1,055 research outputs found
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
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.
Supramolecularly directed rotary motion in a photoresponsive receptor
Stimuli-controlled motion at the molecular level has fascinated chemists already for several decades. Taking inspiration from the myriad of dynamic and machine-like functions in nature, a number of strategies have been developed to control motion in purely synthetic systems. Unidirectional rotary motion, such as is observed in ATP synthase and other motor proteins, remains highly challenging to achieve. Current artificial molecular motor systems rely on intrinsic asymmetry or a specific sequence of chemical transformations. Here, we present an alternative design in which the rotation is directed by a chiral guest molecule, which is able to bind non-covalently to a light-responsive receptor. It is demonstrated that the rotary direction is governed by the guest chirality and hence, can be selected and changed at will. This feature offers unique control of directional rotation and will prove highly important in the further development of molecular machinery
Organic nanofibers embedding stimuli-responsive threaded molecular components
While most of the studies on molecular machines have been performed in
solution, interfacing these supramolecular systems with solid-state
nanostructures and materials is very important in view of their utilization in
sensing components working by chemical and photonic actuation. Host polymeric
materials, and particularly polymer nanofibers, enable the manipulation of the
functional molecules constituting molecular machines, and provide a way to
induce and control the supramolecular organization. Here, we present
electrospun nanocomposites embedding a self-assembling rotaxane-type system
that is responsive to both optical (UV-visible light) and chemical (acid/base)
stimuli. The system includes a molecular axle comprised of a dibenzylammonium
recognition site and two azobenzene end groups, and a dibenzo[24]crown-8
molecular ring. The dethreading and rethreading of the molecular components in
nanofibers induced by exposure to base and acid vapors, as well as the
photoisomerization of the azobenzene end groups, occur in a similar manner to
what observed in solution. Importantly, however, the nanoscale mechanical
function following external chemical stimuli induces a measurable variation of
the macroscopic mechanical properties of nanofibers aligned in arrays, whose
Young's modulus is significantly enhanced upon dethreading of the axles from
the rings. These composite nanosystems show therefore great potential for
application in chemical sensors, photonic actuators and environmentally
responsive materials.Comment: 39 pages, 16 figure
4-Hydroxy-1-naphthaldehydes: proton transfer or deprotonation
A series of naphthaldehydes, including a Mannich base, have been investigated by UV-Vis spectroscopy, NMR and theoretical methods to explore their potential tautomerism. In the case of 4-hydroxy-1-naphthaldehyde concentration dependent deprotonation has been detected in methanol and acetonitrile. For 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (a Mannich base) an intramolecular proton transfer involving the OH group and the piperidine nitrogen occurs. In acetonitrile the equilibrium is predominantly at the OH-form, whereas in methanol the proton transferred tautomer is the preferred form. In chloroform and toluene, the OH form is completely dominant. Both 4-hydroxy-1-naphthaldehyde and 4-methoxy-1-naphthaldehyde (fixed enol form) show dimerization in the investigated solvents and the crystallographic data, obtained for the latter, confirm the existence of a cyclic dimer
Long-term outcome of COVID-19 patients treated with helmet noninvasive ventilation vs. high-flow nasal oxygen: a randomized trial
Background: Long-term outcomes of patients treated with helmet noninvasive ventilation (NIV) are unknown: safety concerns regarding the risk of patient self-inflicted lung injury and delayed intubation exist when NIV is applied in hypoxemic patients. We assessed the 6-month outcome of patients who received helmet NIV or high-flow nasal oxygen for COVID-19 hypoxemic respiratory failure. Methods: In this prespecified analysis of a randomized trial of helmet NIV versus high-flow nasal oxygen (HENIVOT), clinical status, physical performance (6-min-walking-test and 30-s chair stand test), respiratory function and quality of life (EuroQoL five dimensions five levels questionnaire, EuroQoL VAS, SF36 and Post-Traumatic Stress Disorder Checklist for the DSM) were evaluated 6 months after the enrollment. Results: Among 80 patients who were alive, 71 (89%) completed the follow-up: 35 had received helmet NIV, 36 high-flow oxygen. There was no inter-group difference in any item concerning vital signs (N = 4), physical performance (N = 18), respiratory function (N = 27), quality of life (N = 21) and laboratory tests (N = 15). Arthralgia was significantly lower in the helmet group (16% vs. 55%, p = 0.002). Fifty-two percent of patients in helmet group vs. 63% of patients in high-flow group had diffusing capacity of the lungs for carbon monoxide < 80% of predicted (p = 0.44); 13% vs. 22% had forced vital capacity < 80% of predicted (p = 0.51). Both groups reported similar degree of pain (p = 0.81) and anxiety (p = 0.81) at the EQ-5D-5L test; the EQ-VAS score was similar in the two groups (p = 0.27). Compared to patients who successfully avoided invasive mechanical ventilation (54/71, 76%), intubated patients (17/71, 24%) had significantly worse pulmonary function (median diffusing capacity of the lungs for carbon monoxide 66% [Interquartile range: 47–77] of predicted vs. 80% [71–88], p = 0.005) and decreased quality of life (EQ-VAS: 70 [53–70] vs. 80 [70–83], p = 0.01). Conclusions: In patients with COVID-19 hypoxemic respiratory failure, treatment with helmet NIV or high-flow oxygen yielded similar quality of life and functional outcome at 6 months. The need for invasive mechanical ventilation was associated with worse outcomes. These data indicate that helmet NIV, as applied in the HENIVOT trial, can be safely used in hypoxemic patients. Trial registration Registered on clinicaltrials.gov NCT04502576 on August 6, 202
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