125,301 research outputs found
Simulation of Heme using DFT+U: a step toward accurate spin-state energetics
We investigate the DFT+U approach as a viable solution to describe the
low-lying states of ligated and unligated iron heme complexes. Besides their
central role in organometallic chemistry, these compounds represent a
paradigmatic case where LDA, GGA, and common hybrid functionals fail to
reproduce the experimental magnetic splittings. In particular, the imidazole
pentacoordinated heme is incorrectly described as a triplet by all usual DFT
flavors. In this study we show that a U parameter close to 4 eV leads to spin
transitions and molecular geometries in quantitative agreement with
experiments, and that DFT+U represents an appealing tool in the description of
iron porphyrin complexes, at a much reduced cost compared to correlated
quantum-chemistry methods. The possibility of obtaining the U parameter from
first-principles is explored through a self-consistent linear-response
formulation. We find that this approach, which proved to be successful in other
iron systems, produces in this case some overestimation with respect to the
optimal values of U.Comment: To be published in The Journal of Physical Chemistry B 30 pages, 15
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Poly(triazolyl methacrylate) glycopolymers as potential targeted unimolecular nanocarriers
© The Royal Society of Chemistry 2019.Synthetic glycopolymers are increasingly investigated as multivalent ligands for a range of biological and biomedical applications. This study indicates that glycopolymers with a fine-tuned balance between hydrophilic sugar pendant units and relatively hydrophobic polymer backbones can act as single-chain targeted nanocarriers for low molecular weight hydrophobic molecules. Non-covalent complexes formed from poly(triazolyl methacrylate) glycopolymers and low molecular weight hydrophobic guest molecules were characterised through a range of analytical techniques-DLS, SLS, TDA, fluorescence spectroscopy, surface tension analysis-and molecular dynamics (MD) modelling simulations provided further information on the macromolecular characteristics of these single chain complexes. Finally, we show that these nanocarriers can be utilised to deliver a hydrophobic guest molecule, Nile red, to both soluble and surface-immobilised concanavalin A (Con A) and peanut agglutinin (PNA) model lectins with high specificity, showing the potential of non-covalent complexation with specific glycopolymers in targeted guest-molecule delivery.Peer reviewedFinal Published versio
Antiferromagnetic spin-coupling between MnII and amminium radical cation ligands: models for coordination polymer magnets
One and two electron oxidation of the manganese(II) complex [L2Mn(hfac)2] {L = 4'',4'''-di-tert-butyl-2',2'',2'''trimethoxy-{4-(4'-diphenylaminophenyl)pyridine} were studied by ultra violet/ visible/ near infra red spectroscopy, cyclic voltammetry and magnetometry. A one-electron oxidation converts the triarylamine ligand to its radical cation and gives a complex in which the antiferromagnetic coupling between the spin on the ligand and that on the metal J/kb is -1.5 K. In a dilute frozen matrix and at low temperature this behaves as an S = 2 system. A two electron oxidation gives [L2Mn(hfac)2]2.+ which at low enough temperatures behaves as an S = 3/2 system but the spin-coupling between the metal and the ligand is weaker (J/kb = -0.3 K). The weakness of these spin-couplings mean that MnII/amminium radical cation complexes are not promising systems on which to base coordination polymer magnets. The equivalent copper(II) complex [L2Cu(hfac)2] was also investigated but this decomposes when an attempt is made to oxidise the ligand to its amminium radical cation
Anion–arene adducts: C–H hydrogen bonding, anion– interaction, and carbon bonding motifs
This article summarizes experimental and theoretical evidence for the existence of four distinct binding modes for complexes of anions with charge-neutral arenes. These include C–H hydrogen bonding and three motifs involving the arene– system—the noncovalent anion– interaction, weakly covalent interaction, and strongly covalent interaction
On global deformation quantization in the algebraic case
We give a proof of Yekutieli's global algebraic deformation quantization
result which does not rely on the choice of local sections of the bundle of
affine coordinate systems. Instead we use an argument inspired by algebraic De
Rham cohomology.Comment: 60 pages; references added; relation to Hinich's work explaine
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