Fragility of iron-based glasses

The viscosity of various iron-based bulk-glass-forming liquids is measured around the glass transition, and the associated fragility is calculated. Fragility is found to vary broadly between compositions, from a low value of ~43, which indicates fairly “strong” liquid behavior, to ~65, well within the region of “fragile” behavior. Despite a strong covalent bonding identified in the structure of this class of metal/metalloid glasses, their liquid fragility can be remarkably high, exceeding even the very fragile palladium and platinum bulk-glass formers. An inverse correlation between glass-forming ability and fragility is identified, suggesting that iron-based glasses are effectively “kinetically” stabilized

Variation of Sound Velocity in Fatigued Aluminum 2024-T4 as a Function fo Hydrostatic Pressure

It is well known that a pressure or stress derivative measurement of the sound velocity gives information about the nonlinear elastic properties of the material under investigation. Over the last several decades numerous experiments on various solids using uniaxial stress apparatus or oil-filled hydrostatic pressure chambers have been reported. In most cases the pressure or stress must be increased to several thousand kilobars to obtain reasonable measurements. The necessity of using such high pressure usually results from the low sensitivity of the devices or techniques used to measure the change in the sound velocity

Lunar hand tools

Tools useful for operations and maintenance tasks on the lunar surface were determined and designed. Primary constraints are the lunar environment, the astronaut's space suit and the strength limits of the astronaut on the moon. A multipurpose rotary motion tool and a collapsible tool carrier were designed. For the rotary tool, a brushless motor and controls were specified, a material for the housing was chosen, bearings and lubrication were recommended and a planetary reduction gear attachment was designed. The tool carrier was designed primarily for ease of access to the tools and fasteners. A material was selected and structural analysis was performed on the carrier. Recommendations were made about the limitations of human performance and about possible attachments to the torque driver

Observation of an apparent first-order glass transition in ultrafragile Pt–Cu–P bulk metallic glasses

An experimental study of the configurational thermodynamics for a series of near-eutectic Pt_(80-x)Cu_xP₂₀ bulk metallic glass-forming alloys is reported where 14 < x < 27. The undercooled liquid alloys exhibit very high fragility that increases as x decreases, resulting in an increasingly sharp glass transition. With decreasing x, the extrapolated Kauzmann temperature of the liquid, T_K, becomes indistinguishable from the conventionally defined glass transition temperature, T_g. For x < 17, the observed liquid configurational enthalpy vs. T displays a marked discontinuous drop or latent heat at a well-defined freezing temperature, T_(gm). The entropy drop for this first-order liquid/glass transition is approximately two-thirds of the entropy of fusion of the crystallized eutectic alloy. Below T_(gm), the configurational entropy of the frozen glass continues to fall rapidly, approaching that of the crystallized eutectic solid in the low T limit. The so-called Kauzmann paradox, with negative liquid entropy (vs. the crystalline state), is averted and the liquid configurational entropy appears to comply with the third law of thermodynamics. Despite their ultrafragile character, the liquids at x = 14 and 16 are bulk glass formers, yielding fully glassy rods up to 2- and 3-mm diameter on water quenching in thin-wall silica tubes. The low Cu content alloys are definitive examples of glasses that exhibit first-order melting

Single-nucleotide polymorphism-based genetic risk score and patient age at prostate cancer diagnosis

Importance: Few studies have evaluated the association between a single-nucleotide polymorphism-based genetic risk score (GRS) and patient age at prostate cancer (PCa) diagnosis. Objectives: To test the association between a GRS and patient age at PCa diagnosis and to compare the performance of a GRS with that of family history (FH) in PCa risk stratification. Design, Setting, and Participants: A cohort study of 3225 white men was conducted as a secondary analysis of the Reduction by Dutasteride of Prostate Cancer Events (REDUCE) chemoprevention trial, a 4-year, randomized, double-blind, placebo-controlled multicenter study conducted from March 2003 to April 2009 to evaluate the safety and efficacy of dutasteride in reducing PCa events. Participants were confirmed to be cancer free by prostate biopsy (6-12 cores) within 6 months prior to the study and underwent 10 core biopsies every 2 years per protocol. The dates for performing data analysis were from July 2016 to October 2019. Interventions: A well-established, population-standardized GRS was calculated for each participant based on 110 known PCa risk-associated single-nucleotide polymorphisms, which is a relative risk compared with the general population. Men were classified into 3 GRS risk groups based on predetermined cutoff values: low (\u3c0.50), average (0.50-1.49), and high (≥1.50). Main Outcomes and Measures: Prostate cancer diagnosis-free survival among men of different risk groups. Results: Among 3225 men (median age, 63 years [interquartile range, 58-67 years]) in the study, 683 (21%) were classified as low risk, 1937 (60%) as average risk, and 605 (19%) as high risk based on GRS alone. In comparison, 2789 (86%) were classified as low or average risk and 436 (14%) as high risk based on FH alone. Men in higher GRS risk groups had a PCa diagnosis-free survival rate that was worse than that of those in the lower GRS risk group (χ2 = 53.3; P \u3c .001 for trend) and in participants with a negative FH of PCa (χ2 = 45.5; P \u3c .001 for trend). Combining GRS and FH further stratified overall genetic risk, indicating that 957 men (30%) were at high genetic risk (either high GRS or positive FH), 1667 men (52%) were at average genetic risk (average GRS and negative FH), and 601 men (19%) were at low genetic risk (low GRS and negative FH). The median PCa diagnosis-free survival was 74 years (95% CI, 73-75 years) for men at high genetic risk, 77 years (95% CI, 75 to \u3e80 years) for men at average genetic risk, and more than 80 years (95% CI, \u3e80 to \u3e80 years) for men at low genetic risk. In contrast, the median PCa diagnosis-free survival was 73 years (95% CI, 71-76 years) for men with a positive FH and 77 years (95% CI, 76-79 years) for men with a negative FH. Conclusions and Relevance: This study suggests that a GRS is significantly associated with patient age at PCa diagnosis. Combining FH and GRS may better stratify inherited risk than FH alone for developing personalized PCa screening strategies

Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways—the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol—the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates—suggest that it might find extensive applications in heterocycle synthesis

Manipulation of Muscle Creatine and Glycogen Changes Dual X-ray Absorptiometry Estimates of Body Composition

Standardizing a dual x-ray absorptiometry (DXA) protocol is thought to provide a reliable measurement of body composition. Purpose: We investigated the effects of manipulating muscle glycogen and creatine content independently and additively on DXA estimates of lean mass. Method: Eighteen well-trained male cyclists undertook a parallel group application of creatine loading (n = 9) (20 g·d−1 for 5 d loading; 3 g·d−1 maintenance) or placebo (n = 9) with crossover application of glycogen loading (12 v 6 g·kg−1 BM per day for 48 h) as part of a larger study involving a glycogen-depleting exercise protocol. Body composition, total body water, muscle glycogen and creatine content were assessed via DXA, bioelectrical impedance spectroscopy and standard biopsy techniques. Changes in the mean were assessed using the following effect-size scale: > 0.2 small, > 0.6, moderate, > 1.2 large and compared with the threshold for the smallest worthwhile effect of the treatment. Results: Glycogen loading, both with and without creatine loading, resulted in substantial increases in estimates of lean body mass (mean ± SD; 3.0% ± 0.7% and 2.0% ± 0.9%) and leg lean mass (3.1% ± 1.8% and 2.6% ± 1.0%) respectively. A substantial decrease in leg lean mass was observed after the glycogen depleting condition (−1.4% ± 1.6%). Total body water showed substantial increases after glycogen loading (2.3% ± 2.3%), creatine loading (1.4% ± 1.9%) and the combined treatment (2.3% ± 1.1%). Conclusions: Changes in muscle metabolites and water content alter DXA estimates of lean mass during periods in which minimal change in muscle protein mass is likely. This information needs to be considered in interpreting the results of DXA-derived estimates of body composition in athletes