Taming of Singlet Oxygen: Towards Artificial Oxygen Carriers Based on 1,4-Dialkylnaphthalenes

Naphthalene endoperoxides are known as convenient sources of singlet oxygen (O₂, ¹Δ_g), which is the major product of endoperoxide cycloreversion reaction. However, their potential as carriers of ground-state molecular oxygen (O₂, ³Σ_g) similar to artificial oxygen carriers remains largely unexplored. This is due to the extreme reactivity and cytotoxic effects of the released singlet oxygen. We now report that a compound with a bimodular design, which incorporates an endoperoxide and an efficient physical quencher of singlet oxygen, 1,4-diazabicyclo[2.2.2]octane (DABCO), produces exclusively ground-state molecular oxygen. This result, coupled with the fact that oxygen release rates from endoperoxides are highly amenable to fine-tuning in a very broad range, and open to targeting by ligand attachment, raises the potential of these compounds far above any comparable chemical, or even biochemical sources. In cell culture experiments, we showed that the addition of the endoperoxide-quencher conjugate can enhance and sustain cell proliferation.     

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation

The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.     

Exact inversion of decomposable interval type-2 fuzzy logic systems

It has been demonstrated that type-2 fuzzy logic systems are much more powerful tools than ordinary (type-1) fuzzy logic systems to represent highly nonlinear and/or uncertain systems. As a consequence, type-2 fuzzy logic systems have been applied in various areas especially in control system design and modelling. In this study, an exact inversion methodology is developed for decomposable interval type-2 fuzzy logic system. In this context, the decomposition property is extended and generalized to interval type-2 fuzzy logic sets. Based on this property, the interval type-2 fuzzy logic system is decomposed into several interval type-2 fuzzy logic subsystems under a certain condition on the input space of the fuzzy logic system. Then, the analytical formulation of the inverse interval type-2 fuzzy logic subsystem output is explicitly driven for certain switching points of the Karnik–Mendel type reduction method. The proposed exact inversion methodology driven for the interval type-2 fuzzy logic subsystem is generalized to the overall interval type-2 fuzzy logic system via the decomposition property. In order to demonstrate the feasibility of the proposed methodology, a simulation study is given where the beneficial sides of the proposed exact inversion methodology are shown clearly.     

Stripping voltammetric analysis of dicofol on graphene-modified glassy carbon electrode

Ionics - This study is related to the development of a highly sensitive and selective electrode for the electroanalysis of dicofol (DCF) by the modification of a glassy carbon electrode (GCE) with...     

Second law analysis of water flow through smooth microtubes under adiabatic conditions

In the study, a second law analysis for a steady-laminar flow of water in adiabatic microtubes has been conducted. Smooth microtubes with the diameters between 50 and 150 μm made of fused silica were used in the experiments. Considerable temperature rises due to viscous dissipation and relatively high pressure losses of flow were observed in experiments. To identify irreversibility of flow, rate of entropy generation from the experiments have been determined in the laminar flow range of Re = 20-2200. The second law of thermodynamics was applied to predict the entropy generation. The results of model taken from the literature, proposed to predict the temperature rise caused by viscous heating, correspond well with the experimental data. The second law analysis results showed that the flow characteristics in the smooth microtubes distinguish substantially from the conventional theory for flow in the larger tubes with respect to viscous heating/dissipation (temperature rise of flow) total entropy generation rate and lost work.     

A high temperature diffraction-resistance study of chalcopyrite, CuFeS2

The electrical, magnetic and structural properties of synthetic chalcopyrite, CuFeS₂, have been studied up to 873 K using DC resistance measurements performed in-situ during neutron powder diffraction experiments. Under ambient conditions the material adopts the accepted structural model for CuFeS₂ in the space group I4?2d, with the magnetic moment of the Fe³⁺ cations aligned along [001]. The electrical resistivity is around 0.3 Ω cm under ambient conditions, consistent with semiconductor character, and decreases slightly with increase in temperature until a more abrupt fall occurs in the region 750-800 K. This abrupt change in resistivity is accompanied by a structural transition to a cubic zinc blende structured phase (space group F4?3m) in which Cu⁺ and Fe³⁺ cations are disordered over the same tetrahedral crystallographic sites and by a simultaneous loss of long-range magnetic order. The implications of these results are discussed in the context of previous studies of the chalcopyrite system.     

Conversion of carbon dioxide to cyclic carbonates using diimine Ru(II) complexes as catalysts

Cationic diimine Ru(II) complexes were synthesized and tested as catalysts for the formation of cyclic organic carbonates from CO₂ and liquid epoxides (propylene oxide, epichlorohydrine, 1,2‐epoxybutane and styrene oxide) which served as both reactant and solvent. The reaction rates not only depended on the type of ligand, but also on reaction conditions such as temperature, pressure, base, the epoxide substrates and the use of an additional solvent. Reaction rates in terms of turnover frequencies up to 4050 mol_product mol_cat.^?1 h^?1 at 99% selectivity were achieved by optimizing the diimine ligand as well as the reaction temperature and CO₂ pressure. Consistent with CV measurements, the electron donating group on the p‐position of the aryl ring accelerated the reaction rate. Copyright © 2008 John Wiley & Sons, Ltd.     

Electroless Pd and Ag deposition kinetics of the composite Pd and Pd/Ag membranes synthesized from agitated plating baths

The atomic absorption spectroscopy (AAS) has been successfully utilized for the measurement of the Pd and Ag ion concentrations in the plating baths and to elucidate the effects of temperature, initial metal ion and reducing agent concentrations and agitation on the electroless plating kinetics of Pd and Ag metals. The initial metal ion concentrations for Pd and Ag were varied over a range of 8.2–24.5 mM and 3.1–12.5 mM, respectively. The plating reactions were conducted in a constant temperature electroless plating bath over a temperature range of 20–60 °C and an initial hydrazine concentration range of 1.8–5.4 mM. It was found that the electroless plating of both Pd and Ag were strongly affected by the external mass transfer in the absence of bath agitation. The external mass transfer limitations for both Pd and Ag deposition have been minimized at or above an agitation rate of 400 rpm, resulting in a maximum conversion of the plating reaction at 60 °C and dramatically shortened plating times with the added advantage of uniform deposition morphology. The derivation of the differential rate laws and the estimation of the reaction orders and the activation energies for the electroless Pd and Ag kinetics were conducted via non-linear regression analysis based on the method of initial rates. For a constant-volume batch reactor, the integrated rate law was solved to calculate the conversion and the reactant concentrations as a function of plating time. The model fits were in good agreement with the experimental data. Furthermore, the bath agitation and the plating conditions used in the kinetics study were adopted for the synthesis of 16–20 μm thick composite Pd/Ag membranes (10–12 wt% Ag) and a pure-Pd membrane with a hydrogen selective dense Pd layer as thin as 4.7 μm. While hydrogen permeance of the Pd/Ag membranes A and B at 450 °C were 28 and 32 m³/m²-h-atm^0.5, the H₂ permeance for the 4.7 μm thick pure-Pd membrane at 400 °C was as high as 63 m³/m²-h-atm^0.5_. The long-term permeance testing of all the membranes synthesized from agitated plating baths resulted in a relatively slow leak growth due primarily to the improved morphology obtained via the bath agitation and modified plating conditions.