Optical sensing and switching with designed molecules

Abstract: Some of the recent research in optical sensor and switch molecules at Queen’s University of Belfast is outlined. The ion-induced absorption spectral changes of molecules with ICT (Internal Charge Transfer) excited states are used to demonstrate superposed logic where multiple logic configurations are simultaneously observable. Similar spectral effects in multi-receptor structures give rise to XOR logic. The ion-induced luminescent spectral changes of molecules with ICT excited states can be combined with the phenomenon of Photoinduced Electron Transfer (PET) to exemplify tristable systems. Insights can also be gained into the luminescence effects initiated in designed molecules by transition metal ions in non-aqueous media. The ion-induced luminescent spectral changes of PET systems with one or two receptors display YES and AND logic respectively. The latter yield coincidence sensors for the direct detection of ion pairs. Overall, interesting optical sensors and switches can be produced from rather small molecules when the latter are fitted with ion-receptors.peer-reviewe

Molecular Memory with Downstream Logic Processing Exemplified by Switchable and Self-indicating Guest Capture and Release

Molecular-logic based computation (MLBC) has grown by accumulating many examples of combinational logic gates and a few sequential variants. In spite of many inspirations being available in biology, there are virtually no examples of MLBC in chemistry where sequential and combinational operations are integrated. Here we report a simple alcohol-ketone redox interconversion which switches a macrocycle between a large or small cavity, with erect aromatic walls which create a deep hydrophobic space or with collapsed walls respectively. Small aromatic guests can be captured or released in an all or none manner upon chemical command. During capture, the fluorescence of the alcohol macrocycle is quenched via fluorescent photoinduced electron transfer switching, meaning that its occupancy state is self-indicated. This represents a chemically-driven RS Flip-Flop, one of whose outputs is fed into an INHIBIT gate. Processing of outputs from memory stores is seen in the injection of packaged neurotransmitters into synaptic clefts for onward neural signalling. Overall, capture-release phenomena from discrete supermolecules now have a Boolean basis

Encapsulation in an alginate–goats’ milk–inulin matrix improves survival of probiotic Bifidobacterium in simulated gastrointestinal conditions and goats’ milk yoghurt

In this work, a new encapsulating matrix, alginate–goats’ milk–inulin, was used to encapsulate Bifidobacterium animalis subsp. lactis BB‐12. The addition of inulin resulted in capsules with a compact structure, and a higher probiotic cell count under simulated gastrointestinal conditions and in probiotic goats’ milk yoghurt during refrigerated storage. Encapsulation of the probiotic bacteria led to slower post‐acidification yoghurts. The results of this study showed that the alginate–goats’ milk–inulin matrix has potential to be used as a new encapsulation material to encapsulate probiotics for use in goats’ milk‐based probiotic fermented dairy products, avoiding the cross‐contamination caused by using capsules based on cows’ milk

Three-dimensional quantitative porosity characterization of syringe- versus hand-mixed set epoxy resin root canal sealer

© 2015, Associacao Brasileira de Divulgacao Cientifica. All rights reserved.The aim of the present study was to compare the porosity characteristics of AH Plus Jet™ syringe-mix and the conventional hand-mixed AH Plus root canal sealers by three-dimensional quantitative high-resolution micro-computed tomography (micro-CT). Seven test specimens were prepared from each tested sealer by a single operator following the manufacturer’s instructions and poured into pre-lubricated plastic split-ring moulds. Set sealer test specimens were scanned using a micro-CT device and the shadow images were reconstructed into cross-sectional slices. The evaluated parameters were (i) total pore count, (ii) total pore volume and mean pore volume, (iii) total porosity (% of pore volume in relation to total sealer volume) and (iv) mean pore distance to the sealer lateral external surface. In both groups, most pores were localized within the external sealer perimeter (0.05 mm from the external surface). Hand-mixed AH Plus specimens showed statistically significant higher mean total pore count, total pore volume and total porosity (p=0.001) than the syringe-mixed specimens. However, mean pore sizes in AH Plus syringe-mixed specimens were significantly higher (p=0.046) than the AH Plus hand-mixed counterparts. Hand-mixed AH Plus was associated with higher total mean pore count, volume and total porosity compared to syringe mixed AH Plus.Link_to_subscribed_fulltex

Synthesis and Characterization of a Heteroleptic Ru(II) Complex of Phenanthroline Containing Oligo-Anthracenyl Carboxylic Acid Moieties

In an effort to develop new ruthenium(II) complexes, this work describes the design, synthesis and characterization of a ruthenium(II) functionalized phenanthroline complex with extended π-conjugation. The ligand were L1 (4,7-bis(2,3-dimethylacrylic acid)-1,10-phenanthroline), synthesized by a direct aromatic substitution reaction, and L2 (4,7-bis(trianthracenyl-2,3-dimethylacrylic acid)-1,10-phenanthroline), which was synthesized by the dehalogenation of halogenated aromatic compounds using a zero-valent palladium cross-catalyzed reaction in the absence of magnesium-diene complexes and/or cyclooctadienyl nickel (0) catalysts to generate a new carbon-carbon bond (C-C bond) polymerized hydrocarbon units. The ruthenium complex [RuL1L2(NCS)2] showed improved photophysical properties (red-shifted metal-to-ligand charge-transfer transition absorptions and enhanced molar extinction coefficients), luminescence and interesting electrochemical properties. Cyclic and square wave voltammetry revealed five major redox processes. The number of electron(s) transferred by the ruthenium complex was determined by chronocoulometry in each case. The results show that processes I, II and III are multi-electron transfer reactions while processes IV and V involved one-electron transfer reaction. The photophysical property of the complex makes it a promising candidate in the design of chemosensors and photosensitizers, while its redox-active nature makes the complex a potential mediator of electron transfer in photochemical processes

Fluorescent logic systems for sensing and molecular computation: structure–activity relationships in edge-detection

Molecular logic-based computation continues to throw up new applications in sensing and switching, the newest of which is the edge detection of objects. The scope of this phenomenon is mapped out by the use of structure-activity relationships, where several structures of the molecules and of the objects are examined. The different angles and curvatures of the objects are followed with good-fidelity in the visualized edges, even when the objects are in reverse video