1,474 research outputs found
A Classical Density-Functional Theory for Describing Water Interfaces
We develop a classical density functional for water which combines the White
Bear fundamental-measure theory (FMT) functional for the hard sphere fluid with
attractive interactions based on the Statistical Associating Fluid Theory
(SAFT-VR). This functional reproduces the properties of water at both long and
short length scales over a wide range of temperatures, and is computationally
efficient, comparable to the cost of FMT itself. We demonstrate our functional
by applying it to systems composed of two hard rods, four hard rods arranged in
a square and hard spheres in water
Optimal refrigerator
We study a refrigerator model which consists of two -level systems
interacting via a pulsed external field. Each system couples to its own thermal
bath at temperatures and , respectively ().
The refrigerator functions in two steps: thermally isolated interaction between
the systems driven by the external field and isothermal relaxation back to
equilibrium. There is a complementarity between the power of heat transfer from
the cold bath and the efficiency: the latter nullifies when the former is
maximized and {\it vice versa}. A reasonable compromise is achieved by
optimizing the product of the heat-power and efficiency over the Hamiltonian of
the two system. The efficiency is then found to be bounded from below by
(an analogue of the Curzon-Ahlborn
efficiency), besides being bound from above by the Carnot efficiency
. The lower bound is reached in the
equilibrium limit . The Carnot bound is reached (for a finite
power and a finite amount of heat transferred per cycle) for . If
the above maximization is constrained by assuming homogeneous energy spectra
for both systems, the efficiency is bounded from above by and
converges to it for .Comment: 12 pages, 3 figure
Minimal Work Principle and its Limits for Classical Systems
The minimal work principle asserts that work done on a thermally isolated
equilibrium system, is minimal for the slowest (adiabatic) realization of a
given process. This principle, one of the formulations of the second law, is
operationally well-defined for any finite (few particle) Hamiltonian system.
Within classical Hamiltonian mechanics, we show that the principle is valid for
a system of which the observable of work is an ergodic function. For
non-ergodic systems the principle may or may not hold, depending on additional
conditions. Examples displaying the limits of the principle are presented and
their direct experimental realizations are discussed.Comment: 4 + epsilon pages, 1 figure, revte
Atomic scale engines: Cars and wheels
We introduce a new approach to build microscopic engines on the atomic scale
that move translationally or rotationally and can perform useful functions such
as pulling of a cargo. Characteristic of these engines is the possibility to
determine dynamically the directionality of the motion. The approach is based
on the transformation of the fed energy to directed motion through a dynamical
competition between the intrinsic lengths of the moving object and the
supporting carrier.Comment: 4 pages, 3 figures (2 in color), Phys. Rev. Lett. (in print
MHz Unidirectional Rotation of Molecular Rotary Motors
A combination of cryogenic UV-vis and CD spectroscopy and transient absorption spectroscopy at ambient temperature is used to study a new class of unidirectional rotary molecular motors. Stabilization of unstable intermediates is achieved below 95 K in propane solution for the structure with the fastest rotation rate, and below this temperature measurements on the rate limiting step in the rotation cycle can be performed to obtain activation parameters. The results are compared to measurements at ambient temperature using transient absorption spectroscopy, which show that behavior of these motors is similar over the full temperature range investigated, thereby allowing a maximum rotation rate of 3 MHz at room temperature under suitable irradiation conditions
Reliability of fluctuation-induced transport in a Maxwell-demon-type engine
We study the transport properties of an overdamped Brownian particle which is
simultaneously in contact with two thermal baths. The first bath is modeled by
an additive thermal noise at temperature . The second bath is associated
with a multiplicative thermal noise at temperature . The analytical
expressions for the particle velocity and diffusion constant are derived for
this system, and the reliability or coherence of transport is analyzed by means
of their ratio in terms of a dimensionless P\'{e}clet number. We find that the
transport is not very coherent, though one can get significantly higher
currents.Comment: 14 pages, 5 figure
Photochemistry of [Ru(pytz)(btz)2]2+and Characterization of a κ1-btz Ligand-Loss Intermediate
We report the synthesis, characterisation and photochemical reactivity of the triazole-containing complex [Ru(pytz)(btz)2]2+ (1, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, btz = 1,1’-dibenzyl-4,4’-bi-1,2,3-triazolyl). The UV-visible absorption spectrum of 1 exhibits pytz- and btz-centred 1MLCT bands at 365 and 300 nm respectively. Upon photo-excitation, acetonitrile solutions of 1 undergo conversion to the ligand loss intermediate, trans-[Ru(pytz)(2-btz)(1-btz)(NCMe)]2+ (2, 363 = 0.013) and ultimately to the ligand loss product trans-[Ru(pytz)(btz)(NCMe)2]2+ (3), both of which are observed and characterised by 1H NMR spectroscopy. Time-dependent density functional theory calculations reveal that the S1 state of the complex has primarily HOMOLUMO pytz-based 1MLCT character. Data show that the 3MLCT and 3MC states are in close energetic proximity ( 0.11 eV to 2 d.p.) and that the T1 state from a single point triplet state calculation at the S0 geometry suggests 3MC character. Optimisation of the T1 state of the complex starting from the ground state geometry leads to elongation of the two Ru-N(btz) bonds cis to the pytz ligand to 2.539 and 2.544 Å leading to a psuedo 4-coordinate 3MC state rather than the 3MLCT state. The work therefore provides additional insights into the photophysical and photochemical properties of ruthenium triazole-containing complexes and their excited state dynamics
Macroscopic transport by synthetic molecular machines
Nature uses molecular motors and machines in virtually every significant biological process, but demonstrating that simpler artificial structures operating through the same gross mechanisms can be interfaced with—and perform physical tasks in—the macroscopic world represents a significant hurdle for molecular nanotechnology. Here we describe a wholly synthetic molecular system that converts an external energy source (light) into biased brownian motion to transport a macroscopic cargo and do measurable work. The millimetre-scale directional transport of a liquid on a surface is achieved by using the biased brownian motion of stimuli-responsive rotaxanes (‘molecular shuttles’) to expose or conceal fluoroalkane residues and thereby modify surface tension. The collective operation of a monolayer of the molecular shuttles is sufficient to power the movement of a microlitre droplet of diiodomethane up a twelve-degree incline.
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Polyacrylamide Bead Sensors for in vivo Quantification of Cell-Scale Stress in Zebrafish Development
Mechanical stress exerted and experienced by cells during tissue morphogenesis and organ formation plays an important role in embryonic development. While techniques to quantify mechanical stresses in vitro are available, few methods exist for studying stresses in living organisms. Here, we describe and characterize cell-like polyacrylamide (PAAm) bead sensors with well-defined elastic properties and size for in vivo quantification of cell-scale stresses. The beads were injected into developing zebrafish embryos and their deformations were computationally analyzed to delineate spatio-temporal local acting stresses. With this computational analysis-based cell-scale stress sensing (COMPAX) we are able to detect pulsatile pressure propagation in the developing neural rod potentially originating from polarized midline cell divisions and continuous tissue flow. COMPAX is expected to provide novel spatio-temporal insight into developmental processes at the local tissue level and to facilitate quantitative investigation and a better understanding of morphogenetic processes. © 2019, The Author(s)
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