Search results for "Rotation"
showing 10 items of 935 documents
Interplay of Chiral Side Chains and Helical Main Chains in Polyisocyanates
1996
Here we describe the synthesis of seven new copolymer series prepared by copolymerization of hexyl isocyanate with seven new chiral azo chromophores with an isocyano functionality. The resulting copolyisocyanates (Nylon 1) possess a helical polymer conformation. In the cases in which the chiral group and polymer chain are linked to the same phenyl ring (copolymer series VI-IX) a transfer of chirality to the polymer chain is possible. I.e. one helical twist sense is preferred in this case. By variation of the chiral center, polymers with preferable right- or left-handed helical conformation are accessible. The photochemical isomerization of the azo chromophore (trans → cis) is possible in hi…
Confinement of chiral molecules in reverse micelles: FT-IR, polarimetric and VCD investigation on the state of dimethyl tartrate in sodium bis(2-ethy…
2008
Abstract The state of d and l -dimethyl tartrate confined within dry sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles dispersed in CCl 4 has been investigated by FT-IR spectroscopy, polarimetry, and vibrational circular dichroism (VCD). Measurements have been performed at 25 °C as a function of the solubilizate-to-surfactant molar ratio ( R ) at a fixed AOT concentration (0.158 M). The analysis of experimental data is consistent with the hypothesis that both enantiomers of dimethyl tartrate are mainly entrapped in the reverse micelles and located in proximity to the surfactant head-group region. The formation of this interesting self-organized chiral nanostructure involves som…
Separation, isolation and stereochemical assignment of imazalil enantiomers and their quantitation in an in vitro toxicity test
2016
A simple method for the separation of the enantiomers of the fungicide imazalil was developed. Racemic imazalil was separated into its enantiomers with an enantiomeric purity of 99% using HPLC-UV with an enantioselective column (permethylated cyclodextrin) operated in reversed phase mode (water with 0.2% trimethylamine and 0.08% acetic acid and methanol). The absolute configuration of the separated enantiomers was assigned and unequivocally confirmed by optical rotation as well as by vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) combined with ab-initio calculations. The same enantioselective column was also used to develop an HPLC-MS/MS method for the quantifi…
Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.
2013
Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Ta…
Enhanced Spatial Navigation Skills in Sequence-Space Synesthetes
2018
Contains fulltext : 219554.pdf (Publisher’s version ) (Closed access) Individuals with sequence-space synesthesia (SSS) perceive sequences like months, days and numbers in certain spatial arrangements. Several cognitive benefits have been associated with SSS, such as enhanced mental rotation, more vivid visual imagery and an advantage in spatial processing. The current study aimed to further investigate these cognitive benefits, focusing on spatial navigation skills, to explore if their enhanced sensitivity to spatial relations is reflected in enhanced navigational performance. Synesthetes were distinguished from controls by means of a questionnaire, a consistency test and drawings. A virtu…
Right-handers and left-handers have different representations of their own hand
1998
The visual control of our own hand when dealing with an object and the observation of interactions between other people's hand and objects can be involved in the construction of internal representations of our own hand, as well as in hand recognition processes. Therefore, a different effect on handedness recognition is expected when subjects are presented with hands holding objects with either a congruent or an incongruent type of grip. Such an experiment was carried out on right-handed and left-handed subjects. We expected that the different degree of lateralisation in motor activities observed in the two populations [J. Herron, Neuropsychology of left- handedness, Academic Press, New York…
Rotational diffusion of colloid spheres in concentrated suspensions studied by deuteron NMR
1997
We present a study of the application of deuteron-nuclear magnetic resonance spectroscopy (NMR) to the investigation of the rotational diffusion of spherical colloidal particles. We performed NMR pulse experiments on colloidal suspensions of polystyrene latex spheres in water-glycerol mixtures in a wide range of particle volume fractions \ensuremath{\varphi} from the dilute suspension up to \ensuremath{\varphi}=0.504. We have analyzed the stimulated echo NMR signal in the time domain. The full shape of the orientational correlation function deviates from an exponential behavior in the whole \ensuremath{\varphi} range examined. We evaluate the rotational diffusion coefficient and calculate i…
A simple proof of the polylog counting ability of first-order logic
2007
The counting ability of weak formalisms (e.g., determining the number of 1's in a string of length N ) is of interest as a measure of their expressive power, and also resorts to complexity-theoretic motivations: the more we can count the closer we get to real computing power. The question was investigated in several papers in complexity theory and in weak arithmetic around 1985. In each case, the considered formalism (AC 0 -circuits, first-order logic, Δ 0 ) was shown to be able to count up to a polylogarithmic number. An essential part of the proofs is the construction of a 1-1 mapping from a small subset of {0, ..., N - 1} into a small initial segment. In each case the expressibility of …
Nearly tight bounds on the learnability of evolution
2002
Evolution is often modeled as a stochastic process which modifies DNA. One of the most popular and successful such processes are the Cavender-Farris (CF) trees, which are represented as edge weighted trees. The Phylogeny Construction Problem is that of, given /spl kappa/ samples drawn from a CF tree, output a CF tree which is close to the original. Each CF tree naturally defines a random variable, and the gold standard for reconstructing such trees is the maximum likelihood estimator of this variable. This approach is notoriously computationally expensive. We show that a very simple algorithm, which is a variant on one of the most popular algorithms used by practitioners, converges on the t…
Efficient formulation of a two-noded geometrically exact curved beam element
2021
The article extends the formulation of a 2D geometrically exact beam element proposed by Jirasek et al. (2021) to curved elastic beams. This formulation is based on equilibrium equations in their integrated form, combined with the kinematic relations and sectional equations that link the internal forces to sectional deformation variables. The resulting first-order differential equations are approximated by the finite difference scheme and the boundary value problem is converted to an initial value problem using the shooting method. The article develops the theoretical framework based on the Navier-Bernoulli hypothesis, with a possible extension to shear-flexible beams. Numerical procedures …