Comparison of time reversal symmetric and asymmetric nano-swimmers oriented with an electric field in soft matter.

Using molecular dynamics simulations, we compare the motion of a nanoswimmer based on Purcell's suggested motor with a time asymmetrical cycle with the motion of the same molecular motor with a time symmetrical cycle. We show that Purcell's theorem still holds at the nanoscale, despite the local structure and the medium's fluctuations. Then, with the purpose of both orienting the swimmer's displacement and increasing the breakdown of the theorem, we study the effect of an electric field on a polarized version of these swimmers. For small and large fields, the time asymmetrical swimmer is more efficient, as suggested by Purcell. However, we find a field range for which Purcell's theorem is broken for the time symmetric motor. Results suggest that the breakdown of the theorem arises from the competition of the orientation field and Brownian forces, while for larger fields, the field destroys the effect of fluctuations restoring the theorem.

Light mediated emergence of surface patterns in azopolymers at low temperatures.

Polymer thin films doped with azobenzene molecules do have the ability to organize themselves in spontaneous surface relief gratings (SRG) under irradiation using a single polarized beam. To shed some light on this still unexplained phenomenon, we use a new method that permits us to access experimentally the very first steps of the pattern formation process. By decreasing the temperature, we slow down the formation and organization of patterns, due to the large increase in the viscosity and relaxation time of the azopolymer. As a result, decreasing the temperature allows us to access and study much shorter time scales, in the physical mechanisms underlying the pattern formation, than those previously reported. We find that the patterns organize themselves in sub-structures which size increases with the temperature, following the diffusion coefficient evolution of the material. This result suggests that the pattern formation and organization are mainly governed by diffusive processes, in agreement with some theories of SRG formation. Upon decreasing the temperature further, we observe the emergence of small voids located at the junction of the sub-structures.

Stimuli thresholds for isomerization-induced molecular motions in azobenzene-containing materials.

We use large-scale molecular dynamics simulations of the isomerizations of azobenzene molecules diluted inside a simple molecular material to investigate the effect of a modification of the cis isomer shape on the induced diffusion mechanism. To this end we simulate incomplete isomerizations, modifying the amplitude of the trans-to-cis isomerization. We find thresholds in the evolution of the host molecules mobility with the isomerization amplitude, a result predicted by the cage-breaking mechanism hypothesis (Teboul, V.; Saiddine, M.; Nunzi, J. M.; Accary, J. B. J. Chem. Phys. 2011, 134, 114517) and by the gradient pressure mechanism theory (Barrett, C. J.; Rochon, P. L.; Natansohn, A. L. J. Chem. Phys. 1998, 109, 1505-1516.). Above the threshold the diffusion then increases linearly with the variation of the chromophore size induced by the isomerization.

A toy model mimicking cage effect, structural fluctuations, and kinetic constraints in supercooled liquids.

In this work, we implement new toy models coined to reproduce the cage effect with variants including structural fluctuations and different kinetic constraints. We introduce structural fluctuations in the models from a distribution of the cages opening probabilities and a kinetic constraint from a variation of that probability with the local number of molecules involved in the creation of the cage. We model separately the caging mean field experienced by each molecule, and the cooperative mechanism with the kinetic constraint condition. We find that strong dynamic heterogeneities are present in the models with kinetic constraints. We find that the heterogeneities do not depend on the cage escaping probabilities, while the heterogeneities increase sharply with the strengthening of the kinetic constraint conditions.

Induced cooperative motions in a medium driven at the nanoscale: searching for an optimum excitation period.

Recent results have shown the appearance of induced cooperative motions called dynamic heterogeneity during the isomerization of diluted azobenzene molecules in a host glass-former. In this paper, we raise the issue of the coupling between these "artificial" heterogeneities and the isomerization period. How do these induced heterogeneities differ in the saturation regime and in the linear response regime? Is there a maximum of the heterogeneous motion versus the isomerization rate, and why? Is the heterogeneity evolution with the isomerization rate connected with the diffusion or relaxation time evolution? We use out-of-equilibrium molecular dynamics simulations to answer these questions. We find that the heterogeneity increases in the linear response regime for large isomerization periods and small perturbations. In contrast, the heterogeneity decreases in the saturation regime, i.e., when the isomerization half-period (τp/2) is smaller than the relaxation time of the material (τα). This result enables a test of the effect of cooperative motions on the dynamics using the chromophores as Maxwell demons that destroy or stimulate the cooperative motions. Because the heterogeneities increase in the linear regime and then decrease in the saturation regime, we find a maximum for τp/2≈τα. The induced excitation concentration follows a power-law evolution versus the isomerization rate and then saturates. As a consequence, the α relaxation time is related to the excitation concentration with a power law, a result in qualitative agreement with recent findings in constrained models. This result supports a common origin for the heterogeneities with constrained models and a similar relation to the excitation concentration.

How does the isomerization rate affect the photoisomerization-induced transport properties of a doped molecular glass-former?

We investigate the effect of the isomerization rate f on the microscopic mechanisms at the origin of the massive mass transport found in glass-formers doped with isomerizing azobenzene molecules that result in surface relief gratings formation. To this end we simulate the isomerization of dispersed probe molecules embedded into a molecular host glass-former. The host diffusion coefficient first increases linearly with f and then saturates. The saturated value of the diffusion coefficient and of the viscosity does not depend on f but increases with temperature while the linear response for these transport coefficients depends only slightly on the temperature. We interpret this saturation as arising from the appearance of increasingly soft regions around the probes for high isomerization rates, a result in qualitative agreement with experiments. These two different physical behaviors, linear response and saturation, are reminiscent of the two different unexplained mass transport mechanisms observed for small or large light intensities (for small intensities the molecules move towards the dark regions while for large intensities they move towards the illuminated regions).

Formation of surface relief gratings: effect of the density of the host material.

We use molecular dynamics simulations to investigate the effect of the density of the host material on the isomerization-induced diffusion mechanism that results in surface relief gratings formation. We find that a decrease in density increases the diffusion coefficient in a similar way for driven and spontaneous diffusion. This result suggests that the driving mechanism depends only slightly on the density of the host material. The pressure variations during the isomerization process decrease when the driven diffusion increases due to material softening for smaller densities. These results suggest that the pressure variations are not at the origin of the driven motions. The relative local density variation around the probe is also weakly dependent on the mean density of the host material as long as the material structure is preserved.

Time versus temperature rescaling for coarse grain molecular dynamics simulations.

Coarse graining procedures are intended to well reproduce the structure of a material while increasing the simulations efficiency. However, the dynamics usually accelerates with coarse graining and a scaling procedure has to be used for dynamical data calculations. Most often a simple time-scaling coefficient is used for this purpose. However, for low temperature liquids this simple scaling procedure is questionable. Because supercooled liquids in their approach to the glass transition temperature do not follow a simple dynamics. In order to test if this scaling procedure is still pertinent at low temperature, we use molecular dynamics simulations of a coarse grain model of the methylmethacrylate molecule compared to simulations with the All atom model. We compare two different rescaling procedures, a time rescale and a temperature rescale procedure. Using these two procedures we compare the behaviors of the mean square displacements, the incoherent scattering functions, the self and distinct part of the Van Hove correlation functions and the non-Gaussian parameters. Results show that the temperature rescaling procedure reproduces well the All atom dynamical data at low temperatures, while the time rescaling procedure is correct only in the Brownian regime. We also find that the melting and the glass-transition temperatures are relatively well reproduced with the temperature rescaling procedure.

An isomerization-induced cage-breaking process in a molecular glass former below T(g).

A recent experimental [P. Karageorgiev, D. Neher, B. Schulz, B. Stiller, U. Pietsch, M. Giersig, L. Brehmer, Nature Mater. 4, 699 (2005)] study has found liquidlike diffusion below the glass-transition temperature in azobenzene-containing materials under irradiation. This result suggests that the isomerization-induced massive mass transport that leads to surface relief gratings formation in these materials, is induced by this huge increase of the matrix diffusion coefficient around the probe. In order to investigate the microscopic origin of the increase of the diffusion, we use molecular dynamics simulations of the photoisomerization of probe dispersed red 1 molecules dispersed inside a glassy molecular matrix. Results show that the increased diffusion is due to an isomerization-induced cage-breaking process. A process that explains the induced cooperative motions recently observed in these photoactive materials.

Procedure volume is one determinant of centre effect in mechanically ventilated patients.

Survival rates vary significantly between intensive care units, most notably in patients requiring mechanical ventilation (MV). The present study sought to estimate the effect of hospital MV volume on hospital mortality. We included 179,197 consecutive patients who received mechanical ventilation in 294 hospitals. Multivariate logistic regression models with random intercepts were used to estimate the effect of annual MV volume in each hospital, adjusting for differences in severity of illness and case mix. Median annual MV volume was 162 patients (interquartile range 99-282). Hospital mortality in MV patients was 31.4% overall, 40.8% in the lowest annual volume quartile and 28.2% in the highest quartile. After adjustment for severity of illness, age, diagnosis and organ failure, higher MV volume was associated with significantly lower hospital mortality among MV patients (OR 0.9985 per 10 additional patients, 95% CI 0.9978-0.9992; p = 0.0001). A significant centre effect on hospital mortality persisted after adjustment for volume effect (p < 0.0001). Our study demonstrated higher hospital MV volume to be independently associated with increased survival among MV patients. Significant differences in outcomes persisted between centres after adjustment for hospital MV volume, supporting a role for other significant determinants of the centre effect.

Isomerization-induced surface relief gratings formation: A comparison between the probe and the matrix dynamics.

We report molecular dynamics simulations of the effect of the photoisomerization of probe molecules on the nonequilibrium dynamics of a bulk amorphous matrix. Is it the matrix or the probe that drives the dynamics in SRG formation? In the first picture, the probe isomerization induces the motion of the probe inside the matrix. The motion of the probe then induces molecular motions inside the matrix. In the second picture, the probe isomerization induces a modification of the matrix diffusion mechanism. The diffusion of the matrix then induces the motion of the embedded probe. To answer this question, we compare the motion of the probe molecules and the motion of the matrix molecules in various thermodynamic conditions. We show that when the isomerization is switched on, the matrix molecules surrounding the probe move faster than the probe. Around the probe, the structural relaxation time of the matrix molecules is shorter than the probe relaxation time and the diffusion of the matrix molecules is larger than the probe diffusion. These results show that the matrix motions drive the dynamics.

Isomerization-induced dynamic heterogeneity in a glass former below and above T(g).

We report the first molecular dynamics simulations of the effect of the photoisomerization of probe molecules on the nonequilibrium dynamics of a glassy or supercooled molecular material. We show that the isomerization of the probe molecules creates a new mobile dynamic heterogeneity inside the matrix. Together with these induced cooperative motions, we find an important increase of the diffusion coefficient leading to liquidlike diffusion below the glass-transition temperature. This result could explain the massive mass transport that leads to surface relief grating formation in azobenzene containing amorphous materials. We find that the isomerization process controls the heterogeneity and the non-gaussian parameter of the material, leading to extremely rapid variations of these quantities.

[ICU performance: results of a French study involving 80,000 ICU stays]. / Performance en réanimation: résultats du PHRC Sfar-SRLF.

OBJECTIVE: The Standard Mortality Ratio (SMR), comparing the observed in-hospital mortality to the predicted, may measure the intensive care units (ICU) performance. STUDY DESIGN: Multicentric retrospective national study. METHODS: A probability model using a severity score such SAPS II calculated the predicted mortality rate. A national French study has been undertaken to compare the SMR of ICUs and looked for explanation. RESULTS: One hundred six units, 34 were medical (32%), 18 surgical (17%) and 57 medical/surgical (51%) participated to the study. Forty-six ICUs (43%) were located in teaching hospitals. The SMR of the 87,099 stays was 0.84 (0.82-0.85). The SMR of ICUs varied from 0.41 to 1.55. Ten units had a SMR>0.85, which suggested a low performance. They had more stays for cardiovascular failures, as compared with others. The best units (SMR<0.82) had more stays for drug overdose. The SMR increased with the number of organ failures, from 0.47 with zero failure to 1.11 with 4 or more organ failures. The stays with cardiovascular failure, either unique or associated, had a higher SMR. The 7935 stays with a drug overdose had a SMR of 0.12 (0.10-0.14), which suggested a bad calibration of the model in theses cases. CONCLUSION: The case mix must be taken in account when comparing the ICUs performance by the mean of SMR, particularly when the units admitted a lot of drug overdoses.

Confinement of molecular liquids: consequences on thermodynamic, static and dynamical properties of benzene and toluene.

We relate the dynamical behavior of molecular liquids confined in mesoscopic cylindrical pores to the thermodynamic properties, heat capacity and density and to the static structure by combining different experimental methods (H-NMR, calorimetry, elastic and inelastic neutron scattering, numerical simulations). The crystallization process is greatly reduced or avoided by confinement under standard cooling conditions, instead a glass transition temperature T(g) at the 1000s time scale can be observed. The pore averaged local structure of the confined liquid is not noticeably affected when "excluded-volume" corrections are carefully applied, but follows the density changes reflected by the Bragg peak intensities of the porous matrices. The pore size dependence of T(g) is dominated by two factors, surface interaction and finite-size effect. For the smallest pores ([Formula: see text], [Formula: see text] being the van der Waals radius of a molecule), one observes an increase of T(g) and a broadening of the transition region, related to the interaction with the surface that induces a slowing-down of the molecules close to the wall. This is confirmed by neutron scattering experiments and molecular-dynamics simulations at shorter time scales and higher temperatures, which indicate a remaining fraction of frozen molecules. For larger pore sizes, taking the decrease of density under confinement conditions into account, a decrease of T(g) is observed. This could be related to finite-size effects onto the putative cooperativity length that is often invoked to explain glass formation. However, no quantitative determination of this length (not to mention its T-dependence) can be extracted, since the interaction with the wall itself introduces an additional length that adds to the complexity of the problem.