Stimulus-Mediated Ultrastable Radical Formation

Organic radicals are reactive, often short-lived species typically formed through either the addition of a chemical agent or photochemical means. On account of their open-shell electronic structure they have attracted attention based upon their magnetic properties and desirable spectroscopic behaviour. Redox sensitive molecules such as viologen (V) undergo one-electron reductions to form radical species. These species hold significant potential in myriad applications but are limited as they are rapidly quenched by oxygen in air. Using methyl viologen as an example, we show that the MV radical (MV+·) can be formed through electrochemical, chemical, photochemical and a novel thermal stimulus in various Deep Eu- tectic Solvents (DES) and was found to be exceptionally stable. The conductive properties of DES allowed for fabrication of an aerobic electrochromic device through a straightforward, economical approach. Our report represents a unique approach to extend reactive radical lifetimes in air without alteration of the parent structure.J.A.M. would like to acknowledge the EPSRC for a PhD studentship (EP/K503009/1). O.A.S. acknowledges ERC Consolidator grant CAM-RIG (No.726470) and UK Engineering and Physical Sciences Research Council grant EP/L027151/1. M.F.K. and E.R. acknowledge Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group and the EPSRC (IAA Follow-on Fund)

Optical imaging of luminescence for in vivo quantification of gene electrotransfer in mouse muscle and knee

BACKGROUND: Optical imaging is an attractive non-invasive way to evaluate the expression of a transferred DNA, mainly thanks to its lower cost and ease of realization. In this study optical imaging was evaluated for monitoring and quantification of the mouse knee joint and tibial cranial muscle electrotransfer of a luciferase encoding plasmid. Optical imaging was applied to study the kinetics of luciferase expression in both tissues. RESULTS: The substrate of luciferase (luciferin) was injected either intraperitonealy (i.p.) or in situ into the muscle or the knee joint. Luminescence resulting from the luciferase-luciferin reaction was measured in vivo with a cooled CCD camera and/or in vitro on tissue lysate. Maximal luminescence of the knee joint and muscle after i.p. (2.5 mg) or local injection of luciferin (50 μg in the knee joint, 100 μg in the muscle) were highly correlated. With the local injection procedure adopted, in vivo and in vitro luminescences measured on the same muscles significantly correlated. Luminescence measurements were reproducible and the signal level was proportional to the amount of plasmid injected. In vivo luciferase activity in the electrotransfered knee joint was detected for two weeks. Intramuscular electrotransfer of 0.3 or 3 μg of plasmid led to stable luciferase expression for 62 days, whereas injecting 30 μg of plasmid resulted in a drop of luminescence three weeks after electrotransfer. These decreases were partially associated with the development of an immune response. CONCLUSION: A particular advantage of the i.p. injection of substrate is a widespread distribution at luciferase production sites. We have also highlighted advantages of local injection as a more sensitive detection method with reduced substrate consumption. Besides, this route of injection is relatively free of uncontrolled parameters, such as diffusion to the target organ, crossing of biological barriers and evidencing variations in local enzymatic kinetics, probably related to the reaction medium in the targeted organ. Optical imaging was shown to be a sensitive and relevant technique to quantify variations of luciferase activity in vivo. Further evaluation of the effective amount of luciferase in a given tissue by in vivo optical imaging relies on conditions of the enzymatic reaction and light absorption and presently requires in vitro calibration for each targeted organ

Electromagnetically induced transparency in inhomogeneously broadened Lambda-transition with multiple excited levels

Electromagnetically induced transparency (EIT) has mainly been modelled for three-level systems. In particular, a considerable interest has been dedicated to the Lambda-configuration, with two ground states and one excited state. However, in the alkali-metal atoms, which are commonly used, hyperfine interaction in the excited state introduces several levels which simultaneously participate in the scattering process. When the Doppler broadening is comparable with the hyperfine splitting in the upper state, the three-level Lambda model does not reproduce the experimental results. Here we theoretically investigate the EIT in a hot vapor of alkali-metal atoms and demonstrate that it can be strongly reduced due to the presence of multiple excited levels. Given this model, we also show that a well-designed optical pumping enables to significantly recover the transparency

Surface-Bound Cucurbit[8]uril Catenanes on Magnetic Nanoparticles Exhibiting Molecular Recognition.

We demonstrate the preparation of surface-bound cucurbit[8]uril (CB[8]) catenanes on silica nanoparticles (NPs), where CB[8] was employed as a tethered supramolecular "handcuff" to selectively capture target guest molecules. In this catenane, CB[8] was threaded onto a methyl viologen (MV(2+) ) axle and immobilized onto silica NPs. The formation of CB[8] catenanes on NPs were confirmed by UV/Vis titration experiments and lithographic characterization, demonstrating a high density of CB[8] on the silica NPs surface, 0.56 nm(-2) . This CB[8] catenane system exhibits specific molecular recognition towards certain aromatic molecules such as perylene bis(diimide), naphthol and aromatic amino acids, and thus it can act as a nanoscale molecular receptor for target guests. Furthermore, we also demonstrate its use as an efficient and recyclable nano-platform for peptide separation. By embedding magnetic NPs inside silica NPs, separation could be achieved by simply applying an external magnetic field. Moreover, the peptides captured by the catenanes could be released by reversible single-electron reduction of MV(2+) . The entire process demonstrated high recoverability.X. Ren thanks the CSC Cambridge Scholarship for financial support and Dr. Ziyi Yu for template preparation. Y. Wu is financially supported by the EP/L504920/1, J. Liu by the Marie Curie FP7 SASSYPOL ITN (607602) programme, and G. Wu by the Leverhulme Trust.This is the author accepted manuscript. The final version is available from Wiley at http://dx.doi.org/10.1002/asia.201600875

Aryl-viologen pentapeptide self-assembled conductive nanofibers.

A pentapeptide sequence was functionalized with an asymmetric arylated methyl-viologen (AVI3D2) and through controllable β-sheet self-assembly, conductive nanofibers were formed. Using a combination of spectroscopic techniques and conductive atomic force microscopy, we investigated the molecular conformation of the resultant AVI3D2 fibers and how their conductivity is affected by β-sheet self-assembly. These conductive nanofibers have potential for future exploration as molecular wires in optoelectronic applications.ERC (‘ASPiRe’, 240629) Marie Curie (FP7 ‘SASSYPOL’ ITN, 607602

Transparent Films Made of Highly Scattering Particles

Today, colloids are widely employed in various products from creams and coatings to electronics. The ability to control their chemical, optical, or electronic features by controlling their size and shape explains why these materials are so widely preferred. Nevertheless, altering some of these properties may also lead to some undesired side effects, one of which is an increase in optical scattering upon concentration. Here, we address this strong scattering issue in films made of binary colloidal suspensions. In particular, we focus on raspberry-type polymeric particles made of a spherical polystyrene core decorated by small hemispherical domains of acrylate with an overall positive charge, which display an unusual stability against aggregation in aqueous solutions. Their solid films display a brilliant red color due to Bragg scattering but appear completely white on account of strong scattering otherwise. To suppress the scattering and induce transparency, we prepared films by hybridizing them with oppositely charged PS particles with a size similar to that of the bumps on the raspberries. We report that the smaller PS particles prevent raspberry particle aggregation in solid films and suppress scattering by decreasing the spatial variation of the refractive index inside the film. We believe that the results presented here provide a simple strategy to suppress strong scattering of larger particles to be used in optical coatings

Synthesis of Conducting Polymer-Metal Nanoparticle Hybrids Exploiting RAFT Polymerization.

The direct covalent attachment of conducting polymers (CP) to nanoparticles (NP) to form CP-NP nanohybrids is of great interest for optoelectronic device applications. Hybrids formed by covalently anchoring CP to NP, rather than traditional blending or bilayer approaches, is highly desirable. CP-NP nanohybrids have increased interfacial surface area between the two components, facilitating rapid exciton diffusion at the p-n heterojunction. These materials take advantage of the facile solution processability, lightweight characteristics, flexibility, and mechanical strength associated with CPs, and the broad spectral absorption, photostability, and high charge carrier mobility of NPs. We demonstrate the ability to polymerize a hole transporting (HT) polymer utilizing reversible-addition-fragmentation chain transfer (RAFT) polymerization and its subsequent rapid aminolysis to yield a thiol-terminated HT polymer. Subsequent facile attachment to gold (Au) and silver (Ag) NPs and cadmium selenide (CdSe) quantum dots (QDs), to form a number of CP-NP systems is demonstrated and characterized. CP-NP nanohybrids show broad spectral absorptions ranging from UV through visible to the near IR, and their facile synthesis and purification could allow for large scale industrial applications.P.E.W. and S.T.J. contributed equally to this work. E.A.A. thanks Schlumberger for financial support. This work was supported in part by Atomic Weapons Establishment (AWE), the Walters-Kundert foundation, and an ERC Starting Investigator grant (ASPiRe, 240629).This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/mz500645c

Single-molecule force spectroscopy quantification of adhesive forces in cucurbit[8]uril host-guest ternary complexes.

Cucurbit[8]uril (CB[8]) heteroternary complexes display certain characteristics making them well-suited for molecular level adhesives. In particular, the ability to control adhesion through careful choice of host-guest binding pairs enables specific, fully reversible adhesion. Understanding the effect of the environment on the adhesive system is also critical when developing new molecular level adhesives. Here we explore the binding forces involved in the methyl viologen · CB[8] · napthol heteroternary complex using single-molecule force spectroscopy (SMFS) under a variety of conditions. From SMFS, the interaction of a single ternary complex was found to be in the region of 140 pN. Additionally, a number of surface interactions could be readily differentiated using the SMFS technique allowing for a deeper understanding of the dynamic heteroternary CB[8] system on the single-molecule scale.This work was supported in part by the Engineering and Physical Sciences Research Council (EPSRC), the Walters-Kundert Charitable Trust and an ERC Starting Investigator grant (ASPiRe, 240629). ZWK, ERJ, YL thank the Royal Society of Chemistry for a grant allowing travel to Tsinghua University to carry out this research. YY would like to acknowledge financial support from the Young Scientists of the National Science Foundation of China (21304052). YL thanks the Chinese Overseas Scholarship Trust for financial support. JdB thanks the Marie Curie Actions program for financial support. PEW thanks the Atomic Weapons and Energy Commission and the Melville Laboratory for Polymer Synthesis for financial support

Single-molecule force spectroscopy quantification of adhesive forces in cucurbit[8]uril host-guest ternary complexes.

Cucurbit[8]uril (CB[8]) heteroternary complexes display certain characteristics making them well-suited for molecular level adhesives. In particular, the ability to control adhesion through careful choice of host-guest binding pairs enables specific, fully reversible adhesion. Understanding the effect of the environment on the adhesive system is also critical when developing new molecular level adhesives. Here we explore the binding forces involved in the methyl viologen · CB[8] · napthol heteroternary complex using single-molecule force spectroscopy (SMFS) under a variety of conditions. From SMFS, the interaction of a single ternary complex was found to be in the region of 140 pN. Additionally, a number of surface interactions could be readily differentiated using the SMFS technique allowing for a deeper understanding of the dynamic heteroternary CB[8] system on the single-molecule scale.This work was supported in part by the Engineering and Physical Sciences Research Council (EPSRC), the Walters-Kundert Charitable Trust and an ERC Starting Investigator grant (ASPiRe, 240629). ZWK, ERJ, YL thank the Royal Society of Chemistry for a grant allowing travel to Tsinghua University to carry out this research. YY would like to acknowledge financial support from the Young Scientists of the National Science Foundation of China (21304052). YL thanks the Chinese Overseas Scholarship Trust for financial support. JdB thanks the Marie Curie Actions program for financial support. PEW thanks the Atomic Weapons and Energy Commission and the Melville Laboratory for Polymer Synthesis for financial support