Spin-state dynamics of a photochromic iron(II) complex and its immobilization on oxide surfaces via phenol anchors

This work presents a detailed study of the photo-induced spin-state dynamics of the photochromic iron(II) complex 1, where the metal ion is in the field of a tripodal hexa-imine ligand with protolysable phenol groups. The nature of the complex’s ground state has been identified as a spin singlet by ¹H NMR and steady-state UV/vis spectroscopies, and its distorted octahedral structure was analyzed via crystal structure determination. Sub-picosecond and nanosecond time-resolved laser flash photolysis experiments identify the long-lived quintet state of 1 as the selective product of photoexcitation in the UV/vis spectral region. Thermal barriers of spin-state interconversion as a function of solvent and added base are derived from temperature-dependent rates of transient decay. Ground-state recovery is found to be significantly affected by the solvent and is strongly enhanced, in particular, by base-driven solvolysis of the ligand’s phenol groups. Partial spontaneous deprotonation of the phenolic hydroxyl groups of 1 seems to prevail on metal oxide surfaces, i.e. on alumina. Composite materials, like 1 at Al₂O₃, that retain the characteristic spectral features of the parent iron(II) complex can be readily obtained by wet impregnation of hydrous alumina with solutions of 1.     

On the receptivity and nonparallel stability of traveling disturbances in rotating-disk flow

The generation and evolution of small amplitude long wavelength traveling disturbances in rotating-disk flow is the subject of this paper. The steady rotational speed of the disk is perturbed so as to introduce high-frequency oscillations in the flow field. Secondly, we introduce surface imperfections on the disk such as roughness elements. The interaction of these two disturbances will generate the instability waves whose evolution is governed by parabolic partial differential equations which are solved numerically. It is found that, for the class of disturbances considered here (wavelength on the order of Reynolds number), eigensolutions exist which decay or grow algebraically in the radial direction. However, these solutions grow only for frequencies larger than 4.58 times the steady rotational speed of the disk. The computed receptivity coefficient shows that there is an optimum size of roughness for which these modes are preferentially excited. The width of these roughness elements in the radial direction is about 0.1r ₀ ^* where r ₀ ^* is the radial location of the roughness. It is also found that the receptivity coefficient is larger for a negative spanwise wave number than for a positive one. The cumulative wave pattern produced from the roughness site shows that the typical wave angles for these disturbances are about –26° with about seven waves around the circumference. This is in contrast with the wave angles of 10°–14° found for the 30 or so inviscid cross-flow vortices.This work was sponsored by NASA Langley Research Center under Contracts NAS1-18240 (P.B. and M.R.M.) and NAS1-18605 (P.H.).     

On the nonlinear interfacial instability of rotating core-annual flow

The interfacial stability of rotating core-annular flows is investigated. The linear and nonlinear effects are considered for the case when the annular region is very thin. Both asymptotic and numerical methods are used to solve the flow in the core and film regions which are coupled by a difference in viscosity and density. The long-time behavior of the fluid-fluid interface is determined by deriving its nonlinear evolution in the form of a modified Kuramoto-Sivashinsky equation. We obtain a generalization of this equation to three dimensions. The flows considered are applicable to a wide array of physical problems where liquid films are used to lubricate higher- or lower-viscosity core fluids, for which a concentric arrangement is desired. Linearized solutions show that the effects of density and viscosity stratification are crucial to the stability of the interface. Rotation generally destabilizes nonaxisymmetric disturbances to the interface, whereas the centripetal forces tend to stabilize flows in which the film contains the heavier fluid. Nonlinear effects allow finite-amplitude helically traveling waves to exist when the fluids have different viscosities.This research was partially supported by the National Aeronautics and Space Administration under NASA Contract No. NAS1-18605 while the second author was in residence at the Institute for Computer Applications in Science and Engineering (ICASE), NASA Langley Research Center, Hampton, VA 23665. This work was also supported by the Science and Engineering Research Council.     

Three's a crowd – stabilisation,structure, and applications of DNA triplexes

DNA is a strikingly flexible molecule and can form a variety of secondary structures, including the triple helix, which is the subject of this review. The DNA triplex may be formed naturally, during homologous recombination, or can be formed by the introduction of a synthetic triplex forming oligonucleotide (TFO) to a DNA duplex. As the TFO will bind to the duplex with sequence specificity, there is significant interest in developing TFOs with potential therapeutic applications, including using TFOs as a delivery mechanism for compounds able to modify or damage DNA. However, to combine triplexes with functionalised compounds, a full understanding of triplex structure and chemical modification strategies, which may increase triplex stability or in vivo degradation, is essential – these areas will be discussed in this review. Ruthenium polypyridyl complexes, which are able to photooxidise DNA and act as luminescent DNA probes, may serve as a suitable photophysical payload for a TFO system and the developments in this area in the context of DNA triplexes will also be reviewed.

Triplex-forming oligonucleotides can target specific DNA sequences by binding in the duplex major groove. Chemical modifications and ligand binding have been explored, for use in a variety of biological applications.     

Effect of ZnO Nanofiller on Structural and Electrochemical Performance Improvement of Solid Polymer Electrolytes Based on Polyvinyl Alcohol–Cellulose Acetate–Potassium Carbonate Composites

In this study, a solution casting method was used to prepare solid polymer electrolytes (SPEs) based on a polymer blend comprising polyvinyl alcohol (PVA), cellulose acetate (CA), and potassium carbonate (K₂CO₃) as a conducting salt, and zinc oxide nanoparticles (ZnO-NPs) as a nanofiller. The prepared electrolytes were physicochemically and electrochemically characterized, and their semi-crystalline nature was established using XRD and FESEM. The addition of ZnO to the polymer–salt combination resulted in a substantial increase in ionic conductivity, which was investigated using impedance analysis. The size of the semicircles in the Cole–Cole plots shrank as the amount of nanofiller increased, showing a decrease in bulk resistance that might be ascribed to an increase in ions due to the strong action of the ZnO-NPs. The sample with 10 wt % ZnO-NPs was found to produce the highest ionic conductivity, potential window, and lowest activation energy (E_a) of 3.70 × 10^–3 Scm^–1, 3.24 V, and 6.08 × 10^–4 eV, respectively. The temperature–frequency dependence of conductivity was found to approximately follow the Arrhenius model, which established that the electrolytes in this study are thermally activated. Hence, it can be concluded that, based on the improved conductivity observed, SPEs based on a PVA-CA-K₂CO₃/ZnO-NPs composite could be applicable in all-solid-state energy storage devices.