David Hull

Journal of Optimization Theory and Applications -     

Viscoelastic-mapping of cellulose nanofibrils using low-total-force contact resonance force microscopy (LTF-CRFM)

Cellulose - Low-total-force contact resonance force microscopy (LTF-CRFM), an atomic force microscopy method, is introduced as a non-destructive means to quantify the local viscoelastic loss...     

George Leitmann

Journal of Optimization Theory and Applications -     

Concomitant Polymorphism in an Organic Solid: Molecular and Crystal Structure and Intra- and Intermolecular Potential Contributions to tert-Butyl and Methyl Group Rotation

We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state ¹H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations.     

Ultra-sensitive analysis based on electrochemistry,electrokinetic and magnetic preconcentration of analytes

Some of the challenges with detection of ultra-low concentrations of analytes are to achieve sufficient sensitivity of the measurement and to direct the analyte species to the sensor (electrode) surface. This review describes various strategies that are available to address these challenges: method of electrocatalytic amplification, electrochemical measurements performed in combination with electrokinetic preconcentration of analytes, ultra-sensitive analysis utilizing increased surface area and also the manipulation by the magnetic force.     

PEG–Anthracene Hydrogels as an On‐Demand Stiffening Matrix To Study Mechanobiology

There is a growing interest in materials that can dynamically change their properties in the presence of cells to study mechanobiology. Herein, we exploit the 365 nm light mediated [4+4] photodimerization of anthracene groups to develop cytocompatible PEG‐based hydrogels with tailorable initial moduli that can be further stiffened. A hydrogel formulation that can stiffen from 10 to 50 kPa, corresponding to the stiffness of a healthy and fibrotic heart, respectively, was prepared. This system was used to monitor the stiffness‐dependent localization of NFAT, a downstream target of intracellular calcium signaling using a reporter in live cardiac fibroblasts (CFbs). NFAT translocates to the nucleus of CFbs on stiffening hydrogels within 6 h, whereas it remains cytoplasmic when the CFbs are cultured on either 10 or 50 kPa static hydrogels. This finding demonstrates how dynamic changes in the mechanical properties of a material can reveal the kinetics of mechanoresponsive cell signaling pathways that may otherwise be missed in cells cultured on static substrates.     

Convex solubility parameters for polymers

Solubility parameters are certain measurable quantities that are observed to influence the ability of a solvent to fully dissolve a polymer. Current theory partitions the intermolecular forces between dispersion, polar, and hydrogen bonding interactions, thereby generating a three‐dimensional solubility parameter space. The Hansen solubility parameters of a polymer are taken to be the center of a sphere obtained from the best fit of the coordinates of good solvents in the parameter space. Investigations of several polymers (lignin, polyethersulfone, and bitumen) show that the convex hull of all known good solvents in the three‐dimensional parameter space also gives a meaningful interpretation of the solubility region. Several methods for computing the convex solubility parameters of a polymer from the convex solubility region are described. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1089–1097     

Photochemical Reactions in the Synthesis of Protein–Drug Conjugates

The ability to modify biologically active molecules such as antibodies with drug molecules, fluorophores or radionuclides is crucial in drug discovery and target identification. Classic chemistry used for protein functionalisation relies almost exclusively on thermochemically mediated reactions. Our recent experiments have begun to explore the use of photochemistry to effect rapid and efficient protein functionalisation. This article introduces some of the principles and objectives of using photochemically activated reagents for protein ligation. The concept of simultaneous photoradiosynthesis of radiolabelled antibodies for use in molecular imaging is introduced as a working example. Notably, the goal of producing functionalised proteins in the absence of pre-association (non-covalent ligand-protein binding) introduces requirements that are distinct from the more regular use of photoactive groups in photoaffinity labelling. With this in mind, the chemistry of thirteen different classes of photoactivatable reagents that react through the formation of intermediate carbenes, electrophiles, dienes, or radicals, is assessed.     

PhI(OTf)2 Does Not Exist (Yet)**

PhI(OTf)₂ has been used for the past 30 years as a strong I(III) oxidant for organic and inorganic transformations. It has been reported to be generated in situ from the reactions of either PhI(OAc)₂ or PhI=O with two equivalents of trimethylsilyl trifluoromethanesulfonate (TMS-OTf). In this report it is shown that neither of these reactions generate a solution with spectroscopic data consistent with PhI(OTf)₂, with supporting theoretical calculations, and thus this compound should not be invoked as the species acting as the oxidant for transformations that have been associated with its use.