Controlling Spatiotemporal Mechanics of Supramolecular Hydrogel Networks with Highly Branched Cucurbit[8]uril Polyrotaxanes

Attempts to rationally tune the macroscopic mechanical performance of supramolecular hydrogel networks through noncovalent molecular interactions have led to a wide variety of supramolecular materials with desirable functions. While the viscoelastic properties are dominated by temporal hierarchy (crosslinking kinetics), direct mechanistic studies on spatiotemporal control of supramolecular hydrogel networks, based on host-guest chemistry, have not yet been established. Here, supramolecular hydrogel networks assembled from highly branched cucurbit[8]uril-threaded polyrotaxanes (HBP-CB[8] ) and naphthyl-functionalized hydroxyethyl cellulose (HECNp) are reported, exploiting the CB[8] host-guest complexation. Mechanically locking CB[8] host molecules onto a highly branched hydrophilic polymer backbone, through selective binary complexation with viologen derivatives, dramatically increases the solubility of CB[8]. Additionally, the branched architecture enables tuning of material dynamics of the supramolecular hydrogel networks via both topological (spatial hierarchy) and kinetic (temporal hierarchy) control. Relationship between macroscopic properties (time- and temperature-dependent rheological properties, thermal stability, and reversibility), spatiotemporal hierarchy, and chain dynamics of the highly branched polyrotaxane hydrogel networks is investigated in detail. Such kind of tuning of material mechanics through spatiotemporal hierarchy improves our understanding of the challenging relationship between design of supramolecular polymeric materials and their complex viscoelasticity, and also highlights a facile strategy to engineer dynamic supramolecular materials.Ministry of Education of Malaysia and Universiti Teknologi MARA, Marie Curie Fellowship. Grant Number: 65836

The Engineering Exchange: widening access to engineering expertise in London

The Engineering Exchange (EngEx) at University College London was established in 2014 to support engagement between engineering researchers and local communities. Building on the 'science shop' tradition within STS, the purpose of the EngEx is to provide community groups with access to engineering expertise and to ensure community needs are reflected in research projects and priorities. The EngEx runs training courses for engineers and researchers, facilitates events to generate collaborative research projects, and responds to ad hoc enquiries from community groups. Projects have addressed a wide range of issues including the demolition and refurbishment of social housing, reintroducing freight transport on London's canals, a community design charette, community infrastructure planning, improving delivery logistics to reduce air pollution, and preservation of an historic steam ship. This paper will present the outcomes of the evaluation of training and research programmes for engineers and community partners, and on the wider university

Mapping SERS in CB:Au Plasmonic Nanoaggregates

In order to optimize surface-enhanced Raman scattering (SERS) of noble metal nanostructures for enabling chemical identification of analyte molecules, careful design of nanoparticle structures must be considered. We spatially map the local SERS enhancements across individual micro-aggregates comprised of monodisperse nanoparticles separated by rigid monodisperse 0.9 nm gaps and show the influence of depositing these onto different underlying substrates. Experiments and simulations show that the gaps between neighbouring nanoparticles dominate the SERS enhancement far more than the gaps between nanoparticles and substrate

Cucurbit[7]uril as a Supramolecular Artificial Enzyme for Diels–Alder Reactions

The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) is a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyse Diels–Alder reactions for a number of substituted and unreactive N-allyl-2-furfurylamines under biomimetic conditions, without the need for protecting groups, yielding powerful synthons in previously unreported mild conditions. CB[7] rearranges the substrate in a highly reactive conformation and shields it from the aqueous environment, thereby mimicking the mode of action of a natural Diels–Alderase. These findings can be directly applied to the phenomenon of product inhibition observed in natural Diels–Alderase enzymes, and pave the way toward the development of novel, supramolecular-based green catalysts.O.A.S. and A.P. acknowledge an ERC starting investigator grant (ASPiRe 240629) and EPSRC Programme Grant (NOtCH, EP/L027151/1) for the support, G.W. thanks the Leverhulme Trust (Natural material innovation for sustainable living) for the support, S.J.B. thanks the European Commission for a Marie Curie Fellowship (NANOSPHERE, 658360), E.R. gratefully acknowledges financial support from EPSRC (EP/N020669/1), E.M. and X.L. acknowledge the American Chemical Society Petroleum Research Fund (PRF No. 51053-ND4), the Department of Chemistry and Biochemistry, the College of Arts and Sciences and the Vice President for Research at Ohio University

Plasmonic tunnel junctions for single-molecule redox chemistry

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots. Here, surface-enhanced Raman spectroscopy allows us to track these hot-electron-induced chemical reduction processes in a series of different aromatic molecules. We demonstrate that by increasing the tunnelling barrier height and the dephasing strength, a transition from coherent to hopping electron transport occurs, enabling observation of redox processes in real time at the single-molecule level.We acknowledge financial support from EPSRC grants EP/G060649/1, EP/I012060/1, EP/L027151/1, ERC grant LINASS 320503. F.B. acknowledges support from the Winton Programme for the Physics of Sustainability. S.J.B. thanks the European Commission for a Marie Curie Fellowship (NANOSPHERE, 658360). M.K. thanks the European Commission for a Marie Curie Fellowship (SPARCLEs, 7020005). P.N. acknowledges support from the Harvard University Center for the Environment (HUCE). R.C. acknowledges support from the Dr Manmohan Singh scholarship from St John’s College. C.C. acknowledges support from the UK National Physical Laboratories. R.S. acknowledges computational resources provided by the Center for Computational Innovations (CCI) at Rensselaer Polytechnic Institute

Gravito-electromagnetic analogies

We reexamine and further develop different gravito-electromagnetic (GEM) analogies found in the literature, and clarify the connection between them. Special emphasis is placed in two exact physical analogies: the analogy based on inertial fields from the so-called "1+3 formalism", and the analogy based on tidal tensors. Both are reformulated, extended and generalized. We write in both formalisms the Maxwell and the full exact Einstein field equations with sources, plus the algebraic Bianchi identities, which are cast as the source-free equations for the gravitational field. New results within each approach are unveiled. The well known analogy between linearized gravity and electromagnetism in Lorentz frames is obtained as a limiting case of the exact ones. The formal analogies between the Maxwell and Weyl tensors are also discussed, and, together with insight from the other approaches, used to physically interpret gravitational radiation. The precise conditions under which a similarity between gravity and electromagnetism occurs are discussed, and we conclude by summarizing the main outcome of each approach.Comment: 60 pages, 2 figures. Improved version (compared to v2) with some re-write, notation improvements and a new figure that match the published version; expanded compared to the published version to include Secs. 2.3 and

Transfer of molecular recognition information from DNA nanostructures to gold nanoparticles

DNA nanotechnology offers unparalleled precision and programmability for the bottom-up organization of materials. This approach relies on pre-assembling a DNA scaffold, typically containing hundreds of different strands, and using it to position functional components. A particularly attractive strategy is to employ DNA nanostructures not as permanent scaffolds, but as transient, reusable templates to transfer essential information to other materials. To our knowledge, this approach, akin to top-down lithography, has not been examined. Here we report a molecular printing strategy that chemically transfers a discrete pattern of DNA strands from a three-dimensional DNA structure to a gold nanoparticle. We show that the particles inherit the DNA sequence configuration encoded in the parent template with high fidelity. This provides control over the number of DNA strands and their relative placement, directionality and sequence asymmetry. Importantly, the nanoparticles produced exhibit the site-specific addressability of DNA nanostructures, and are promising components for energy, information and biomedical applications

Measurement of Beam-Spin Asymmetries for Deep Inelastic π+\pi^+ Electroproduction

We report the first evidence for a non-zero beam-spin azimuthal asymmetry in the electroproduction of positive pions in the deep-inelastic region. Data have been obtained using a polarized electron beam of 4.3 GeV with the CLAS detector at the Thomas Jefferson National Accelerator Facility (JLab). The amplitude of the $\sin\phi$ modulation increases with the momentum of the pion relative to the virtual photon, $z$, with an average amplitude of $0.038 \pm 0.005 \pm 0.003$ for $0.5 < z < 0.8$ range.Comment: 5 pages, RevTEX4, 3 figures, 2 table