Search results for "force"
showing 10 items of 3423 documents
Molecular self-assembly on an insulating surface: interplay between substrate templating and intermolecular interactions
2012
We report on molecular self-assembly of biphenyl-4,4'-dicarboxylic acid (BPDCA) on CaCO3(10 (1) over bar4) under ultra-high vacuum conditions. Two-dimensional, ordered islands are obtained upon deposition at room temperature, coexisting with a streaky structure that is ascribed to individual, mobile molecules forming a two-dimensional gas-like phase. High-resolution non-contact atomic force microscopy (NC-AFM) images of the molecular islands reveal an ordered inner structure that is dominated by rows of molecules aligned side by side running along the [(42) over bar 61] crystallographic direction. A detailed analysis of these rows exhibits inter-row distances that are multiples of the calci…
Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium const…
2007
The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphin…
ChemInform Abstract: Microwave-Assisted Tandem Organocatalytic Peptide-Coupling Intramolecular aza-Michael Reaction: α,β-Unsaturated N-Acyl Pyrazoles…
2015
Conjugated N-acyl pyrazoles are successfully employed in the organocatalytic enantioselective intramolecular aza-Michael reaction as ester surrogates.
N-(tert-butoxycarbonylglycyl-alpha,beta-dehydrophenylalanylglycylphenylalanyl)-4-nitroaniline.
2000
In the crystal structure of the tetrapeptide Boc0–Gly1–ΔPhe2–Gly3–Phe4–p-NA (p-NA is para-nitroaniline), C33H36N6O8, there are two independent molecules differing in conformation in the asymmetric part of the unit cell. All the amino acids in the peptide are linked trans to each other. The torsion angles in the main chain of both molecules are close to the values of the type β-II turn. Two intramolecular and three intermolecular N—H⋯O hydrogen bonds stabilize the conformation of each of the molecules.
Steel Fibres: Effective Way to Prevent Failure of the Concrete Bonded with FRP Sheets
2016
Although the efficiency of steel fibres for improving mechanical properties (cracking resistance and failure toughness) of the concrete has been broadly discussed in the literature, the number of studies dedicated to the fibre effect on structural behaviour of the externally bonded elements is limited. This experimental study investigates the influence of steel fibres on the failure character of concrete elements strengthened with external carbon fibre reinforced polymer sheets. The elements were subjected to different loading conditions. The test data of four ties and eight beams are presented. Different materials were used for the internal bar reinforcement: in addition to the conventiona…
The role of the transfer group in the intramolecular [5+2] cycloadditions of substituted β-hydroxy-γ-pyrones: a DFT analysis
2005
The intramolecular [5+2] cycloaddition reactions of a series of 3-OR (R=SiMe3, H, CHO, Me) substituted β-hydroxy-γ-pyrones bearing tethered alkenes were studied using DFT methods at the B3LYP/6–31G* level. The role of the transfer R group was analyzed considering two alternative channels: (i) in channel a the process is initialized by the transfer of the R group with formation of an oxidopyrylium ylide intermediate, which is followed of an intramolecular [5+2] cycloaddition; (ii) in channel b, the process is initialized by the intramolecular [5+2] cycloaddition on the γ-pyrone followed by the transfer of the R group. Copyright © 2005 John Wiley & Sons, Ltd.
Asymmetric synthesis of polycyclic 3-fluoroalkylproline derivatives by intramolecular azomethine ylide cycloaddition
2019
The asymmetric synthesis of polycyclic fluorinated proline derivatives has been accomplished by means of an intramolecular azomethine ylide cycloaddition with fluorinated dipolarophiles. Thus, the reaction of benzaldehydes bearing a trifluoromethyl alkene in ortho position with an azomethine ylide precursor derived from chiral 2-amino indanol takes place with excellent levels of diastereoselectivity, with simultaneous generation of four stereocenters. In order to determine the influence of the fluorine moiety in the process, starting material bearing non-fluorinated alkenes were synthesised. In this case, a dramatic drop of selectivity occurred, which indicates that the role of the fluorine…
Exploring the exchange interaction in a mixed valence {CoII4CoIII2} hexanuclear cluster with novel topology
2012
Abstract Reaction between [Co2(μ-OH2)(μ-Piv)2(Piv)2(HPiv)4] and a (salicylidene)ethanolamine ligand under ambient reaction conditions, affords hexanuclear complexes [CoIII2CoII4(Piv)8(HPiv)2(L)2(OH)2] (1–2). Both products have been characterized crystallographically and found to be mixed-valent, containing divalent and trivalent Co centers. Down to 30 K, the variable-temperature magnetic susceptibility data are dominated by the single-ion properties of high spin Co(II) centers with distorted-octahedral coordination geometries. Below this temperature, the effect of intramolecular ferromagnetic exchange interactions becomes apparent. Magnetic data has been analyzed in terms of ground isolated…
Synthesis, characterization and magnetic properties of mixed-valence iron complexes with 2-pyridyl oximes
2018
Two new mixed-valence iron complexes with 2-pyridyl oximes, [Fe(mpko)3Fe(H2O)2(NO3)](NO3)·2H2O (1) (mpko− = methyl(2-pyridyl)ketone oximate) and [{Fe(dpko)3}2Fe](ClO4)·4H2O (2) (dpko− = bis(2-pyridyl)ketone oximate), have been prepared by reaction of FeIII with mpkoH in methanol (1) and FeII with dpkoH in methanol/water (2). Dinuclear FeII(low-spin)FeIII(high-spin) and trinuclear FeII(low-spin)FeIII(high-spin)FeII(low-spin) cations are present in the crystal structure of 1 and 2, respectively. Intermolecular hydrogen bonds in 1 lead to weak antiferromagnetic interactions between pairs of neighboring FeIII centers, which allows observation of single-ion zero-field splitting effects.
Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions
2015
Noncovalent interactions drive the self-assembly of weakly interacting molecular systems to form supramolecular aggregates, which play a major role in nanotechnology and biochemistry. In this work, we present a thorough assessment of the performance of different double-hybrid density functionals (PBE0-DH-NL, revPBE0-DH-NL, B2PLYP-NL, and TPSS0-DH-NL), as well as their parent hybrid and (meta)GGA functionals, in combination with the most modern version of the nonlocal (NL) van der Waals correction. It is shown that this nonlocal correction can be successfully coupled with double-hybrid density functionals thanks to the short-range attenuation parameter b, which has been optimized against ref…