Post doped nitrogen-decorated hollow carbon spheres as a support for Co Fischer-Tropsch catalysts

In this study the outer surface of porous hollow carbon spheres (HCSs) materials were functionalized by N-doping using a post-synthesis method and they were used as a Fischer-Tropsch catalyst support. Melamine was used as the nitrogen source, and carbonization was performed at different temperatures (600 and 900 °C) to introduce variable levels of N into the HCSs, with different bonding configurations. This procedure allowed for the incorporation of up to 13% N. Our results show that post-synthesis N-doping introduced marginal defects into the carbon framework and this did not affect the thermal stability of the materials. XPS studies revealed that the surface content on these materials varied and provided evidence for temperature-tunable bonding configurations. Effects associated with post-synthesis N-doping were apparent on the Co catalyst (˜10 wt.%) properties such as the inhibited reduction caused by a metal-support interaction observed by the H2-TPR and in situ PXRD techniques. As a consequence the Fischer-Tropsch performance was influenced as both the activity and stability were improved on the catalysts supported on the N-doped materials. TEM analysis of the spent catalysts demonstrated the influence of N-doping on the sintering characteristics of Co, with particles > 30 nm measured on the N-free catalyst while N-doped samples had sizes < 15 nm

A sinter resistant Co Fischer-Tropsch catalyst promoted with Ru and supported on titania encapsulated by mesoporous silica

One of the pathways responsible for the deactivation of Fischer-Tropsch catalysts is the loss of active metal surface area due to nanoparticle agglomeration. To combat this effect efforts have been made to increase the interaction between the metal nanoparticles and the support using materials like silica. In this study, the supported metal particles were covered with a highly porous layer of silica to stabilize the Co nanoparticles on a titania support both during reduction and under reaction conditions. Co3O4 nanoparticles (size range: 8–12 nm) supported on titania were stabilized by coating them with a thin layer of mesoporous silica ( ∼ 4 nm) to make Fischer-Tropsch catalysts that are less prone to sintering (Co/TiO2@mSiO2). To mitigate the strong metal support interactions brought about by the titania and silica a Ru promoter was loaded together with the cobalt nanoparticles onto the titania (CoRu/TiO2@mSiO2). Temperature programmed XRD studies on the evolution of the Co metal nanoparticles showed that there was no significant particle size growth under reduction conditions in the temperature range from 30 to 600 °C. Chemisorption studies following reduction under hydrogen at 350 °C and 450 °C gave results consistent with the in situ XRD data when compared to the Co/TiO2. Fischer-Tropsch synthesis on the Co/TiO2@mSiO2 and CoRu/TiO2@mSiO2 catalysts encapsulated inside the mesoporous silica shell exhibited good catalytic performance without any display of significant mass transport limitations that might arise due to a silica shell coating of the active sites. For these two catalysts the Fischer-Tropsch activity increased with reduction temperature without any significant negative changes in their selectivity due to sintering, while the activity on Co/TiO2 decreased due to Co nanoparticle sintering

CCNE1 and survival of patients with tubo-ovarian high-grade serous carcinoma: An Ovarian Tumor Tissue Analysis consortium study

BACKGROUND: Cyclin E1 (CCNE1) is a potential predictive marker and therapeutic target in tubo-ovarian high-grade serous carcinoma (HGSC). Smaller studies have revealed unfavorable associations for CCNE1 amplification and CCNE1 overexpression with survival, but to date no large-scale, histotype-specific validation has been performed. The hypothesis was that high-level amplification of CCNE1 and CCNE1 overexpression, as well as a combination of the two, are linked to shorter overall survival in HGSC. METHODS: Within the Ovarian Tumor Tissue Analysis consortium, amplification status and protein level in 3029 HGSC cases and mRNA expression in 2419 samples were investigated. RESULTS: High-level amplification (>8 copies by chromogenic in situ hybridization) was found in 8.6% of HGSC and overexpression (>60% with at least 5% demonstrating strong intensity by immunohistochemistry) was found in 22.4%. CCNE1 high-level amplification and overexpression both were linked to shorter overall survival in multivariate survival analysis adjusted for age and stage, with hazard stratification by study (hazard ratio [HR], 1.26; 95% CI, 1.08-1.47, p = .034, and HR, 1.18; 95% CI, 1.05-1.32, p = .015, respectively). This was also true for cases with combined high-level amplification/overexpression (HR, 1.26; 95% CI, 1.09-1.47, p = .033). CCNE1 mRNA expression was not associated with overall survival (HR, 1.00 per 1-SD increase; 95% CI, 0.94-1.06; p = .58). CCNE1 high-level amplification is mutually exclusive with the presence of germline BRCA1/2 pathogenic variants and shows an inverse association to RB1 loss. CONCLUSION: This study provides large-scale validation that CCNE1 high-level amplification is associated with shorter survival, supporting its utility as a prognostic biomarker in HGSC

Localization of type 1 diabetes susceptibility to the MHC class I genes HLA-B and HLA-A

The major histocompatibility complex (MHC) on chromosome 6 is associated with susceptibility to more common diseases than any other region of the human genome, including almost all disorders classified as autoimmune. In type 1 diabetes the major genetic susceptibility determinants have been mapped to the MHC class II genes HLA-DQB1 and HLA-DRB1 (refs 1-3), but these genes cannot completely explain the association between type 1 diabetes and the MHC region. Owing to the region's extreme gene density, the multiplicity of disease-associated alleles, strong associations between alleles, limited genotyping capability, and inadequate statistical approaches and sample sizes, which, and how many, loci within the MHC determine susceptibility remains unclear. Here, in several large type 1 diabetes data sets, we analyse a combined total of 1,729 polymorphisms, and apply statistical methods - recursive partitioning and regression - to pinpoint disease susceptibility to the MHC class I genes HLA-B and HLA-A (risk ratios >1.5; Pcombined = 2.01 × 10-19 and 2.35 × 10-13, respectively) in addition to the established associations of the MHC class II genes. Other loci with smaller and/or rarer effects might also be involved, but to find these, future searches must take into account both the HLA class II and class I genes and use even larger samples. Taken together with previous studies, we conclude that MHC-class-I-mediated events, principally involving HLA-B*39, contribute to the aetiology of type 1 diabetes. ©2007 Nature Publishing Group

The clinical and genetic spectrum of inherited glycosylphosphatidylinositol deficiency disorders

Inherited glycosylphosphatidylinositol deficiency disorders (IGDs) are a group of rare multisystem disorders arising from pathogenic variants in glycosylphosphatidylinositol anchor pathway (GPI-AP) genes. Despite associating 24 of at least 31 GPI-AP genes with human neurogenetic disease, prior reports are limited to single genes without consideration of the GPI-AP as a whole and with limited natural history data. In this multinational retrospective observational study, we systematically analyse the molecular spectrum, phenotypic characteristics, and natural history of 83 individuals from 75 unique families with IGDs, including 70 newly reported individuals: the largest single cohort to date. Core clinical features were developmental delay or intellectual disability (DD/ID, 90%), seizures (83%), hypotonia (72%), and motor symptoms (64%). Prognostic and biologically significant neuroimaging features included cerebral atrophy (75%), cerebellar atrophy (60%), callosal anomalies (57%), and symmetric restricted diffusion of the central tegmental tracts (60%). Sixty-one individuals had multisystem involvement including gastrointestinal (66%), cardiac (19%), and renal (14%) anomalies. Though dysmorphic features were appreciated in 82%, no single dysmorphic feature had a prevalence >30%, indicating substantial phenotypic heterogeneity. Follow-up data were available for all individuals, 15 of whom were deceased at the time of writing. Median age at seizure onset was 6 months. Individuals with variants in synthesis stage genes of the GPI-AP exhibited a significantly shorter time to seizure onset than individuals with variants in transamidase and remodelling stage genes of the GPI-AP (P=0.046). Forty individuals had intractable epilepsy. The majority of individuals experienced delayed or absent speech (95%); motor delay with non-ambulance (64%); and severe-to-profound DD/ID (59%). Individuals with a developmental epileptic encephalopathy (51%) were at greater risk of intractable epilepsy (P=0.003), non-ambulance (P=0.035), ongoing enteral feeds (P<0.001), and cortical visual impairment (P=0.007). Serial neuroimaging showed progressive cerebral volume loss in 87.5% and progressive cerebellar atrophy in 70.8%, indicating a neurodegenerative process. Genetic analyses identified 93 unique variants (106 total), including 22 novel variants. Exploratory analyses of genotype-phenotype correlations using unsupervised hierarchical clustering identified novel genotypic predictors of clinical phenotype and long-term outcome with meaningful implications for management. In summary, we expand both the mild and severe phenotypic extremities of the IGDs; provide insights into their neurological basis; and, vitally, enable meaningful genetic counselling for affected individuals and their families

Convalescent plasma in patients admitted to hospital with COVID-19 (RECOVERY): a randomised controlled, open-label, platform trial

SummaryBackground Azithromycin has been proposed as a treatment for COVID-19 on the basis of its immunomodulatoryactions. We aimed to evaluate the safety and efficacy of azithromycin in patients admitted to hospital with COVID-19.Methods In this randomised, controlled, open-label, adaptive platform trial (Randomised Evaluation of COVID-19Therapy [RECOVERY]), several possible treatments were compared with usual care in patients admitted to hospitalwith COVID-19 in the UK. The trial is underway at 176 hospitals in the UK. Eligible and consenting patients wererandomly allocated to either usual standard of care alone or usual standard of care plus azithromycin 500 mg once perday by mouth or intravenously for 10 days or until discharge (or allocation to one of the other RECOVERY treatmentgroups). Patients were assigned via web-based simple (unstratified) randomisation with allocation concealment andwere twice as likely to be randomly assigned to usual care than to any of the active treatment groups. Participants andlocal study staff were not masked to the allocated treatment, but all others involved in the trial were masked to theoutcome data during the trial. The primary outcome was 28-day all-cause mortality, assessed in the intention-to-treatpopulation. The trial is registered with ISRCTN, 50189673, and ClinicalTrials.gov, NCT04381936.Findings Between April 7 and Nov 27, 2020, of 16 442 patients enrolled in the RECOVERY trial, 9433 (57%) wereeligible and 7763 were included in the assessment of azithromycin. The mean age of these study participants was65·3 years (SD 15·7) and approximately a third were women (2944 [38%] of 7763). 2582 patients were randomlyallocated to receive azithromycin and 5181 patients were randomly allocated to usual care alone. Overall,561 (22%) patients allocated to azithromycin and 1162 (22%) patients allocated to usual care died within 28 days(rate ratio 0·97, 95% CI 0·87–1·07; p=0·50). No significant difference was seen in duration of hospital stay (median10 days [IQR 5 to >28] vs 11 days [5 to >28]) or the proportion of patients discharged from hospital alive within 28 days(rate ratio 1·04, 95% CI 0·98–1·10; p=0·19). Among those not on invasive mechanical ventilation at baseline, nosignificant difference was seen in the proportion meeting the composite endpoint of invasive mechanical ventilationor death (risk ratio 0·95, 95% CI 0·87–1·03; p=0·24).Interpretation In patients admitted to hospital with COVID-19, azithromycin did not improve survival or otherprespecified clinical outcomes. Azithromycin use in patients admitted to hospital with COVID-19 should be restrictedto patients in whom there is a clear antimicrobial indication

Equilibrium ion exchange studies of Ni2+ on homoionic forms of clinoptilolite

A natural zeolite (clinoptilolite) that is mined in KwaZulu-Natal, South Africa, was evaluated for the removal of Ni2+ from wastewater. In particular, the effect of zeolite modification on Ni2+ removal from synthetic wastewater was investigated. The natural clinoptilolite was pretreated with 2 M metal chlorides for 24 h to yield near homoionic Na+, K+ and Ca2+ forms. A comparison of the isotherms for the Na+-Ni2+, K+-Ni2+, Ca2+-Ni2+ and natural-Ni2+ systems gave insight into how the displaced ion affects the selectivity of the clinoptilolite for Ni2+. The Na+, K+ and natural forms show highly selective convex isotherms whereas the Ca2+ form has a concave graph suggesting that the selectivity series is Ca2+&gt; Ni2+&gt; (Na+, K+, natural). Thermodynamic properties revealed that the Ni2+ sorption capacity increases as the values of the equilibrium constant and Gibbs free energy increase with increasing temperature from 298.15 K to 348.15 K. The enthalpy change was positive for all forms of clinoptilolite; values of 26.00 kJ/mol, 18.72 kJ/mol and 42.05 kJ/mol were obtained for exchange of Ni2+ into Na+, K+ and Ca2+ forms, respectively. The positive changes in enthalpy provide an indication that the sorption reaction is endothermic for Ni(II). The Gibbs free energy values were all negative except for Ca2+-exchanged clinoptilolite at 298.15 K and 308.15 K, for which the values were positive 3.10 kJ/mol and 0.53 kJ/mol, respectively. The entropy values for Ni2+ sorption were also positive; values of 0.12 kJ/mol.K, 0.08 kJ/mol.K and 0.14 kJ/mol.K were obtained for the Na+, K+ and Ca2+ forms, respectively. As expected, the enthalpy obtained from the Van’t Hoff plot is dependent not only on the metal ion being adsorbed, but also on the ion being displaced. Pretreatment of the zeolite enhances the removal efficiency provided that monovalent ions are used for the pretreatment. Thus clinoptilolite is an effective low-cost absorbent for the removal of Ni2+ from aqueous solutions

Confronting Child Maltreatment Through Recreation

By David L. Jewell, College at Brockport professor emeritus. Includes chapter by College at Brockport faculty members Joseph E. Balog and Linda F. Balog: Children under stress. Rev. ed of: Confronting child abuse through recreation.https://digitalcommons.brockport.edu/bookshelf/1245/thumbnail.jp

Advances and challenges with SOEC high temperature co-electrolysis of CO2/H2O: Materials development and technological design

Higher electrolysis efficiency than that achieved with conventional electrolysis and integrated fuel production would help to reduce dependence on bio-energy further. In this regard, solid oxide electrolyzer (SOEC) technology is of particular interest because of its unrivaled conversion efficiency, due to the favorable thermodynamics and kinetics at higher operating temperatures. In particular, SOEC high-temperature co-electrolysis (HTCE) of CO2/H2O can convert CO2 into valuable chemicals and fuels, which will help to reduce reliance on fossil fuels and mitigate greenhouse gas emissions. In this report, we present a comprehensive overview of recent research progress made with SOEC HTCE of CO2/H2O. The main focus areas are the development history, the basic principle and the reaction mechanism of HTCE of CO2/H2O using SOEC. The fuel electrode and oxygen electrode materials for SOEC HTCE of CO2/H2O are classified and introduced. The factors that affect the co-electrolysis reaction process are also described in detail, and the optimization strategy of the process conditions is explained to provide a better understanding of the SOEC HTCE process. The challenges and possible future development directions are also suggested, as guidance for future research

Ruthenium nanoparticles encapsulated inside porous hollow carbon spheres: A novel catalyst for Fischer-Tropsch synthesis

Two novel Ru Fischer–Tropsch (FT) catalysts were made that were supported on the inside of two hollow carbon spheres that differed in terms of their shell porosity. Mesoporous Stober spheres were made and Ru deposited on the silica. The Ru/silica spheres were encapsulated with carbon deposited by CVD (toluene) or from resorcinol/formaldehyde. Removal of the silica gave Ru@HCS (dRu = 5.5) and Ru@MHCS (3.2 nm) that had carbon shells (d = ca. 20 nm) with different physicochemical properties as evidenced by the TEM, nitrogen adsorption-desorption, TGA, Raman spectroscopy and XRD measurements. FT studies were performed on the two catalysts (10 bar; 190/220/250 °C; 2/1 ratio H2/CO). Classical Fischer–Tropsch data was obtained indicating that the catalysts could access the reactants and that FT products could escape from the inside of the spheres (acting as a nanoreactor). Activity data indicated diffusion control of CO/H2 into the nanoreactor and selectivity data indicated an alpha value of 0.74–0.78 (220 °C). Typical product selectivity associated with small Ru particles was observed and the methane content increased with reaction temperature. No substantial Ru sintering occurred below 220 °C. It is thus seen that the porosity of the two hollow carbon architectures is suitable for the FT polymerization reaction