in mica is considered to be suppressed by the drying treatment, which could be responsible for the inactivated photochemical WOC.     

Dielectric Multilayer Including Azobenzene Polymer Liquid Crystal with Non-quarter-wave Stack

Dielectric multilayer including azobenzene polymer liquid crystal acts as a one-dimensional photonic crystal and has optical-switchable reflection bands. The reflection intensity can be controlled by irradiation of ultraviolet (UV) or visible light, in which the optical switch is based on cis-trans photoisomerization. An increase in the number of layers prevents photoresponse in the multilayer including azobenzen layers because UV or visible light for control cis-trans isomerization hardly reach the bottom of the multilayer due to exponential decay of light intensity. In this study, the multilayer consisting of thin azobenzene layers is investigated. According to numerical calculations, the non-quarter-wave structured multilayer has multiwavelength reflection band. Angular dependence of reflection color from multiwavelength stopband is also studied using the XYZ color space. The non-quarter-wave multilayer suppresses reflection color change compared with conventional quarter-wave multilayer.