1,677 research outputs found
Well-Tempered Metadynamics Simulations Predict the Structural and Dynamic Properties of a Chiral 24-Atom Macrocycle in Solution
Inspired by therapeutic potential, the molecular engineering of macrocycles is garnering increased interest. Exercising control with design, however, is challenging due to the dynamic behavior that these molecules must demonstrate in order to be bioactive. Herein, the value of metadynamics simulations is demonstrated: the free-energy surfaces calculated reveal folded and flattened accessible conformations of a 24-atom macrocycle separated by barriers of c.a. 6 kT under experimentally relevant conditions. Simulations reveal that the dominant conformer is folded-an observation consistent with a solid-state structure determined by X-ray crystallography and a network of rOes established by 1H NMR. Simulations suggest that the macrocycle exists as a rapidly interconverting pair of enantiomeric, folded structures. Experimentally, 1H NMR shows a single species at room temperature. However, at lower temperature, the interconversion rate between these enantiomers becomes markedly slower, resulting in the decoalescence of enantiotopic methylene protons into diastereotopic, distinguishable resonances due to the persistence of conformational chirality. The emergence of conformational chirality provides critical experimental support for the simulations, revealing the dynamic nature of the scaffold-a trait deemed critical for oral bioactivity
Breakdown of scale-invariance in the coarsening of phase-separating binary fluids
We present evidence, based on lattice Boltzmann simulations, to show that the
coarsening of the domains in phase separating binary fluids is not a
scale-invariant process. Moreover we emphasise that the pathway by which phase
separation occurs depends strongly on the relation between diffusive and
hydrodynamic time scales.Comment: 4 pages, Latex, 4 eps Figures included. (higher quality Figures can
be obtained from [email protected]
Recommended from our members
Short contacts between chains enhancing luminescence quantum yields and carrier mobilities in conjugated copolymers
Abstract: Efficient conjugated polymer optoelectronic devices benefit from concomitantly high luminescence and high charge carrier mobility. This is difficult to achieve, as interchain interactions, which are needed to ensure efficient charge transport, tend also to reduce radiative recombination and lead to solid-state quenching effects. Many studies detail strategies for reducing these interactions to increase luminescence, or modifying chain packing motifs to improve percolation charge transport; however achieving these properties together has proved elusive. Here, we show that properly designed amorphous donor-alt-acceptor conjugated polymers can circumvent this problem; combining a tuneable energy gap, fast radiative recombination rates and luminescence quantum efficiencies >15% with high carrier mobilities exceeding 2.4 cm2/Vs. We use photoluminescence from exciton states pinned to close-crossing points to study the interplay between mobility and luminescence. These materials show promise towards realising advanced optoelectronic devices based on conjugated polymers, including electrically-driven polymer lasers
Evolution of white matter damage in amyotrophic lateral sclerosis
Objective
To characterize disease evolution in amyotrophic lateral sclerosis using an event‐based model designed to extract temporal information from cross‐sectional data. Conventional methods for understanding mechanisms of rapidly progressive neurodegenerative disorders are limited by the subjectivity inherent in the selection of a limited range of measurements, and the need to acquire longitudinal data.
Methods
The event‐based model characterizes a disease as a series of events, each comprising a significant change in subject state. The model was applied to data from 154 patients and 128 healthy controls selected from five independent diffusion MRI datasets acquired in four different imaging laboratories between 1999 and 2016. The biomarkers modeled were mean fractional anisotropy values of white matter tracts implicated in amyotrophic lateral sclerosis. The cerebral portion of the corticospinal tract was divided into three segments.
Results
Application of the model to the pooled datasets revealed that the corticospinal tracts were involved before other white matter tracts. Distal corticospinal tract segments were involved earlier than more proximal (i.e., cephalad) segments. In addition, the model revealed early ordering of fractional anisotropy change in the corpus callosum and subsequently in long association fibers.
Interpretation
These findings represent data‐driven evidence for early involvement of the corticospinal tracts and body of the corpus callosum in keeping with conventional approaches to image analysis, while providing new evidence to inform directional degeneration of the corticospinal tracts. This data‐driven model provides new insight into the dynamics of neuronal damage in amyotrophic lateral sclerosis
Demonstration of tunable three-body interactions between superconducting qubits
Nonpairwise multi-qubit interactions present a useful resource for quantum
information processors. Their implementation would facilitate more efficient
quantum simulations of molecules and combinatorial optimization problems, and
they could simplify error suppression and error correction schemes. Here we
present a superconducting circuit architecture in which a coupling module
mediates 2-local and 3-local interactions between three flux qubits by design.
The system Hamiltonian is estimated via multi-qubit pulse sequences that
implement Ramsey-type interferometry between all neighboring excitation
manifolds in the system. The 3-local interaction is coherently tunable over
several MHz via the coupler flux biases and can be turned off, which is
important for applications in quantum annealing, analog quantum simulation, and
gate-model quantum computation.Comment: 14 pages, 11 figure
Measurements of Flavour Dependent Fragmentation Functions in Z^0 -> qq(bar) Events
Fragmentation functions for charged particles in Z -> qq(bar) events have
been measured for bottom (b), charm (c) and light (uds) quarks as well as for
all flavours together. The results are based on data recorded between 1990 and
1995 using the OPAL detector at LEP. Event samples with different flavour
compositions were formed using reconstructed D* mesons and secondary vertices.
The \xi_p = ln(1/x_E) distributions and the position of their maxima \xi_max
are also presented separately for uds, c and b quark events. The fragmentation
function for b quarks is significantly softer than for uds quarks.Comment: 29 pages, LaTeX, 5 eps figures (and colour figs) included, submitted
to Eur. Phys. J.
Bose-Einstein Correlations in e+e- to W+W- at 172 and 183 GeV
Bose-Einstein correlations between like-charge pions are studied in hadronic
final states produced by e+e- annihilations at center-of-mass energies of 172
and 183 GeV. Three event samples are studied, each dominated by one of the
processes W+W- to qqlnu, W+W- to qqqq, or (Z/g)* to qq. After demonstrating the
existence of Bose-Einstein correlations in W decays, an attempt is made to
determine Bose-Einstein correlations for pions originating from the same W
boson and from different W bosons, as well as for pions from (Z/g)* to qq
events. The following results are obtained for the individual chaoticity
parameters lambda assuming a common source radius R: lambda_same = 0.63 +- 0.19
+- 0.14, lambda_diff = 0.22 +- 0.53 +- 0.14, lambda_Z = 0.47 +- 0.11 +- 0.08, R
= 0.92 +- 0.09 +- 0.09. In each case, the first error is statistical and the
second is systematic. At the current level of statistical precision it is not
established whether Bose-Einstein correlations, between pions from different W
bosons exist or not.Comment: 24 pages, LaTeX, including 6 eps figures, submitted to European
Physical Journal
W+W- production and triple gauge boson couplings at LEP energies up to 183 GeV
A study of W-pair production in e+e- annihilations at Lep2 is presented,
based on 877 W+W- candidates corresponding to an integrated luminosity of 57
pb-1 at sqrt(s) = 183 GeV. Assuming that the angular distributions of the
W-pair production and decay, as well as their branching fractions, are
described by the Standard Model, the W-pair production cross-section is
measured to be 15.43 +- 0.61 (stat.) +- 0.26 (syst.) pb. Assuming lepton
universality and combining with our results from lower centre-of-mass energies,
the W branching fraction to hadrons is determined to be 67.9 +- 1.2 (stat.) +-
0.5 (syst.)%. The number of W-pair candidates and the angular distributions for
each final state (qqlnu,qqqq,lnulnu) are used to determine the triple gauge
boson couplings. After combining these values with our results from lower
centre-of-mass energies we obtain D(kappa_g)=0.11+0.52-0.37,
D(g^z_1)=0.01+0.13-0.12 and lambda=-0.10+0.13-0.12, where the errors include
both statistical and systematic uncertainties and each coupling is determined
setting the other two couplings to the Standard Model value. The fraction of W
bosons produced with a longitudinal polarisation is measured to be
0.242+-0.091(stat.)+-0.023(syst.). All these measurements are consistent with
the Standard Model expectations.Comment: 48 pages, LaTeX, including 13 eps or ps figures, submitted to
European Physical Journal
Bose-Einstein Correlations of Three Charged Pions in Hadronic Z^0 Decays
Bose-Einstein Correlations (BEC) of three identical charged pions were
studied in 4 x 10^6 hadronic Z^0 decays recorded with the OPAL detector at LEP.
The genuine three-pion correlations, corrected for the Coulomb effect, were
separated from the known two-pion correlations by a new subtraction procedure.
A significant genuine three-pion BEC enhancement near threshold was observed
having an emitter source radius of r_3 = 0.580 +/- 0.004 (stat.) +/- 0.029
(syst.) fm and a strength of \lambda_3 = 0.504 +/- 0.010 (stat.) +/- 0.041
(syst.). The Coulomb correction was found to increase the \lambda_3 value by
\~9% and to reduce r_3 by ~6%. The measured \lambda_3 corresponds to a value of
0.707 +/- 0.014 (stat.) +/- 0.078 (syst.) when one takes into account the
three-pion sample purity. A relation between the two-pion and the three-pion
source parameters is discussed.Comment: 19 pages, LaTeX, 5 eps figures included, accepted by Eur. Phys. J.
A Measurement of Rb using a Double Tagging Method
The fraction of Z to bbbar events in hadronic Z decays has been measured by
the OPAL experiment using the data collected at LEP between 1992 and 1995. The
Z to bbbar decays were tagged using displaced secondary vertices, and high
momentum electrons and muons. Systematic uncertainties were reduced by
measuring the b-tagging efficiency using a double tagging technique. Efficiency
correlations between opposite hemispheres of an event are small, and are well
understood through comparisons between real and simulated data samples. A value
of Rb = 0.2178 +- 0.0011 +- 0.0013 was obtained, where the first error is
statistical and the second systematic. The uncertainty on Rc, the fraction of Z
to ccbar events in hadronic Z decays, is not included in the errors. The
dependence on Rc is Delta(Rb)/Rb = -0.056*Delta(Rc)/Rc where Delta(Rc) is the
deviation of Rc from the value 0.172 predicted by the Standard Model. The
result for Rb agrees with the value of 0.2155 +- 0.0003 predicted by the
Standard Model.Comment: 42 pages, LaTeX, 14 eps figures included, submitted to European
Physical Journal
- …