Investigating Ionic Effects Applied to Water Based Organocatalysed Aldol Reactions

Saturated aqueous solutions of various common salts were examined for their effect on aqueous aldol reactions catalysted by a highly active C2-symmetric diprolinamide organocatalyst developed in our laboratory. With respect to the aldol reaction between cyclohexanone and 4-nitrobenzaldehyde, deionised water was always a superior medium to salt solutions though some correlation to increasing anion size and depression in enantiomeric excess could be observed. Additionally, the complete inhibition of catalyst activity observed when employing tap water could be alleviated by the inclusion of ethylenediaminetetraacetate (EDTA) into the aqueous media prior to reaction initiation. Extension of these reaction conditions demonstrated that these ionic effects vary on a case-to-case basis depending on the ketone/aldehyde combination

A Review of Solvate Ionic Liquids: Physical Parameters and Synthetic Applications

Solvate Ionic Liquids (SILs) are a relatively new class of ionic liquids consisting of a coordinating solvent and salt, that give rise to a chelate complex with very similar properties to ionic liquids. Herein is the exploration of the reported Kamlet-Taft parameters, Gutmann Acceptor numbers and the investigation of chelating effects through NMR spectroscopy of multiple atomic nuclei. These properties are related to the application of SILs as reaction media for organic reactions. This area is also reviewed here, including the implication in catalysis for the Aldol and Kabachnik-Fields reactions and electrocyclization reactions such as Diels-Alder and [2+2] cycloaddition. Solvate ILs exhibit many interesting properties and hold great potential as a solvent for organic transformations

Bioinspired Hard–Soft Interface Management for Superior Performance in Carbon Fibre Composites

Nature has evolved to create materials of unmatched performance governed by the interfacial interactions between hard and soft surfaces. Typically, in a carbon fibre composite, one polymer and one type of carbon fibre is used throughout a laminate. In this work, we use a carbon fibre surface modification approach to vary the fibre–matrix interface throughout the laminate to tailor the soft–hard interfaces. We demonstrate this effect using reclaimed carbon fibre materials in a thermoset polymer, then extend this concept to a thermoplastic polymer matrix–polypropylene. The thermoset specimens examined in this work consist of 5 carbon fibre plies, featuring 0, 1, 3 or 5 surface-modified layers located at the centre of the composite. The largest improvements in physical properties for these composites (yield strength, ultimate flexural strength, and tensile modulus) were found when only 1 modified layer of carbon fibre was placed directly within the centre of the composite. Subsequent investigations revealed that for a polypropylene matrix, where the surface chemistry is tailored specifically for polypropylene, improvements are also observed when mixed surface chemistries are used. This work shows that surface modification of reclaimed carbon fibres as non-woven mats can provide significant improvements in mechanical properties performance for structural composites when used in strategically advantageous locations throughout the composite

Green chemiluminescence from a bis-cyclometalated iridium(III) complex with an ancillary bathophenanthroline disulfonate ligand

The reaction of a fluorinated iridium complex with cerium(IV) and organic reducing agents generates an intense emission with a significant hypsochromic shift compared to contemporary chemically-initiated luminescence from metal complexes

Comparison of solvate ionic liquids and DMSO as an in vivo delivery and storage media for small molecular therapeutics

BACKGROUND: Solvate ionic liquids (SILs) are a new class of ionic liquids that are equimolar solutions of lithium bistrifluoromethanesulfonimide in either triglyme or tetraglyme, referred to as G3LiTFSA and G4LiTFSA, respectively. SILs play a role in energy storage lithium batteries, and have been proposed as potential alternatives to traditional organic solvents such as DMSO. G3TFSA and G4TFSA have been shown to exhibit no toxicity in vivo up to 0.5% (v/v), and solubilize small compounds (N,N-diethylaminobenzaldehyde) with full penetrance, similar to DMSO delivered DEAB. Herein, we compare the effects of storage (either at room temperature or - 20 °C) on DEAB solubilized in either DMSO, G3TFSA or G4TFSA to investigate compound degradation and efficacy. RESULTS: The findings show that DEAB stored at room temperature (RT) for 4 months solubilized in either G3TFSA, G4TFSA or DMSO displayed no loss of penetrance. The same was observed with stock solutions stored at - 20 °C for 4 months; however G4TFSA remained in a liquid state compared to both G3TFSA and DMSO. Moreover, we examined the ability of G3TFSA and G4TFSA to solubilize another small molecular therapeutic, the FGFR antagonist SU5402. G4TFSA, unlike G3TFSA solubilized SU5402 and displayed similar phenotypic characteristics and reduced dlx2a expression as reported and shown with SU5402 in DMSO; albeit more penetrative. CONCLUSION: This study validates the use of these ionic liquids as a potential replacement for DMSO in vivo as organic solubilizing agents

Charge transfer complex formation between organic interlayers drives light-soaking in large area perovskite solar cells

Light soaking (LS) is a well-known but poorly understood phenomenon in perovskite solar cells (PSCs) which significantly affects device efficiency and stability. LS is greatly reduced in large-area inverted PSCs when a PC61BM electron transport layer (ETL) is replaced with C60, where the ETL is commonly in contact with a thin bathocuproine (BCP) interlayer. Herein, we identify the key molecular origins of this LS effect using a combination of surface photovoltage, ambient photoemission spectroscopy, Raman spectroscopy, integrated with density functional theory simulations. We find that BCP forms a photoinduced charge-transfer (CT) complex with both C60 and PC61BM. The C60/BCP complex accelerates C60 dimer formation, leading to a favourable cascading energetic landscape for electron extraction and reduced recombination loss. In contrast, the PC61BM/BCP complex suppresses PC61BM dimer formation, meaning that PC61BM dimerisation is not the cause of LS. Instead, it is the slow light-induced formation of the PC61BM/BCP CT complex itself, and the new energetic transport levels associated with it, which cause the much slower and stronger LS effect of PC61BM based PSCs. These findings provide key understanding of photoinduced ETL/BCP interactions and their impact on the LS effect in PSCs

The effects of social service contact on teenagers in England

Objective: This study investigated outcomes of social service contact during teenage years. Method: Secondary analysis was conducted of the Longitudinal Survey of Young People in England (N = 15,770), using data on reported contact with social services resulting from teenagers’ behavior. Outcomes considered were educational achievement and aspiration, mental health, and locus of control. Inverse-probability-weighted regression adjustment was used to estimate the effect of social service contact. Results: There was no significant difference between those who received social service contact and those who did not for mental health outcome or aspiration to apply to university. Those with contact had lower odds of achieving good exam results or of being confident in university acceptance if sought. Results for locus of control were mixed. Conclusions: Attention is needed to the role of social services in supporting the education of young people in difficulty. Further research is needed on the outcomes of social services contact