Search results for "structural"
showing 10 items of 5047 documents
Biomolecular-solvent stereodynamic coupling probed by deuteration.
1983
Thermodynamic interpretation of experiments with isotopically perturbed solvent supports the view that solvent stereodynamics is directly relevant to thermodynamic stability of biomolecules. According with the current understanding of the structure of the aqueous solvent, in any stereodynamic configuration of the latter, connectivity pathways are identifiable for their topologic and order properties. Perturbing the solvent by isotopic substitution or, e.g., by addition of co-solvents, can therefore be viewed as reinforcing or otherwise perturbing these topologic structures. This microscopic model readily visualizes thermodynamic interpretation. In conclusion, the topologic stereodynamic str…
Coupling of the guanosine glycosidic bond conformation and the ribonucleotide cleavage reaction: implications for barnase catalysis.
2007
To examine the possible relationship of guanine-dependent GpA conformations with ribonucleotide cleavage, two potential of mean force (PMF) calculations were performed in aqueous solution. In the first calculation, the guanosine glycosidic (Gχ) angle was used as the reaction coordinate, and computations were performed on two GpA ionic species: protonated (neutral) or deprotonated (negatively charged) guanosine ribose O2 ′. Similar energetic profiles featuring two minima corresponding to the anti and syn Gχ regions were obtained for both ionic forms. For both forms the anti conformation was more stable than the syn, and barriers of ∼4 kcal/mol were obtained for the anti → syn transition. Str…
Self-Diffusion of Associating Star-Shaped Polymers
2016
The dynamics of associating bonds in transient polymer networks exerts a paramount influence on their relaxation and time-dependent mechanical properties. In particular, diffusive motion of polymers mediated by the dissociation and association equilibrium of reversible junctions can affect the materials’ structural stability, dynamic mechanical properties, and a broad spectrum of functionality that arises from the constant motion of polymer chains. In this work, forced Rayleigh scattering is used to measure the diffusion of terpyridine end-functionalized four-arm poly(ethylene glycol) polymers transiently interlinked by zinc ions in organic solvent across a wide range of length and time sca…
Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization
2018
Chemical functionalization is a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, increase their processability and stability, tune their functionalities and, even, create new 2D materials. This is typically achieved through post-synthetic functionalization by anchoring molecules on the surface of an exfoliated 2D crystal, but it inevitably alters the long-range structural order of the material. Here we present a pre-synthetic approach that allows the isolation of crystalline, robust and magnetic functionalized monolayers of coordination polymers. A series of five isostructural layered magnetic coordination polymers based on Fe(ii) centres a…
Mode I interlaminar fracture toughness of thin-ply laminates with CNT webs at the crack interface
2019
Abstract Pristine and functionalized carbon nanotube (CNT) webs were introduced at the interlaminar region of two different thin-ply carbon fibre reinforced polymer systems (NTPT 402 prepreg, and TeXtreme/SE84LV). The Mode I interlaminar fracture toughness (ILFT) for the NTPT 402 material was substantially lower. In contrast when SE84LV resin was used, the resistance curves were virtually unchanged and with no depreciation in the steady state value of the ILFT. This demonstrates that a careful choice of the resin is essential to permit the embedding of CNT webs in thin-ply laminates without compromising structural performance and opens a new way towards the development of multifunctional th…
13C NMR study of aromatic ring-substituted (E)-3-phenylpropenals and (2E,4E)-5-phenylpenta-2,4-dienals
1990
13C and 1H chemical shifts together with C,H and H,H coupling constants are presented for (E)-3-phenylpropenal, (2E,4E)-5-phenylpenta-2,4-dienal and their o-OCH3- and o-, m- and p-NO2-substituted derivatives. The SCSs calculated for the aldehyde chains show similar effects on the ring carbons, except in the para position where the shorter chain causes a 3.3 ppm deshielding and the longer chain a 1.0 ppm shielding effect. This shift difference is reflected in all the ring-substituted derivatives of the two series of aldehydes, but not in the one-bond C,H coupling constants. The effect of aromatic ring substitution on 2J(C,CHO) seems to be mainly inductive in origin. The importance of the str…
Structure of 5,17-dimethyl-11,23-dioctylcalix[4]arene
1991
The title compound C46O4H60 crystallizes in the triclinic space group, P¯1, witha=11.584(2),b=16.261(2),c=11.172(1) A,α=103.15(8),β=95.68(1),γ=96.85(1)°. The structure was solved by direct methods, and refined by weighted full-matrix least squares toR=0.097. This is the second calix[4]arene with two different alkyl substituents atpara positions of the phenolic rings. The macrocycle adopts the cone conformation. Interactions CH3-π are established between two calixarenes related by a center of symmetry. Comparisons are made between the conformation of this molecule and that of symmetrically substituted calix[4]arenes.
A New Structural Motif for an Enantiomerically Pure Metallosupramolecular Pd4L8Aggregate by Anion Templating
2014
An enantiomerically pure BINOL-based bis(3-pyridyl) ligand 1 assembles into a homochiral [Pd4(1)8] complex upon coordination to tetravalent PdII ions. The formation of this aggregate is templated by two tetrafluoroborate counterions that are encapsulated in two peripheral cavities. The resulting structure is a new structural motif for this kind of metallosupramolecular assemblies that arranges the palladium ions in a distorted tetrahedral fashion and forces ligand 1 to adopt two different conformations. Both phenomena are unique and cause an overall three-dimensional structure that has another confined, chiral, and hydrophilic central cavity.
Influence of anthropogenic activity on the lead isotope signature of Thau Lake sediments (southern France): origin and temporal evolution
2000
Lead concentrations and isotopic compositions were determined on both bulk sediments deposited in the Thau lake in southern France during the last 200 years, and leachates derived from a series of sequential leachings of the sediments, making it possible to identify the sources, natural (i.e. indigenous lithologic) or anthropogenic, and to quantify the different inputs of Pb. Two distinct inputs of Pb could be distinguished. One of these corresponds to the terrigenous material entering the basin, representative of the local natural Pb ‘background’. Its supply remained steady most of the time with 206Pb/207Pb ratios of 1.200±0.003, except at the time of heavy storms producing voluminous and …
An investigation on using pre-treated tyre rubber as a replacement of synthetic polymers for bitumen modification
2015
Rubberized bitumen obtained through a swelling process, has widely proven to be a successful technology for asphalt pavement applications and a solution to reduce the dismantling of tyre rubber on landfills. However, this technology presents two main operative issues which needs the adoption of costly special equipment. Firstly, significant high value of High Temperature Viscosity (HTV) which imposes mixing and compaction difficulties and leads to increased energy consumption and emissions. Furthermore, during the hot storage period, phase separation between rubber particles and the base bitumen could occur. Developing Recycled Tyre Rubber Modified Bitumen (RTR-MBs) with improved storage st…