11,042 research outputs found

    DNA modulates solvent isotope effects in a nanopore

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    Here we investigate the modulation of solvent isotope effects by the entry of DNA molecules into individual α-haemolysin nanopores. Solvent isotope effects in D2O versus H2O were enhanced (kH/kD ≈ 1.6) compared to the bulk (kH/kD ≈ 1.2), except when the pore was most blocked (kH/kD ≤ 1.1).Ion current recordings, raw data as recorded in PClamp 10.2 software. NOTE: Some files are in Axon(TM) Binary Format (ABF), a format proprietary to Molecular Devices

    Can dispersion forces govern aromatic stacking in an organic solvent?

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    Experimental support for the dominance of van der Waals dispersion forces in aromatic stacking interactions occurring in organic solution is surprisingly limited. Here, we have examined the size-dependence of aromatic stacking in an organic solvent. The interaction energy was found to vary by ~7.5 kJ mol–1 on going from a phenyl-phenyl to an anthracene-pyrene stack. Strikingly, the experimental data were highly correlated with dispersion energies determined using symmetry-adapted perturbation theory (SAPT), while the induction, exchange, electrostatic and solvation energy components correlated poorly. Both the experimental data and the SAPT-dispersion energies gave high-quality correlations with the change in solvent accessible area upon complexation. Thus, the size-dependence of aromatic stacking interactions is consistent with the dominance of van der Waals dispersion forces even in the presence of a competing polarizable solvent..xyx coordinates of minimised complex geometries, NMR characterisation and titration data

    Molecular balances for measuring non-covalent interactions in solution

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    Non-covalent interactions in solution are subject to modulation by surrounding solvent molecules. This thesis presents two experimental molecular balances that have been used to quantify solvent effects on non-covalent interactions, including electrostatic and dispersion interactions. The first chapter introduces literature where non-covalent interactions have been studied in a range of solvents, particularly those where the effects of aqueous or fluorous solvents have been investigated. These solvents are of particular interest as they both invoke solvophobic effects on organic molecules, but have differing chemical and physical properties. The second chapter describes the adaptation of the Wilcox molecular torsion balance to study interactions between organic and fluorinated carbon chains in a range of solvents. Solvent cohesion was found to be the principle force driving both the alkyl and fluorous chains together in aqueous solvents, where no contribution to the interaction energy arising from dispersion forces could be detected. In fluorous and polar organic solvents evidence was found for weak favourable dispersion interactions between the alkyl chains. In contrast dispersion forces between the chains were found to be disrupted by competitive van der Waals interactions with surrounding solvent molecules in apolar organic solvents. Association of the fluorous chains was found to be solely driven by solvent cohesion. The final chapter describes the design and synthesis of a novel synthetic molecular-balance framework and describes its application to simultaneously measure solvent and substituent effects on the position of conformational equilibria. Despite the simplicity of the model system, surprisingly complicated behaviour emerged from the interplay of conformational, intramolecular and solvent effects. Nonetheless, a large data set of experimental equilibrium constants was analysed using a simple solvent model, which was able to account for both the intuitive and more unusual patterns observed. A means of dissecting electrostatic and solvent effects to reveal pseudo gas-phase behaviour has resulted from the analysis of experimental data obtained in many solvents

    Letter From William Bell Scott to Mr Chambers

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    abstract: Concerning Scott's thanks, his writings about his own works, and a manuscript of "The Nightingale Unheard."Seller's Description: Reads "A.L.S. from Author to Mr. Chambers explaining how busy he is... The sonnet is printed in the book. Fredeman: 56.7 £87.50"Handwritten Note: Unknown handwriting at top right reads "June 1st 1877."Publication Details: "The Nightingale Unheard" published in "Poems" by William Bell Scott.Creation Date Details: Undated range is the author's lifespan.Provenance: Removed from: Poems / by William Bell Scott. Ballads, studies from nature, sonnets, etc. / illustrated by seventeen etchings by the author and L. Alma Tadema. Publisher London : Longmans, Green, 1875. CALL # HAYDEN SPECIAL COLL SPEC PRB-13

    DNA modulates solvent isotope effects in a nanopore 

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    Ion current recordings, raw data as recorded in PClamp 10.2 software. NOTE: Some files are in Axon(TM) Binary Format (ABF), a format proprietary to Molecular Devices.Here we investigate the modulation of solvent isotope effects by the entry of DNA molecules into individual α-haemolysin nanopores. Solvent isotope effects in D2O versus H2O were enhanced (kH/kD ≈ 1.6) compared to the bulk (kH/kD ≈ 1.2), except when the pore was most blocked (kH/kD ≤ 1.1).Watson, Matthew; Cockroft, Scott. (2015). DNA modulates solvent isotope effects in a nanopore, 2013-2015 [dataset]. University of Edinburgh, EaStCHEM School of Chemistry. http://dx.doi.org/10.7488/ds/277

    Protein nanopores as a platform for transmembrane nanodevices

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    Nanopore sensing has seen vast development over the past four decades. The technique originally looked to use electrophysiological methods to study native protein channels. However, it is now possible to exploit these proteins for sensing applications. Herein, we explore methods for covalent and non-covalent modification of a biological nanopore to achieve new functionality. Chapter 1 summarises the history of nanopore technology; from its inception as a method for studying native channels, to its deployment in nanopore sensing. To achieve effective sensing, native proteins have undergone a broad range of chemical modification to achieve enhanced functionality. This chapter explores the amalgamation of biological and solid-state nanopores. Chapter 2 seeks to the monitor the binding and catalytic turnover of substrates within a single cucurbituril molecule captured within a protein nanopore. Previous work has shown that cucurbiturils and cyclodextrins can transiently interact with an α-hemolysin channel. Capture of a single cucurbituril within a protein nanopore was achieved, and the dwell time of the binding events was optimised. Following this, it was demonstrated that observations of the catalysed Diels-Alder could be made at the single-molecule level. However, further optimisation of the resolution would be required to elucidate mechanistic information. Chapter 3 presents methods for in situ chemical functionalisation of a biological nanopore. Here, the focus is upon the chemical modification of a wild-type protein thereby to circumventing the need for mutagenesis. Three target residues are discussed: lysine, methionine and tyrosine. Successful modification was achieved at both the lysine and methionine sites of α-hemolysin. While some provisional success was recorded with tyrosine, the modifications were not reproducible. Chapter 4 introduces preliminary work towards the development of transmembrane molecular machines. This utilises the lysine modification discussed in Chapter 2 to covalently attach established synthetic molecular machines to the channel. Molecular switches, motors and pumps were all explored. Some success was achieved attaching the molecular machines to a protein channel. However, issues with pore stability limited the progress and true machine-like behaviour was not observed

    Scott Belsky in Conversation with DesignByThem - Part One.mp4

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    Watch here as Scott Belsky (CEO/Founder Behance + Author Making Ideas Happen) joins Sydney design duo Sarah Gibson and Nicholas Karlovasitis from DesignByThem to discuss some of the challenges facing creative companies as they try to grow their business. In part one Nick and Sarah get some great advice from Scott about what makes an effective partnership and how to learn from the challenges that can arise. Scott also explains the Behance technique of ?Concepting Teams? with representatives from all areas of the business to brainstorm issues or new ideas

    Cardozo AELJ Author Interview Series: Scott Semaya, Class of 2023

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    The Cardozo AELJ Author Interview Series seeks to give our readers further insight into the Articles and Notes published in the Cardozo Arts & Entertainment Law Journal. In this interview, Scott Semaya discusses his Note, Name, Image and Likeness: Giving College Athletes the Clearest Guidance to Best Profit off Their NIL, which was published in Volume 41, Issue 2. This post was originally published on the Cardozo Arts & Entertainment Law Journal website on June 6, 2023. The original post can be accessed via the Archived Link button above

    Cardozo AELJ Author Interview Series: Scott Semaya, Class of 2023

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    The Cardozo AELJ Author Interview Series seeks to give our readers further insight into the Articles and Notes published in the Cardozo Arts & Entertainment Law Journal. In this interview, Scott Semaya discusses his Note, Name, Image and Likeness: Giving College Athletes the Clearest Guidance to Best Profit off Their NIL, which was published in Volume 41, Issue 2. This post was originally published on the Cardozo Arts & Entertainment Law Journal website on June 6, 2023. The original post can be accessed via the Archived Link button above
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