Effective temperatures in nonequilibrium statistical physics.

This paper summarizes two related effective-temperature analyses of nonequilibrium phenomena: first, dislocations in deforming crystals and, second, chaotic behaviors of defects in thermally driven Rayleigh-Bénard hydrodynamic systems. The results are encouraging for broader applications of this statistical concept.

Fracture toughness of crystalline solids.

This paper describes an attempt to construct a first-principles theory of the fracture toughness of crystalline solids. It is based on the thermodynamic dislocation theory (TDT), which starts with the assertion that dislocations in solids must obey the second law of thermodynamics. A second starting assumption is that fracture is initiated when the tip of a notch is driven to undergo a dynamic shape instability. The results of this analysis are developed in comparison with measurements by Gumbsch and colleagues of the notch toughness of both predeformed and non-predeformed tungsten crystals. The theory includes a simple ad hoc conjecture regarding tip dynamics at small dislocation densities. Nevertheless, its predictions agree quantitatively with the experimental data, including both brittle and ductile fracture, over a wide range of temperatures, loading rates, and initial conditions.

Strongly reducing magnesium(0) complexes.

A complex of a metal in its zero oxidation state can be considered a stabilized, but highly reactive, form of a single metal atom. Such complexes are common for the more noble transition metals. Although rare examples are known for electronegative late-main-group p-block metals or semimetals1-6, it is a challenge to isolate early-main-group s-block metals in their zero oxidation state7-11. This is directly related to their very low electronegativity and strong tendency to oxidize. Here we present examples of zero-oxidation-state magnesium (that is, magnesium(0)) complexes that are stabilized by superbulky, monoanionic, ß-diketiminate ligands. Whereas the reactivity of an organomagnesium compound is typically defined by the nucleophilicity of its organic groups and the electrophilicity of Mg2+ cations, the Mg0 complexes reported here feature electron-rich Mg centres that are nucleophilic and strongly reducing. The latter property is exemplified by the ability to reduce Na+ to Na0. We also present a complex with a linear Mg3 core that formally could be described as a MgI-Mg0-MgI unit. Such multinuclear mixed-valence Mgn clusters are discussed as fleeting intermediates during the early stages of Grignard reagent formation. Their remarkably strong reducing power implies a rich reactivity and application as specialized reducing agents.

Dinitrogen complexation and reduction at low-valent calcium.

Here we report that attempted preparation of low-valent CaI complexes in the form of LCa-CaL (where L is a bulky ß-diketiminate ligand) under dinitrogen (N2) atmosphere led to isolation of LCa(N2)CaL, which was characterized crystallographically. The N2 2- anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N2)CaL acts as a synthon for the low-valent CaI complex LCa-CaL, which was the target of our studies. The N2 2- anion could also be protonated to diazene (N2H2) that disproportionated to hydrazine and N2 The role of Ca d orbitals for N2 activation is discussed.

[Use of the Carina active middle ear implant in otosclerosis patients]. / Einsatz des aktiven Mittelohrimplantats Carina bei Otosklerose.

Patients with otosclerosis can suffer from different grades of combined hearing loss. In addition to surgery (stapedectomy), conventional hearing aids can be used in the treatment of otosclerosis. In cases of severe conductive components in addition to sensorineural hearing loss, treatment with normal hearing aids can be difficult or impossible. In these patients, implantable hearing systems such as cochlear implants represent a possible alternative. The totally implantable Carina middle ear system can be used in patients with even high-grade sensorineural hearing loss. Based on two exemplary cases, the option of using the Carina system in otosclerosis patients and post-implantation results are reported.

Scaling confirmation of the thermodynamic dislocation theory.

The thermodynamic dislocation theory (TDT) is based on two highly unconventional assumptions: first, that driven systems containing large numbers of dislocations are subject to the second law of thermodynamics and second, that the controlling inverse timescale for these systems is the thermally activated rate at which entangled pairs of dislocations become unpinned from each other. Here, we show that these two assumptions predict a scaling relation for steady-state stress as a function of strain rate and that this relation is accurately obeyed over a wide range of experimental data for aluminum and copper. This scaling relation poses a stringent test for the validity of the TDT. The fact that the TDT passes this test means that a wide range of problems in solid mechanics, previously thought to be fundamentally intractable, can now be addressed with confidence.

Brittle-ductile transitions in a metallic glass.

Recent computational and laboratory experiments have shown that brittle-ductile transitions in the notch toughnesses of metallic glasses such as Vitreloy 1 are strongly sensitive to the initial effective disorder (or "fictive") temperature. Glasses with lower effective temperatures are weak and brittle; those with higher effective temperatures are strong and ductile. The analysis of this phenomenon presented here examines the onset of fracture at the tip of a notch as predicted by the shear-transformation-zone theory of spatially varying plastic deformation. The central ingredient of this analysis is an approximation for the dynamics of the plastic zone formed by stress concentration at the notch tip. This zone first shields the tip but then, with increasing stress, expands suddenly, producing a discontinuous transition between brittle and ductile failure in satisfactory agreement with the numerical and experimental observations.

Active site rearrangement and structural divergence in prokaryotic respiratory oxidases.

Cytochrome bd-type quinol oxidases catalyze the reduction of molecular oxygen to water in the respiratory chain of many human-pathogenic bacteria. They are structurally unrelated to mitochondrial cytochrome c oxidases and are therefore a prime target for the development of antimicrobial drugs. We determined the structure of the Escherichia coli cytochrome bd-I oxidase by single-particle cryo-electron microscopy to a resolution of 2.7 angstroms. Our structure contains a previously unknown accessory subunit CydH, the L-subfamily-specific Q-loop domain, a structural ubiquinone-8 cofactor, an active-site density interpreted as dioxygen, distinct water-filled proton channels, and an oxygen-conducting pathway. Comparison with another cytochrome bd oxidase reveals structural divergence in the family, including rearrangement of high-spin hemes and conformational adaption of a transmembrane helix to generate a distinct oxygen-binding site.

Guidelines for the management of postoperative soiling in children with Hirschsprung disease.

Although most children with Hirschsprung disease ultimately achieve functional and comfortable stooling, some will experience a variety of problems after pull-through surgery. The most common problems include soiling, obstructive symptoms, enterocolitis, and failure to thrive. The purpose of this guideline is to present a rational approach to the management of postoperative soiling in children with Hirschsprung disease. The American Pediatric Surgical Association Hirschsprung Disease Interest Group engaged in a literature review and group discussions. Expert consensus was then used to summarize the current state of knowledge regarding causes, methods of diagnosis, and treatment approaches to children with soiling symptoms following pull-through for Hirschsprung disease. Causes of soiling after pull-through are broadly categorized as abnormalities in sensation, abnormalities in sphincter control, and "pseudo-incontinence." A stepwise algorithm for the diagnosis and management of soiling after a pull-through for Hirschsprung disease is presented; it is our hope that this rational approach will facilitate treatment and optimize outcomes.

[Georgia, a country of diverse aid from Germany in the ENT field]. / Georgien, ein Land vielfältiger Hilfen aus Deutschland auf dem HNO-Gebiet.

Following a long-term tradition, several teams of German ENT specialists are currently working in different Georgian clinics on a charitable basis. The current paper describes the structures of the medical and health insurance systems in this southern Caucasian country. The course of medical education for physicians in Georgia is portrayed and differences to the German situation which explain why young Georgian colleagues have difficulties when moving to Germany are highlighted. The paper describes the typical stay of a German ENT specialist in Georgia and also points out how these physicians are in turn supported in their charitable work by medical devices and equipment sent from Germany. Finally, the input that German colleagues can contribute to improving the situation in the Georgian health care system is discussed from the perspective of German ENT specialists and future goals of the cooperation between German and Georgian physicians are summarized.

Thermodynamic analysis of the Livermore molecular-dynamics simulations of dislocation-mediated plasticity.

Results of recent large-scale molecular dynamics simulations of dislocation-mediated solid plasticity are compared with predictions of the statistical thermodynamic theory of these phenomena. These computational and theoretical analyses are in substantial agreement with each other in both their descriptions of strain-rate-dependent steady plastic flows and of transient stress peaks associated with initially small densities of dislocations. The comparisons between the numerical simulations and basic theory reveal inconsistencies in some conventional phenomenological descriptions of solid plasticity.

Yielding transitions and grain-size effects in dislocation theory.

The statistical-thermodynamic dislocation theory developed in previous papers is used here in an analysis of yielding transitions and grain-size effects in polycrystalline solids. Calculations are based on the 1995 experimental results of Meyers, Andrade, and Chokshi [Metall. Mater. Trans. A 26, 2881 (1995)MMTAEB1073-562310.1007/BF02669646] for polycrystalline copper under strain-hardening conditions. The main assertion is that the well-known Hall-Petch effects are caused by enhanced strengths of dislocation sources at the edges of grains instead of the commonly assumed resistance to dislocation flow across grain boundaries. The theory describes rapid transitions between elastic and plastic deformation at yield points; thus it can be used to predict grain-size dependence of both yield stresses and flow stresses.

Evaluation of the long-term cost-effectiveness of IDegLira versus liraglutide added to basal insulin for patients with type 2 diabetes failing to achieve glycemic control on basal insulin in the USA.

BACKGROUND AND AIMS: IDegLira, a fixed ratio combination of insulin degludec and glucagon-like peptide-1 receptor agonist liraglutide, utilizes the complementary mechanisms of action of these two agents to improve glycemic control with low risk of hypoglycemia and avoidance of weight gain. The aim of the present analysis was to assess the long-term cost-effectiveness of IDegLira vs liraglutide added to basal insulin, for patients with type 2 diabetes not achieving glycemic control on basal insulin in the US setting. METHODS: Projections of lifetime costs and clinical outcomes were made using the IMS CORE Diabetes Model. Treatment effect data for patients receiving IDegLira and liraglutide added to basal insulin were modeled based on the outcomes of a published indirect comparison, as no head-to-head clinical trial data is currently available. Costs were accounted in 2015 US dollars ($) from a healthcare payer perspective. RESULTS: IDegLira was associated with small improvements in quality-adjusted life expectancy compared with liraglutide added to basal insulin (8.94 vs 8.91 discounted quality-adjusted life years [QALYs]). The key driver of improved clinical outcomes was the greater reduction in glycated hemoglobin associated with IDegLira. IDegLira was associated with mean costs savings of $17,687 over patient lifetimes vs liraglutide added to basal insulin, resulting from lower treatment costs and cost savings as a result of complications avoided. CONCLUSIONS: The present long-term modeling analysis found that IDegLira was dominant vs liraglutide added to basal insulin for patients with type 2 diabetes failing to achieve glycemic control on basal insulin in the US, improving clinical outcomes and reducing direct costs.

Thermal effects in dislocation theory. II. Shear banding.

The thermodynamic dislocation theory presented in previous papers is used here to describe shear-banding instabilities. Central ingredients of the theory are a thermodynamically defined effective configurational temperature and a formula for the plastic strain rate determined by thermally activated depinning of entangled dislocations. This plastic strain rate is extremely sensitive to variations of the stress and the ordinary temperature. As a result of this sensitivity, the system undergoes rapid shear banding instabilities when ordinary thermal relaxation is slow. It also undergoes rapid changes from elastic to plastic behaviors at yielding transitions.

Guidelines for the management of postoperative obstructive symptoms in children with Hirschsprung disease.

Although most children with Hirschsprung disease ultimately do well, many experience a variety of ongoing problems after pull-through surgery. The most common include obstructive symptoms, soiling, enterocolitis and failure to thrive. The purpose of this guideline is to present a rational approach to the management of postoperative obstructive symptoms in children with Hirschsprung disease. The American Pediatric Surgical Association Board of Governors established a Hirschsprung Disease Interest Group. Group discussions, literature review and expert consensus were then used to summarize the current state of knowledge regarding causes, methods of diagnosis, and treatment approaches to children with obstructive symptoms following pull-through for Hirschsprung disease. Causes of obstructive symptoms post-pull-through include mechanical obstruction; persistent or acquired aganglionosis, hypoganglionosis, or transition zone pull-through; internal sphincter achalasia; disordered motility in the proximal intestine that contains ganglion cells; or functional megacolon caused by stool-holding behavior. An algorithm for the diagnosis and management of obstructive symptoms after a pull-through for Hirschsprung disease is presented. A stepwise, logical approach to the diagnosis and management of patients experiencing obstructive symptoms following pull-through for Hirschsprung disease can facilitate treatment. Level of evidence V.

Thermodynamic dislocation theory of high-temperature deformation in aluminum and steel.

The statistical-thermodynamic dislocation theory developed in previous papers is used here in an analysis of high-temperature deformation of aluminum and steel. Using physics-based parameters that we expect theoretically to be independent of strain rate and temperature, we are able to fit experimental stress-strain curves for three different strain rates and three different temperatures for each of these two materials. Our theoretical curves include yielding transitions at zero strain in agreement with experiment. We find that thermal softening effects are important even at the lowest temperatures and smallest strain rates.

Thermodynamic theory of dislocation-enabled plasticity.

The thermodynamic theory of dislocation-enabled plasticity is based on two unconventional hypotheses. The first of these is that a system of dislocations, driven by external forces and irreversibly exchanging heat with its environment, must be characterized by a thermodynamically defined effective temperature that is not the same as the ordinary temperature. The second hypothesis is that the overwhelmingly dominant mechanism controlling plastic deformation is thermally activated depinning of entangled pairs of dislocations. This paper consists of a systematic reformulation of this theory followed by examples of its use in analyses of experimentally observed phenomena including strain hardening, grain-size (Hall-Petch) effects, yielding transitions, and adiabatic shear banding.

Insufficient Vitamin D Response to Solar Radiation in German Patients with Type 2 Diabetes or Gestational Diabetes.

Vitamin D deficiency is highly prevalent in all forms of diabetes mellitus. Recently, we reported how ultraviolet B (UVB) radiation affected vitamin D [25(OH)D3] concentrations in patients with type 1 diabetes. Our aim was to analyze whether patients with non-autoimmune diabetes, such as type 2 diabetes mellitus (T2DM) and gestational diabetes mellitus (GDM) also show the same vitamin D profile in relation to environmental factors including ambient temperature as an indirect parameter for outdoor activities. We analyzed 25(OH)D3 concentrations of T2DM (n=349) and GDM patients (n=327) at the University Hospital Frankfurt from 2005 to 2007. Additionally, daily UVB and monthly outside air temperature measurements for Frankfurt/Germany were obtained. We detected a positive correlation between UVB irradiation and 25(OH)D3 concentrations of T2DM and GDM patients (rho=0.50 and rho=0.63, p=0.003 and p<0.0001, respectively). UVB irradiation was in summer (April-October) higher than in winter (November-March) (5.6 kJ/m² vs. 0.5 kJ/m², p<0.0001). However, the prevalence of vitamin D deficiency in summer remained high with 76% in T2DM and 59% in GDM. In a stepwise regression analysis for the 25(OH)D3 concentration, significant predictors were outdoor temperature (estimate=0.02, p<0.0001), UVB radiation (estimate=-0.0015, p=0.02), year (2006 vs. 2005 estimate=-0.06, p>0.05, 2007 vs. 2005: estimate=-0.13, p<0.0001) and diabetes type (estimate=0.06, p=0.03). In conclusion, the strong correlation between UVB radiation and 25(OH)D3 concentrations in T2DM and GDM patients determines the seasonal variation. Additional determinants for the 25(OH)D3 concentrations were outdoor temperature, year, and diabetes type. Despite the effects of solar radiation both patients groups remain largely vitamin D deficient during summers.

Thermal effects in dislocation theory.

The mechanical behaviors of polycrystalline solids are determined by the interplay between phenomena governed by two different thermodynamic temperatures: the configurational effective temperature that controls the density of dislocations, and the ordinary kinetic-vibrational temperature that controls activated depinning mechanisms and thus deformation rates. This paper contains a review of the effective-temperature theory and its relation to conventional dislocation theories. It includes a simple illustration of how these two thermal effects can combine to produce a predictive theory of spatial heterogeneities such as shear-banding instabilities. Its main message is a plea that conventional dislocation theories be reformulated in a thermodynamically consistent way so that the vast array of observed behaviors can be understood systematically.

Statistical thermodynamics of strain hardening in polycrystalline solids.

This paper starts with a systematic rederivation of the statistical thermodynamic equations of motion for dislocation-mediated plasticity proposed in 2010 by Langer, Bouchbinder, and Lookman [Acta Mat. 58, 3718 (2010)ACMAFD1359-645410.1016/j.actamat.2010.03.009]. It then uses that theory to explain the anomalous rate-hardening behavior reported in 1988 by Follansbee and Kocks and to explore the relation between hardening rate and grain size reported in 1995 by Meyers et al. A central theme is the need for physics-based, nonequilibrium analyses in developing predictive theories of the strength of polycrystalline materials.