Classification of intraarticular calcaneal fractures: comparison of two classification systems.

PURPOSE: Accurately classifying displaced intraarticular calcaneal fractures (DIACFs) is essential for orthopedic surgeons to choose optimal treatment methods and provide results evaluation and communication. Many authors studying used Sanders classification reported moderate intra- and interobserver reliability. Taking the software opportunity of 3D virtual exarticulation, Goldzak updated French tri-dimensional Utheza classification, providing an alternative framework for classifying DIACFs. The aim of this study was to compare the intra- and interobserver reliability of Sanders versus Goldzak classification systems. METHODS: The CT scans of 30 patients with displaced intraarticular calcaneal fractures, treated in the same trauma center between 2014-2018, were analyzed by 16 medical doctors (specialists and residents in orthopedic surgery, specialists and residents in radiology), and classified according to Sanders and Goldzak classifications. The same images were sent on two separate sessions, in a randomized order. Interobserver reliability and intraobserver reproducibility were assessed using Kappa statistics and Gwet's AC1 coefficient. RESULTS: Interobserver reliability using Gwet reported a value of 0.36 for Goldzak classification and 0.30 for Sanders classification (corresponding to "fair assessment" in both cases). In absence of subclasses, "substantial assessment" was reported for Goldzak classification (Gwet of 0.61) and "moderate assessment" for Sanders classification (Gwet of 0.46). Goldzak system had a greater interobserver reliability in the group of radiology residents. Intraobserver reliability coefficient was 0.60 for Goldzak classification and 0.69 for Sanders classification, indicating a substantial agreement for both classifications. CONCLUSION: Despite the better view of the fracture lines provided by 3D reconstructions, this study failed to prove the superiority of Goldzak classification compared to Sanders classification for DIACFs.

Comprehensive vasodilatation in women with acute heart failure: Novel insights from the GALACTIC randomized controlled trial.

AIMS: Sex-specific differences in acute heart failure (AHF) are both relevant and underappreciated. Therefore, it is crucial to evaluate the risk/benefit ratio and the implementation of novel AHF therapies in women and men separately. METHODS AND RESULTS: We performed a pre-defined sex-specific analysis in AHF patients randomized to a strategy of early intensive and sustained vasodilatation versus usual care in an international, multicentre, open-label, blinded endpoint trial. Inclusion criteria were AHF with increased plasma concentrations of natriuretic peptides, systolic blood pressure ≥100 mmHg, and plan for treatment in a general ward. Among 781 eligible patients, 288 (37%) were women. Women were older (median 83 vs. 76 years), had a lower body weight (median 64.5 vs. 77.6 kg) and lower estimated glomerular filtration rate (median 48 vs. 54 ml/min/1.73 m2 ). The primary endpoint, a composite of all-cause mortality or rehospitalization for AHF at 180 days, showed a significant interaction of treatment strategy and sex (p for interaction = 0.03; hazard ratio adjusted for female sex 1.62, 95% confidence interval 1.05-2.50; p = 0.03). The combined endpoint occurred in 53 women (38%) in the intervention group and in 35 (24%) in the usual care group. The implementation of rapid up-titration of renin-angiotensin-aldosterone system (RAAS) inhibitors was less successful in women versus men in the overall cohort and in patients with heart failure with reduced ejection fraction (median discharge % target dose in patients randomized to intervention: 50% in women vs. 75% in men). CONCLUSION: Rapid up-titration of RAAS inhibitors was less successfully implemented in women possibly explaining their higher rate of all-cause mortality and rehospitalization for AHF. CLINICAL TRIAL REGISTRATION: ClinicalTrials.gov, unique identifier NCT00512759.

Enhanced Solid-State Fluorescence of Flavin Derivatives by Incorporation in the Metal-Organic Frameworks MIL-53(Al) and MOF-5.

The flavin derivatives 10-methyl-isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were incorporated in two alternative metal-organic frameworks, (MOFs) MIL-53(Al) and MOF-5. We used a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders with one-dimensional (1D) pores and an in-situ approach during the synthesis of MOF-5 with its 3D channel network. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 5.2 wt% for 6F-MIA@MOF-5. For the high incorporation yields the probability to have more than one dye molecule in a pore volume is significant. As compared to the flavins in solution, the fluorescence spectrum of these flavin@MOF composites is broadened at the bathocromic side especially for MIA. Time-resolved spectroscopy showed that multi-exponential fluorescence lifetimes were needed to describe the decays. The fluorescence-weighted lifetime of flavin@MOF of 4 ± 1 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of "solid solutions" for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53 due to the formation of various J-aggregates. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photophysical properties of crystalline MIA and the flavin@MOF composites. In the solid flavins, π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores, single flavin molecules represent a major population and the computed MIA@MOF structures do not find π-stacking interactions with the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. To analyze the orientation of flavins in MOFs, we measured fluorescence anisotropy images of single flavin@MOF-5 crystals and a static ensemble flavin@MIL53 microcrystals, respectively. Based on image information, anisotropy distributions and overall curve of the time-resolved anisotropy curves combined with theoretical calculations, we can prove that all fluorescent flavins species have a defined and rather homogeneous orientation in the MOF framework. In MIL-53, the transition dipole moments of flavins are orientated along the 1D channel axis, whereas in MOF-5 we resolved an average orientation that is tilted with respect to the cubic crystal lattice. Notably, the more hydrophobic 6F-MIA exhibits a higher degree order than MIA. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation, defined orientation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.

Influencing factors of urban innovation and development: a grounded theory analysis.

Urban innovation and development are a core driver for promoting the industrial, economic, and social development of cities. However, the factors that affect the innovation and development of cities lack systematic analysis as well as interaction analysis. Based on a multidimensional perspective, this study suggests that natural, economic, and social factors are three major factors conditioning urban innovation and development. A grounded theoretical qualitative method is further adopted to code relevant research literatures, news reports and interview materials, resulting in an onion factors model. We find that natural factors-including environmental quality, geographic location, and city scale-are prerequisite for conditioning urban innovation and development. Economic factors are also key, including economic level, industrial structure, industrial agglomeration, and technological innovation. Social factors are guarantee factors, including administrative hierarchy, cultural environment, population structure, and government management and services, i.e., they are essential for cities to become adaptable in the current dynamic situation. The study provides theoretical support and practical directions for the formulation of policies for urban innovation development.

Using a socio-ecological framework to understand how 8-12-year-olds build and show digital resilience: A multi-perspective and multimethod qualitative study.

Educationalists', researchers', and policy makers' work on children's digital resilience has marginalised the role of the broader context within which digital resilience is constituted, experienced and derived. We aimed to address this lacuna by exploring how pre-teen's digital resilience operates as a dynamic socio-ecological process. Addressing this aim, we employed participatory methods and thematically analysed eight focus groups with children aged 8-12 years (n = 59) and 20 telephone interviews with parents/carers and teachers of 8-12-year-olds and internet safety experts to examine this issue. We used purposive sampling and collected data over three months (January-March 2020). Our analysis constructed a matrix of main themes, constituent, and cross-cutting sub-themes. By placing this within a socio-ecological framework, we illustrate how pre-teens' digital resilience operates within and across differing four levels (individual, home, community and societal) and four domains (learning, recognising, managing, and recovery). The paper advances the literature by illustrating how children can be supported to build and show digital resilience within and across different levels and domains. It is argued that digital resilience should be re-conceptualised as a collective endeavour involving children at an individual level, parents/carers within home environments, youth workers, civil society, teachers, and schools at a community level, along with governments, policymakers, and the education system and internet corporations at a societal level. We conclude by providing practice and research recommendations guiding those supporting children to facilitate opportunities to thrive online.

Whole-genome sequencing of SARS-CoV-2 reveals diverse mutations in circulating Alpha and Delta variants during the first, second, and third waves of COVID-19 in South Kivu, east of the Democratic Republic of the Congo.

OBJECTIVES: We used whole-genome sequencing of SARS-CoV-2 to identify variants circulating in the Democratic Republic of the Congo and obtain molecular information useful for diagnosis, improving treatment, and general pandemic control strategies. METHODS: A total of 74 SARS-CoV-2 isolates were sequenced using Oxford Nanopore platforms. Generated reads were processed to obtain consensus genome sequences. Sequences with more than 80% genome coverage were used for variant calling, phylogenetic analysis, and classification using Pangolin lineage annotation nomenclature. RESULTS: Phylogenetic analysis based on Pangolin classification clustered South Kivu sequences into seven lineages (A.23.1, B.1.1.6, B.1.214, B.1.617.2, B.1.351, C.16, and P.1). The Delta (B.1.617.2) variant was the most dominant and responsible for outbreaks during the third wave. Based on the Wuhan reference genome, 289 distinct mutations were detected, including 141 missenses, 123 synonymous, and 25 insertions/deletions when our isolates were mapped to the Wuhan reference strain. Most of these point mutations were located within the coding sequences of the SARS-CoV-2 genome that includes spike, ORF1ab, ORF3, and nucleocapsid protein genes. The most common mutation was D614G (1841A>G) observed in 61 sequences, followed by L4715L (14143 C>T) found in 60 sequences. CONCLUSION: Our findings highlight multiple introductions of SARS-CoV-2 into South Kivu through different sources and subsequent circulation of variants in the province. These results emphasize the importance of timely monitoring of genetic variation and its effect on disease severity. This work set a foundation for the use of genomic surveillance as a tool for future global pandemic management and control.

Patients' and professionals' perspectives on the consideration of patients' convenient therapy periods as part of personalised rehabilitation: a focus group study with patients and therapists from inpatient neurological rehabilitation.

BACKGROUND: Research on the optimal period for administering health services, especially rehabilitation interventions, is scarce. The aims of this study were to explore the construct of patients' convenient therapy periods and to identify indicators based on the perspectives of patients and different health professionals from inpatient neurological rehabilitation clinics. METHODS: This study was part of a larger project on patients' convenient therapy periods following a mixed methods approach. In the current study a grounded theory approach was employed based on the use of focus group interviews. Focus group interviews were conducted in three different inpatient neurological rehabilitation clinics. Patients and therapists from inpatient neurological rehabilitation clinics who were able to speak and to participate in conversations were included. RESULTS: A total of 41 persons, including 23 patients and 18 therapists, such as music and occupational therapists, participated in a total of six focus group interviews. The analysis of the focus group interviews resulted in the identification of a total of 1261 codes, which could be summarised in fifteen categories. However, these categories could be divided into five indicators and ten impact factors of convenient therapy periods. Identified indicators were verbal and non-verbal communication, mental functions, physiological needs, recreational needs, and therapy initiation. CONCLUSIONS: The results provide initial evidence that convenient therapy periods are clinically relevant for patients and therapists. Different states of patients' ability to effectively participate in a rehabilitation intervention exist. A systematic consideration of patients' convenient therapy periods could contribute to a personalised and more efficient delivery of intervention in neurological rehabilitation. To our knowledge, this study is one of the first attempts to research convenient therapy periods.

Haplotype analysis of the mitochondrial DNA d-loop region reveals the maternal origin and historical dynamics among the indigenous goat populations in east and west of the Democratic Republic of Congo.

This study aimed at assessing haplotype diversity and population dynamics of three Congolese indigenous goat populations that included Kasai goat (KG), small goat (SG), and dwarf goat (DG) of the Democratic Republic of Congo (DRC). The 1169 bp d-loop region of mitochondrial DNA (mtDNA) was sequenced for 339 Congolese indigenous goats. The total length of sequences was used to generate the haplotypes and evaluate their diversities, whereas the hypervariable region (HVI, 453 bp) was analyzed to define the maternal variation and the demographic dynamic. A total of 568 segregating sites that generated 192 haplotypes were observed from the entire d-loop region (1169 bp d-loop). Phylogenetic analyses using reference haplotypes from the six globally defined goat mtDNA haplogroups showed that all the three Congolese indigenous goat populations studied clustered into the dominant haplogroup A, as revealed by the neighbor-joining (NJ) tree and median-joining (MJ) network. Nine haplotypes were shared between the studied goats and goat populations from Pakistan (1 haplotype), Kenya, Ethiopia and Algeria (1 haplotype), Zimbabwe (1 haplotype), Cameroon (3 haplotypes), and Mozambique (3 haplotypes). The population pairwise analysis (FST ) indicated a weak differentiation between the Congolese indigenous goat populations. Negative and significant (p-value <.05) values for Fu's Fs (-20.418) and Tajima's (-2.189) tests showed the expansion in the history of the three Congolese indigenous goat populations. These results suggest a weak differentiation and a single maternal origin for the studied goats. This information will contribute to the improvement of the management strategies and long-term conservation of indigenous goats in DRC.

In Situ Raman Spectroscopy Monitoring of Material Changes During Proton Irradiation.

Organic molecules are prime targets in the search for life on other planetary bodies in the Solar System. Understanding their preservation potential and detectability after ionic irradiation, with fluences potentially representing those received for several millions to billions of years at Mars or in interplanetary space, is a crucial goal for astrobiology research. In order to be able to perform in situ characterization of such organic molecules under ionic irradiation in the near future, a feasibility experiment was performed with polymer test samples to validate the optical configuration and the irradiation chamber geometry. We present here a Raman in situ investigation of the evolution of a series of polymers during proton irradiation. To achieve this goal, a new type of Raman optical probe was designed, which documented that proton irradiation (with a final fluence of 3.1014 at·cm-2) leads to an increase in the background level of the signal, potentially explained by the scission of the polymeric chains and by atom displacements creating defects in the materials. To improve the setup further, a micro-Raman probe and a temperature-controlled sample holder are under development to provide higher spectral and spatial resolutions (by reducing the depth of field and laser spot size), to permit Raman mapping as well as to avoid any thermal effects.

Synthesis and Characterization of Bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) (X = H, p-CH3O, p-Br) with Symmetry- and Distance-Dependent Vibrational Circular Dichroism Enhancement and Sign Inversion.

The enantiopure Schiff bases (R or S)-N-1-(X-C6H4)ethyl-2-hydroxy-1-naphthaldimine {X = H [(R or S)-HL1], p-CH3O [(R or S)-HL2], and p-Br [(R- or S)-HL3]} react with cobalt(II) acetate to give bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) {X = H [Λ/Δ-Co-(R or S)-L1], p-CH3O [Λ/Δ-Co-(R or S)-L2], and p-Br [Λ/Δ-Co-(R or S)-L3]} (1-3), respectively. Induced Λ and Δ chirality originates at the metal center of the C2-symmetric molecule in pseudotetrahedral geometry. Differential scanning calorimetry analyses explored the thermal stability of the complexes, which undergo reversible phase transformation from crystalline solid to isotropic liquid phase for 1 and 3 but irreversible phase transformation for 2. Like other cobalt(II) complexes, compounds 1-3 exhibit a continuous ensemble of absorption and circular dichroism bands, which span from the UV to IR region and can be collected into a superspectrum. Infrared vibrational circular dichroism (IR-VCD) spectra witness the coupling between Co2+-centered low-lying electronic states and ligand-centered vibrations. The coupling produces enhanced and almost monosignate VCD spectra, with both effects being mode-dependent in terms of the A or B symmetry (in the C2 point group) and distance from the Co2+ core.

Insight into the structure-elastic property relationship of calcium silicate glasses: a multi-length scale approach.

Based on a combination of molecular dynamics simulations, and Raman and Brillouin light scattering spectroscopies, we investigate the structure and elastic properties relationship in an archetypical calcium silicate glass system. From molecular dynamics and Raman spectroscopy, we show that the atomic structure at the short and intermediate length scales is made up of long polymerized silicate chains, which adjusts itself by closing the Si-O-Si angles and leaving more space to [CaO]n edge shared polyhedra to strengthen the glass. Using Brillouin spectroscopy, we observe an increase of elastic constants of the glass with the calcium content, as the cohesion of the glass structure is enhanced through an increase of the binding between the cross-linked calcium-silicate frameworks. This result, albeit being simple in its nature, illustrates for the first time the implication of the calcium framework in the elastic behavior of the glass and will contribute substantially to the understanding of the composition-structure-property relationships in multi-component industrial glasses.

Characteristics associated with the risk of psychosis among immigrants and their descendants in France.

OBJECTIVE: To explore the sociodemographic characteristics that might explain the increased incidence of psychosis among immigrants and their descendants in France. METHODS: Data were collected for all subjects with first contact for psychosis aged between 18 and 64 years, in two catchment areas in the Paris region. Incidence rates (IR) and incidence rate ratios (IRR) were adjusted for gender and age. RESULTS: During 805,396 persons-year at risk, we identified 321 cases of first-episode psychosis, of which 129 were immigrants and 78 descendants of immigrants. We found that the geographic origin was associated with the risk of psychosis although generation has little impact. Sub-Saharan African immigrants and their descendants showed the highest risk (IRR = 3.1 and IRR = 2.9, respectively). We observed that living in deprived areas increased the incidence of psychosis (IRR = 1.3, 95CI%: 1.0-1.6), particularly among immigrants (IRR = 1.6; 95% CI: 1.1-2.5). Finally, our study showed that subjects having unstable housing (a proxy for "hard to count population") could inflate the incidence rates among immigrants. CONCLUSION: The current study shows that the increased risk of psychosis in groups with an immigration background in France is associated with their origin and highlights the importance of socioeconomic factors in modulating this risk.

Busulfan-cyclophosphamide versus cyclophosphamide-busulfan as conditioning regimen before allogeneic hematopoietic cell transplantation: a prospective randomized trial.

Busulfan and cyclophosphamide (BuCy) is a frequently used myeloablative conditioning regimen for allogeneic hematopoietic cell transplantation (allo-HCT). Theoretical considerations and pharmacological data indicate that application of busulfan prior to subsequent cyclophosphamide (BuCy) may trigger liver toxicity. Reversing the order of application to cyclophosphamide-busulfan (CyBu) might be preferable, a hypothesis supported by animal data and retrospective studies. We performed a prospective randomized trial to determine impact of order of application of Bu and Cy before allo-HCT in 70 patients with hematological malignancy, 33 patients received BuCy and 37 CyBu for conditioning. In the short term, there were minimal differences in liver toxicity favoring CyBu over BuCy, significant only for alanine amino transferase at day 30 (p = 0.03). With longer follow-up at 4 years, non-relapse mortality (6% versus 27%, p = 0.05) was lower and survival (63% versus 43%, p = 0.06) was higher with CyBu compared to BuCy. Other outcomes, such as engraftment (p = 0.21), acute and chronic graft-versus-host disease (p = 0.40; 0.36), and relapse (p = 0.79), were similar in both groups. We prospectively show evidence that the order of application of Cy and Bu in myeloablative conditioning in allo-HCT patients has impact on outcome.

Increase of network hydrophilicity from sql to lvt supramolecular isomers of Cu-MOFs with the bifunctional 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate linker.

The bifunctional linker 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid (H2mpba) was used for the synthesis of new (square lattice) sql 2D metal-organic frameworks (MOFs) [Cu(Hmpba)2]·L (L = DMF or ACN) in a solvent-mixture of dimethylformamide/water and acetonitrile/water. These sql 2D MOFs are supramolecular isomers of the lvt 3D network [Cu(Hmpba)2]·4MeOH·1H2O (lvt-MeOH) that was synthesized previously by Richardson and co-workers. All these frameworks are potentially porous structures with solvent molecules included in the channels of the as synthesized materials. After activation all three materials showed good CO2 adsorption capacity, demonstrated here for lvt-MeOH for the first time, with a saturation uptake of 113 cm3 g-1 (lvt-MeOH-act.), 111 cm3 g-1 (sql-DMF-act.) and 90 cm3 g-1 (sql-ACN-act.) at 195 K. The flexibility of the lvt-MeOH-act. network is evidenced by a gate-opening effect seen in the CO2 measurement at 195 K and under gravimetric high-pressure CO2 adsorption. According to the water and ethanol sorption measurements the new sql frameworks can be categorized as hydrophobic materials in contrast to the hydrophilic lvt framework. In the lvt-MeOH structure the crystal solvent can be replaced with water to yield the structurally authenticated water-only network lvt-H2O containing 3D arrays of S4-symmetric (H2O)20 clusters.

Carbon Black as Conductive Additive and Structural Director of Porous Carbon Gels.

This work investigates the impact of carbon black (CB) as a porogenic agent and conductive additive in the preparation of electrically conductive nanoporous carbon gels. For this, a series of materials were prepared by the polycondensation of resorcinol/formaldehyde mixtures in the presence of increasing amounts of carbon black. The conductivity of the carbon gel/CB composites increased considerably with the amount of CB, indicating a good dispersion of the additive within the carbon matrix. A percolation threshold of ca. 8 wt.% of conductive additive was found to achieve an adequate "point to point" conductive network. This value is higher than that reported for other additives, owing to the synthetic route chosen, as the additive was incorporated in the reactant's mixture (pre-synthesis) rather than in the formulation of the electrodes ink (post-synthesis). The CB strongly influenced the development of the porous architecture of the gels that exhibited a multimodal mesopore structure comprised of two distinct pore networks. The microporosity and the primary mesopore structure remained rather unchanged. On the contrary, a secondary network of mesopores was formed in the presence of the additive. Furthermore, the average mesopore size and the volume of the secondary network increased with the amount of CB.

Effect of a Strategy of Comprehensive Vasodilation vs Usual Care on Mortality and Heart Failure Rehospitalization Among Patients With Acute Heart Failure: The GALACTIC Randomized Clinical Trial.

Importance: Short-term infusions of single vasodilators, usually given in a fixed dose, have not improved outcomes in patients with acute heart failure (AHF). Objective: To evaluate the effect of a strategy that emphasized early intensive and sustained vasodilation using individualized up-titrated doses of established vasodilators in patients with AHF. Design, Setting, and Participants: Randomized, open-label blinded-end-point trial enrolling 788 patients hospitalized for AHF with dyspnea, increased plasma concentrations of natriuretic peptides, systolic blood pressure of at least 100 mm Hg, and plan for treatment in a general ward in 10 tertiary and secondary hospitals in Switzerland, Bulgaria, Germany, Brazil, and Spain. Enrollment began in December 2007 and follow-up was completed in February 2019. Interventions: Patients were randomized 1:1 to a strategy of early intensive and sustained vasodilation throughout the hospitalization (n = 386) or usual care (n = 402). Early intensive and sustained vasodilation was a comprehensive pragmatic approach of maximal and sustained vasodilation combining individualized doses of sublingual and transdermal nitrates, low-dose oral hydralazine for 48 hours, and rapid up-titration of angiotensin-converting enzyme inhibitors, angiotensin receptor blockers, or sacubitril-valsartan. Main Outcomes and Measures: The primary end point was a composite of all-cause mortality or rehospitalization for AHF at 180 days. Results: Among 788 patients randomized, 781 (99.1%; median age, 78 years; 36.9% women) completed the trial and were eligible for primary end point analysis. Follow-up at 180 days was completed for 779 patients (99.7%). The primary end point, a composite of all-cause mortality or rehospitalization for AHF at 180 days, occurred in 117 patients (30.6%) in the intervention group (including 55 deaths [14.4%]) and in 111 patients (27.8%) in the usual care group (including 61 deaths [15.3%]) (absolute difference for the primary end point, 2.8% [95% CI, -3.7% to 9.3%]; adjusted hazard ratio, 1.07 [95% CI, 0.83-1.39]; P = .59). The most common clinically significant adverse events with early intensive and sustained vasodilation vs usual care were hypokalemia (23% vs 25%), worsening renal function (21% vs 20%), headache (26% vs 10%), dizziness (15% vs 10%), and hypotension (8% vs 2%). Conclusions and Relevance: Among patients with AHF, a strategy of early intensive and sustained vasodilation, compared with usual care, did not significantly improve a composite outcome of all-cause mortality and AHF rehospitalization at 180 days. Trial Registration: ClinicalTrials.gov Identifier: NCT00512759.

Metastable phase equilibria in the ice II stability field. A Raman study of synthetic high-density water inclusions in quartz.

Microthermometric measurements of a synthetic high-density (984 kg m-3) water inclusion in quartz revealed that only part of the super-cooled liquid water (L) transforms to solid ice Ih upon ice nucleation (L → ice Ih + L). While ice nucleation occurs in the ice Ih stability field at -41 °C and 28 MPa the pressure increases instantaneously to 315 MPa into the ice II stability field. At this point, both phases, liquid water and ice Ih are metastable. The coexistence of these two phases was confirmed by Raman spectroscopy and could be traced down to -80 °C. The pressure along this low-temperature metastable extension of the ice Ih melting curve was determined by means of the frequency shift of the ice Ih peak position using both the O-H stretching band around 3100 cm-1 and the lattice translational band around 220 cm-1. At -80 °C and 466 MPa the super-cooled ice Ih melting curve encounters the homogeneous nucleation limit (TH) and the remaining liquid water transformed either to metastable ice IV (ice Ih + L → ice Ih + ice IV) or occasionally to metastable ice III (ice Ih + L → ice Ih + ice III). The nucleation of ice IV resulted in a pressure drop of about 180 MPa. Upon subsequent heating the pressure develops along a slightly negatively sloped ice Ih-ice IV equilibrium line terminating in a triple point at -32.7 °C and 273 MPa, where ice IV melts to liquid water (ice Ih + ice IV → ice Ih + L). Hitherto existing experimental data of the ice IV melting curve (ice IV → L) were found to be in line with the observed ice Ih-ice IV-liquid triple point. If, on the other hand, ice III nucleated at -80 °C (instead of ice IV) the associated pressure drop was about 260 MPa. The ice Ih-ice III-liquid triple point was determined at -22.0 °C and 207 MPa (ice Ih + ice III → ice Ih + L), which is in agreement with previous experimental data.

New eremophilane-type sesquiterpenes and maleimide-bearing compounds from Carpesium abrotanoides L.

Two new eremophilane-type sesquiterpenes, carperemophilanes A and B (1-2), three new maleimide-bearing compounds, carpesiumaleimides A-C (3-5), along with a known sesquiterpene, carabrol (6), were isolated from the ethanol extract of Carpesium abrotanoides L. Their structures were elucidated by analysis of their NMR and MS data as well as by comparison with the literature. The absolute configuration of carperemophilane A (1) was determined by single-crystal X-ray diffraction analysis. All isolated compounds (1-6) were evaluated in vitro for cytotoxicity against two human cancer cell lines MDA-MB-231 and HGC-27 using the MTT method. Compounds 1, 2 and 6 showed cytotoxic activities with IC50 values ranging from 7.45 to 37.35 µM.

Raman Open Database: first interconnected Raman-X-ray diffraction open-access resource for material identification.

Detailed crystallographic information provided by X-ray diffraction (XRD) is complementary to molecular information provided by Raman spectroscopy. Accordingly, the combined use of these techniques allows the identification of an unknown compound without ambiguity. However, a full combination of Raman and XRD results requires an appropriate and reliable reference database with complete information. This is already available for XRD. The main objective of this paper is to introduce and describe the recently developed Raman Open Database (ROD, http://solsa.crystallography.net/rod). It comprises a collection of high-quality uncorrected Raman spectra. The novelty of this database is its interconnectedness with other open databases like the Crystallography Open Database (http://www.crystallography.net/cod and Theoretical Crystallography Open Database (http://www.crystallography.net/tcod/). The syntax adopted to format entries in the ROD is based on the worldwide recognized and used CIF format, which offers a simple way for data exchange, writing and description. ROD also uses JCAMP-DX files as an alternative format for submitted spectra. JCAMP-DX files are compatible to varying degrees with most commercial Raman software and can be read and edited using standard text editors.