Temperature fluctuations and the thermodynamic determination of the cooperativity length in glass forming liquids.

The aim of this paper is to decide which of the two possible thermodynamic expressions for the cooperativity length in glass forming liquids is the correct one. In the derivation of these two expressions, the occurrence of temperature fluctuations in the considered nanoscale subsystems is either included or neglected. Consequently, our analysis gives also an answer to the widely discussed problem whether temperature fluctuations have to be generally accounted for in thermodynamics or not. To this end, the characteristic length-scales at equal times and temperatures for propylene glycol were determined independently from AC calorimetry in both the above specified ways and from quasielastic neutron scattering (QENS), and compared. The result shows that the cooperative length determined from QENS coincides most consistently with the cooperativity length determined from AC calorimetry measurements for the case that the effect of temperature fluctuations is incorporated in the description. This conclusion indicates that-accounting for temperature fluctuations-the characteristic length can be derived by thermodynamic considerations from the specific parameters of the liquid at glass transition and that temperature does fluctuate in small systems.

Probing cooperative liquid dynamics with the mean square displacement.

Literature data for picosecond mean square displacements show that the anharmonicity explains only about half of the fragility (with different fractions for different glass formers). The other half must be ascribed to the Adam-Gibbs mechanism of a growing cooperatively rearranging region. One can measure both influences separately by a simultaneous measurement of liquid and crystal in the coexistence region.

Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments.

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity [Formula: see text] at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size [Formula: see text] vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.

Anisotropic motion of cholesterol in oriented DPPC bilayers studied by quasielastic neutron scattering: the liquid-ordered phase.

Quasielastic neutron scattering (QENS) at two energy resolutions (1 and 14 microeV) was employed to study high-frequency cholesterol motion in the liquid ordered phase (lo-phase) of oriented multilayers of dipalmitoylphosphatidylcholine at three temperatures: T = 20 degrees C, T = 36 degrees C, and T = 50 degrees C. We studied two orientations of the bilayer stack with respect to the incident neutron beam. This and the two energy resolutions for each orientation allowed us to determine the cholesterol dynamics parallel to the normal of the membrane stack and in the plane of the membrane separately at two different time scales in the GHz range. We find a surprisingly high, model-independent motional anisotropy of cholesterol within the bilayer. The data analysis using explicit models of molecular motion suggests a superposition of two motions of cholesterol: an out-of-plane diffusion of the molecule parallel to the bilayer normal combined with a locally confined motion within the bilayer plane. The rather high amplitude of the out-of-plane diffusion observed at higher temperatures (T >/= 36 degrees C) strongly suggests that cholesterol can move between the opposite leaflets of the bilayer while it remains predominantly confined within its host monolayer at lower temperatures (T = 20 degrees C). The locally confined in-plane cholesterol motion is dominated by discrete, large-angle rotational jumps of the steroid body rather than a quasicontinous rotational diffusion by small angle jumps. We observe a significant increase of the rotational jump rate between T = 20 degrees C and T = 36 degrees C, whereas a further temperature increase to T = 50 degrees C leaves this rate essentially unchanged.

How to move things around a hospital: transport logistics at St. Michael's.

Ongoing fiscal restraint challenges hospitals to focus their resources primarily on core services. Support services receive much less attention. This article describes the experience of Toronto's St. Michael's Hospital when it re-engineered its transport logistics by consolidating centralized support services into a logistics department and creating new roles and processes to enhance patient care.

Best laid plans: effective implementation of re-engineering recommendations.

Continuing pressures on health care funding have led most hospitals to undertake re-engineering and restructuring projects to reduce operating expenses. Unfortunately, savings often turn out to be less than anticipated, as the projects falter in the implementation stage. As part of a two-year process improvement and expense reduction project, Toronto's St. Michael's Hospital developed an aggressive and comprehensive implementation process to ensure that it met its savings targets and maintained its financial viability. This article outlines the Hospital's implementation strategy and reviews the project's major challenges and key success factors.

Structural and dielectric properties of synthetic glycolipids in mixtures with water.

Three synthetically produced glycolipids, N-(beta-D-glucopyranosyl)-N-octadecyl-stearoylamide (OSGA), N-(beta-D-glucopyranosyl-N-octadecyl-oleoylamide (OOGA), N-(beta-D-galactopyranosyl)-N-octadecyl-lauroylamide (OLGA) have been studied in different mixtures with water by x-ray diffraction and dielectric measurements with microwaves at 9.4 GHz. The measurements were performed in the temperature range -50-70 degrees C. X-Ray diffraction revealed a direct L(beta') --> H( parallel) transition at 20 degrees C, 60 degrees C, and 45 degrees C depending on the glycolipid species but nearly not on the water content. The hexagonal phases are saturated at a water content of approximately 20 wt%. The lamellar phase absorbs even less water (< 10 wt%). The dielectric data show that in the H( parallel) phase the binding of water is stronger than in the L(beta') phase. In the temperature range below 0 degrees C, OSGA and OOGA show a "subzero transition" due to the freeze-out of water in a separate ice phase. This transition can be seen in an abrupt decrease of the dielectric function because the dielectric response of ice is much smaller at microwave frequencies. OLGA does not show the subzero transition but an additional transition, hexagonal --> distorted hexagonal at 60 degrees C.

Isolated tibial hemimelia in sibs: an autosomal-recessive disorder?

Isolated tibial hemimelia is generally considered to occur sporadically. We report on isolated tibial hemimelia in two sibs born to phenotypically normal parents and review a similar case from the literature. These cases suggest autosomal-recessive inheritance. Whether isolated tibial hemimelia represents a discrete syndrome or an expression of a disorder with wider phenotypic variability remains unclear.

Improvement of amputation level by lower extremity revascularization.

Improvement of amputation level, with a resulting increase in the ambulatory rehabilitation potential, was achieved in ten patients requiring extirpation of the lower extremity because of gangrene. Arterial reconstruction, percutaneous transluminal dilation or chemical lumbar sympathectomy, or a combination of these modalities, was used to achieve primary healing at an amputation site at least one level below that initially suggested by clinical and noninvasive diagnostic means. Patients requiring amputation of the lower extremity who are good candidates for ambulatory rehabilitation should undergo an aggressive diagnostic and therapeutic search for treatable proximal arterial lesions, thereby preserving limb length and increasing the likelihood of independent prosthetic use.

[Accidental laser coagulation of the macula (author's transl)]. / Alzidentelle Laserkoagulation der Makula.

During experimental studies with Q-switched laser radiation a laser beam with an impulse energy of 100 mJ reached the left eye of a patient. Dense vitreal hemorrhage developed; later fundus evaluation revealed coagulation of the macula with circular subretinal bleeding. Six month later a scar with retinal folds was observed at the posterior pole; the visual acuity was 0.1. The accident is compared with previously reported cases.