Nanostructured Molecular-Network Arsenoselenides from the Border of a Glass-Forming Region: A Disproportionality Analysis Using Complementary Characterization Probes.

Binary AsxSe100-x alloys from the border of a glass-forming region (65 < x < 70) subjected to nanomilling in dry and dry-wet modes are characterized by the XRPD, micro-Raman scattering (micro-RS) and revised positron annihilation lifetime (PAL) methods complemented by a disproportionality analysis using the quantum-chemical cluster modeling approach. These alloys are examined with respect to tetra-arsenic biselenide As4Se2 stoichiometry, realized in glassy g-As65Se35, glassy-crystalline g/c-As67Se33 and glassy-crystalline g/c-As70Se30. From the XRPD results, the number of rhombohedral As and cubic arsenolite As2O3 phases in As-Se alloys increases after nanomilling, especially in the wet mode realized in a PVP water solution. Nanomilling-driven amorphization and reamorphization transformations in these alloys are identified by an analysis of diffuse peak halos in their XRPD patterning, showing the interplay between the levels of a medium-range structure (disruption of the intermediate-range ordering at the cost of an extended-range one). From the micro-RS spectroscopy results, these alloys are stabilized by molecular thioarsenides As4Sen (n = 3, 4), regardless of their phase composition, remnants of thioarsenide molecules destructed under nanomilling being reincorporated into a glass network undergoing a polyamorphic transition. From the PAL spectroscopy results, volumetric changes in the wet-milled alloys with respect to the dry-milled ones are identified as resulting from a direct conversion of the bound positron-electron (Ps, positronium) states in the positron traps. Ps-hosting holes in the PVP medium appear instead of positron traps, with ~0.36-0.38 ns lifetimes ascribed to multivacancies in the As-Se matrix. The superposition of PAL spectrum peaks and tails for pelletized PVP, unmilled, dry-milled, and dry-wet-milled As-Se samples shows a spectacular smoothly decaying trend. The microstructure scenarios of the spontaneous (under quenching) and activated (under nanomilling) decomposition of principal network clusters in As4Se2-bearing arsenoselenides are recognized. Over-constrained As6·(2/3) ring-like network clusters acting as pre-cursors of the rhombohedral As phase are the main products of this decomposition. Two spontaneous processes for creating thioarsenides with crystalline counterparts explain the location of the glass-forming border in an As-Se system near the As4Se2 composition, while an activated decomposition process for creating layered As2Se3 structures is responsible for the nanomilling-driven molecular-to-network transition.

X-ray polarization evidence for a 200-year-old flare of Sgr A.

The centre of the Milky Way Galaxy hosts a black hole with a solar mass of about 4 million (Sagittarius A* (Sgr A)) that is very quiescent at present with a luminosity many orders of magnitude below those of active galactic nuclei1. Reflection of X-rays from Sgr A* by dense gas in the Galactic Centre region offers a means to study its past flaring activity on timescales of hundreds and thousands of years2. The shape of the X-ray continuum and the strong fluorescent iron line observed from giant molecular clouds in the vicinity of Sgr A* are consistent with the reflection scenario3-5. If this interpretation is correct, the reflected continuum emission should be polarized6. Here we report observations of polarized X-ray emission in the direction of the molecular clouds in the Galactic Centre using the Imaging X-ray Polarimetry Explorer. We measure a polarization degree of 31% ± 11%, and a polarization angle of -48° ± 11°. The polarization angle is consistent with Sgr A* being the primary source of the emission, and the polarization degree implies that some 200 years ago, the X-ray luminosity of Sgr A* was briefly comparable to that of a Seyfert galaxy.

Polarized x-rays constrain the disk-jet geometry in the black hole x-ray binary Cygnus X-1.

A black hole x-ray binary (XRB) system forms when gas is stripped from a normal star and accretes onto a black hole, which heats the gas sufficiently to emit x-rays. We report a polarimetric observation of the XRB Cygnus X-1 using the Imaging X-ray Polarimetry Explorer. The electric field position angle aligns with the outflowing jet, indicating that the jet is launched from the inner x-ray-emitting region. The polarization degree is 4.01 ± 0.20% at 2 to 8 kiloelectronvolts, implying that the accretion disk is viewed closer to edge-on than the binary orbit. These observations reveal that hot x-ray-emitting plasma is spatially extended in a plane perpendicular to, not parallel to, the jet axis.

Influence of nanosized defects on photoluminescence efficiency of Er3+ ions co-doped with Au2 O3 in a lead boroselenate glass ceramic system: a novel approach using positron annihilation lifetime spectroscopy.

This study consists of the results of an investigation into the influence of the free-volume space (fv ) defects on luminescence efficiency (LE) of erbium ions in Au2 O3 -doped PbO-B2 O3 -SeO2 (PBS) glass ceramics. Glass ceramics containing fixed concentrations of Er3+ ions and varied concentrations of Au2 O3 were synthesized. X-ray diffraction studies indicated that the samples contained Au2 (SeO3 )3 crystalline phase and nano gold metallic particles. The concentration of defects entrenched in the glass ceramics estimated in terms of Au2 O3 content using positron annihilation lifetime spectroscopy measurement indicated the highest content in the glass ceramic containing 0.075 mol% of Au2 O3 . Optical absorption and the photoluminescence (PL) spectra of the glass ceramics were studied in the visible region. The observed increase of PL efficiency was attributed to the enhanced concentration of free-volume imperfections in the samples. A perfect correlation could be achieved between the free-volume fraction and the PL efficiency of erbium ions in these glass ceramics.

The Art of Positronics in Contemporary Nanomaterials Science: A Case Study of Sub-Nanometer Scaled Glassy Arsenoselenides.

The possibilities surrounding positronics, a versatile noninvasive tool employing annihilating positrons to probe atomic-deficient sub-nanometric imperfections in a condensed matter, are analyzed in application to glassy arsenoselenides g-AsxSe100-x (0 < x < 65), subjected to dry and wet (in 0.5% PVP water solution) nanomilling. A preliminary analysis was performed within a modified two-state simple trapping model (STM), assuming slight contributions from bound positron-electron (Ps, positronium) states. Positron trapping in g-AsxSe100-x/PVP nanocomposites was modified by an enriched population of Ps-decay sites in PVP. This was proven within a three-state STM, assuming two additive inputs in an overall trapping arising from distinct positron and Ps-related states. Formalism of x3-x2-CDA (coupling decomposition algorithm), describing the conversion of Ps-decay sites into positron traps, was applied to identify volumetric nanostructurization in wet-milled g-As-Se, with respect to dry-milled ones. Under wet nanomilling, the Ps-decay sites stabilized in inter-particle triple junctions filled with PVP replaced positron traps in dry-milled substances, the latter corresponding to multi-atomic vacancies in mostly negative environments of Se atoms. With increased Se content, these traps were agglomerated due to an abundant amount of Se-Se bonds. Three-component lifetime spectra with nanostructurally- and compositionally-tuned Ps-decay inputs and average lifetimes serve as a basis to correctly understand the specific "rainbow" effects observed in the row from pelletized PVP to wet-milled, dry-milled, and unmilled samples.

Evaluating Pharmacist Impact on Guideline-Directed Medical Therapy in Patients With Reduced Ejection Fraction Heart Failure.

BACKGROUND: Limited literature exists evaluating the ability of a pharmacist to quickly and effectively initiate and manage dose titrations of guideline-directed medication therapy (GDMT) in an outpatient setting. METHODS: This pilot study aimed to investigate the impact of pharmacist-managed, outpatient heart failure management on patients' heart failure outcomes, and health-care-related costs. Retrospective chart review performed on patients referred to pharmacist practicing under collaborative practice agreement. End points included time to achieve individualized target doses of GDMT; beta-blocker dose tolerance; and the clinic's impact on left ventricular ejection fraction (LVEF), hospital admission, and emergency department encounter rates. Descriptive statistics were used to report nominal data. Wilcoxon signed-rank test was used to evaluate continuous variables. RESULTS: Thirty-six patients completed full titration utilizing an average of 4.9 visits over 12.7 weeks. Seventy-eight percent (n = 28) achieved full beta-blocker titration. Seventy-six percent of patients had LVEF >35% after titration versus 43% at baseline. A significant reduction in all-cause hospital admissions was seen during both 13-week and 12-month comparison periods (P < .05). We estimated >US$50 000 annual revenue generation from 0.2 full-time equivalent pharmacist. CONCLUSIONS: Although hypothesis generating, our results support the idea that pharmacist-managed medication titration clinics are effective at completing titration, improving LVEF, and generating revenue.

Genetic Variation of Hepatic Enzymes Influence on ß-Blocker Dose in Patients With Reduced Ejection Fraction Heart Failure.

Beta-blockers such as metoprolol, carvedilol, and bisoprolol are indicated for the treatment of patients with reduced ejection fraction heart failure. Heart failure treatment guidelines call for titration of these medications to specific target doses for morbidity and mortality benefit. Hepatic enzymes are responsible for metabolizing these medications; however, these enzymes are subject to genetic variations (polymorphisms) that can increase or decrease enzyme activity. Metoprolol relies almost exclusively on this enzyme for degradation to inactive metabolites, whereas carvedilol relies on this enzyme only partially for metabolism, and the portion of drug that is metabolized by CYP2D6 becomes active metabolites. The clinical significance of genetic variations in CYP2D6 in heart failure patients requiring treatment with carvedilol and metoprolol remains unclear, and further research is needed before any strong recommendations on treatment approach can be made. However, based on what is known regarding the incidence of genetic variations of this enzyme, it is reasonable to conclude that heart failure patients of European and Asian ancestry may be at a greater risk of intolerance to guideline-directed doses of metoprolol. Patients of North African ancestry may be at a lower risk of intolerance to metoprolol, although limited data are available to conclude. Additionally, due to the significant prevalence of CYP2D6 enzyme variations among all ethnicities, it may be reasonable to consider switching to carvedilol for patients who are unable to fully titrate metoprolol.

PALS probing of photopolymerization shrinkage in densely packed acrylate-type dental restorative composites.

BACKGROUND: Using positron annihilation lifetime spectroscopy (PALS), microstructural changes in commercial dental restorative composites under light-curing polymerization were identified as a modification in mixed positron/Ps trapping, where the decay of positronium (Ps; the bound state of positrons and electrons) is caused by free-volume holes mainly in the polymer matrix, and positron trapping is defined by interfacial free-volume holes in a mixed filler-polymer environment. In loosely packed composites with a filler content of <70-75%, this process was related to the conversion of Ps-to-positron trapping. OBJECTIVES: To disclose such peculiarities in densely packed composites using the example of he commercially available acrylate-based composite ESTA-3® (ESTA Ltd., Kiev, Ukraine), which boasts a polymerization volumetric shrinkage of only 1.5%. MATERIAL AND METHODS: ESTA­3® was used as a commercially available acrylate-based dental restorative composite. A fast-fast coincidence system of 230­ps resolution based on 2 photomultiplier tubes coupled to a BaF2 detector and ORTEC® electronics was used to register lifetime spectra in normal-measurement statistics. The raw PAL spectra were treated using x3-x2-CDA (coupling decomposition algorithm). RESULTS: The annihilation process in the densely packed dental restorative composites (DRCs), as exemplified by the commercially available acrylate-based composite ESTA­3®, is identified as mixed positron/ Ps trapping, where o-Ps decay is caused by free-volume holes in the polymer matrix and interfacial filler-polymer regions, and free positron annihilation is defined by free-volume holes between filler particles. The most adequate model-independent estimation of the polymerization volumetric shrinkage can be done using averaged positron annihilation lifetime. A meaningful description of the transformations in Psand positron-trapping sites under light curing can be developed on the basis of a semiempirical model exploring x3­x2­CDA. There is a strong monolithization of agglomerated filler nanoparticles in these composites, caused by the photo-induced disappearing of positron traps at the cost of Ps-decaying holes. CONCLUSIONS: Governing the polymerization void-evolution process in densely packed DRC ESTA­3® occurs mainly in the filler sub-system as positron-to-Ps trapping conversion, which is the reason for the low corresponding volumetric shrinkage.

Microstructure Hierarchical Model of Competitive e+-Ps Trapping in Nanostructurized Substances: from Nanoparticle-Uniform to Nanoparticle-Biased Systems.

Microstructure hierarchical model considering the free-volume elements at the level of interacting crystallites (non-spherical approximation) and the agglomerates of these crystallites (spherical approximation) was developed to describe free-volume evolution in mechanochemically milled As4S4/ZnS composites employing positron annihilation spectroscopy in a lifetime measuring mode. Positron lifetime spectra were reconstructed from unconstrained three-term decomposition procedure and further subjected to parameterization using x3-x2-coupling decomposition algorithm. Intrinsic inhomogeneities due to coarse-grained As4S4 and fine-grained ZnS nanoparticles were adequately described in terms of substitution trapping in positron and positronium (Ps) (bound positron-electron) states due to interfacial triple junctions between contacting particles and own free-volume defects in boundary compounds. Compositionally dependent nanostructurization in As4S4/ZnS nanocomposite system was imagined as conversion from o-Ps trapping sites to positron traps. The calculated trapping parameters that were shown could be useful to characterize adequately the nanospace filling in As4S4/ZnS composites.

Light-cured dimethacrylate dental restorative composites under a prism of annihilating positrons.

BACKGROUND: Breakthrough resolutions in current biopolymer engineering rely on reliable diagnostics of atomic-deficient spaces over the finest sub-nanometer length scales. One such diagnostic is positron annihilation lifetime spectroscopy, which probes space-time continuum relationships for the interaction between electrons and their antiparticle (positrons) in structural entities like free-volume defects, vacancies, vacancy-like clusters, interfacial voids and pores, etc. OBJECTIVES: This paper is intended to highlight the possibilities of positron annihilation lifetime spectroscopy as an informative instrumentation tool to parameterize free-volume evolution in light-cured dimethacrylate dental restorative composites exemplified by Charisma® (Heraeus Kulzer GmbH, Hanau, Germany) and Dipol® (Oksomat-AN Ltd, Kyiv, Ukraine). MATERIAL AND METHODS: The subjects of the study were the commercially available dimethacrylate-type dental restorative composites Charisma® and Dipol®. The analysis used a fast-fast coincidence system of 230 ps resolution based on 2 photomultiplier tubes coupled to BaF2 scintillator detectors and ORTEC® (ORTEC, Oak Ridge, USA) electronics to register lifetime spectra in normal-measurement statistics evolving ~1 million coincidences. RESULTS: The annihilation process in both composites is identified as mixed positron-Ps (positronium) trapping, where ortho-Ps decaying is caused entirely by free-volume holes in the polymer matrix, and the 2nd component is defined mainly by interfacial free-volume holes between filler nanoparticles and the surrounding polymer. The most appropriate model-independent estimation of photopolymerization volumetric shrinkage in dental restorative composites can be done using averaged positron annihilation lifetime. Partiallyconstrained x4-term analysis of lifetime spectra is less efficient, giving greater scatter of variance with an additional artifact of fixed shortest lifetime allowing unresolved mixing in the 2nd component. A meaningful phenomenological description of transformations in Ps and positron-trapping sites under light curing, which occurs more efficiently in Charisma® than in Dipol® nanocomposites, can be developed at the basis of a semi-empirical model exploring a x3-x2-coupling decomposition algorithm. CONCLUSIONS: A deep understanding of void-evolution processes in dimethacrylate dental composites employing positron annihilation lifetime spectroscopy makes it possible to diagnose, characterize and engineer novel biomaterials for advanced use in medical practice.

Free Volume Structure of Acrylic-Type Dental Nanocomposites Tested with Annihilating Positrons.

Positron annihilation spectroscopy in lifetime measuring mode exploring conventional fast-fast coincidence ORTEC system is employed to characterize free volume structure of commercially available acrylic-type dental restorative composite Charisma® (Heraeus Kulzer GmbH, Germany). The measured lifetime spectra for uncured and light-cured composites are reconstructed from unconstrained x3-term fitting and semi-empirical model exploring x3-x2-coupling decomposition algorithm. The governing channel of positron annihilation in the composites studied is ascribed to mixed positron-Ps trapping, where Ps decaying in the third component is caused entirely by input from free-volume holes in polymer matrix, while the second component is defined by free positron trapping in interfacial free-volume holes between filler nanoparticles and surrounded polymer matrix. Microstructure scenario of the photopolymerization shrinkage includes cross-linking of structural chains in polymer matrix followed by conversion of bound positron-electron (positronium) traps in positron-trapping interfacial free-volume voids in a vicinity of agglomerated filler nanoparticles.

Water-Vapor Sorption Processes in Nanoporous MgO-Al2O3 Ceramics: the PAL Spectroscopy Study.

The water-vapor sorption processes in nanoporous MgO-Al2O3 ceramics are studied with positron annihilation lifetime (PAL) spectroscopy employing positron trapping and positronium (Ps)-decaying modes. It is demonstrated that the longest-lived components in the four-term reconstructed PAL spectra with characteristic lifetimes near 2 and 60-70 ns can be, respectively, attributed to ortho-positronium (o-Ps) traps in nanopores with 0.3- and 1.5-1.8-nm radii. The first o-Ps decaying process includes "pick-off" annihilation in the "bubbles" of liquid water, while the second is based on o-Ps interaction with physisorbed water molecules at the walls of the pores. In addition, the water vapor modifies structural defects located at the grain boundaries in a vicinity of pores, this process being accompanied by void fragmentation during water adsorption and agglomeration during water desorption after drying.

Probing Sub-atomistic Free-Volume Imperfections in Dry-Milled Nanoarsenicals with PAL Spectroscopy.

Structural transformations caused by coarse-grained powdering and fine-grained mechanochemical milling in a dry mode were probed in high-temperature modification of tetra-arsenic tetra-sulfide known as ß-As4S4. In respect to X-ray diffraction analysis, the characteristic sizes of ß-As4S4 crystallites in these coarse- and fine-grained powdered pellets were 90 and 40 nm, respectively. Positron annihilation lifetime spectroscopy was employed to characterize transformations occurred in free-volume structure of these nanoarsenicals. Experimentally measured positron lifetime spectra were parameterized in respect to three- or two-term fitting procedures and respectively compared with those accumulated for single crystalline realgar α-As4S4 polymorph. The effect of coarse-grained powdering was found to result in generation of large amount of positron and positronium Ps trapping sites inside arsenicals in addition to existing ones. In fine-grained powdered ß-As4S4 pellets, the positron trapping sites with characteristic free volumes close to bi- and tri-atomic vacancies were evidently dominated. These defects were supposed to originate from grain boundary regions and interfacial free volumes near aggregated ß-As4S4 crystallites. Thus, the cumulative production of different positron traps with lifetimes close to defect-related lifetimes in realgar α-As4S4 polymorph was detected in fine-grained milled samples.

'Cold' crystallization in nanostructurized 80GeSe2-20Ga2Se3 glass.

'Cold' crystallization in 80GeSe2-20Ga2Se3 chalcogenide glass nanostructurized due to thermal annealing at 380°C for 10, 25, 50, 80, and 100 h are probed with X-ray diffraction, atomic force, and scanning electron microscopy, as well as positron annihilation spectroscopy performed in positron annihilation lifetime and Doppler broadening of annihilation line modes. It is shown that changes in defect-related component in the fit of experimental positron lifetime spectra for nanocrystallized glasses testify in favor of structural fragmentation of larger free-volume entities into smaller ones. Nanocrystallites of Ga2Se3 and/or GeGa4Se8 phases and prevalent GeSe2 phase extracted mainly at the surface of thermally treated samples with preceding nucleation and void agglomeration in the initial stage of annealing are characteristic features of cold crystallization.

Positronics of subnanometer atomistic imperfections in solids as a high-informative structure characterization tool.

Methodological possibilities of positron annihilation lifetime (PAL) spectroscopy applied to characterize different types of nanomaterials treated within three-term fitting procedure are critically reconsidered. In contrast to conventional three-term analysis based on admixed positron- and positronium-trapping modes, the process of nanostructurization is considered as substitutional positron-positronium trapping within the same host matrix. Developed formalism allows estimate interfacial void volumes responsible for positron trapping and characteristic bulk positron lifetimes in nanoparticle-affected inhomogeneous media. This algorithm was well justified at the example of thermally induced nanostructurization occurring in 80GeSe2-20Ga2Se3 glass.