Water-Assisted Oxygen Activation During Selective Oxidation Reactions

The selective functionalization of hydrocarbons with oxygen to produce valuable commodity chemicals is inherently challenging, because of the thermodynamic stability of the complete combustion products. Emerging green synthesis routes and sustainable energy production also rely on the success of selective oxidation reactions. As one of the unselective by-products, water is always present under reaction conditions and numerous studies indicate that the catalytic activity and selectivity of selective oxidation reactions may be tuned by judiciously controlling the water content during the reaction. Some experimentally verified examples include the preferential oxidation of carbon monoxide, direct hydrogen peroxide synthesis, propene epoxidation and alcohol oxidation. Finally, it has been predicted that the direct conversion of methane to methanol can benefit from the right amount of water near the active site during oxygen activation

On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MO\u3csub\u3ex\u3c/sub\u3e Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles

We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylaminecapped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ~2.5 nm in diameter. The catalysts showed high alkene selectivity (\u3e90%) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25– 40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1- octyne reaction orders (~ 0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H2 on an alkyne-covered Au surface

Bifunctional metal phosphide FeMnP films from single source metal organic chemical vapor deposition for efficient overall water splitting

Developing stable and efficient bifunctional catalysts for overall water splitting into hydrogen and oxygen is a critical step in the realization of several clean-energy technologies. Here we report a robust and highly active electrocatalyst that is constructed by deposition of the ternary metal phosphide FeMnP onto graphene-protected nickel foam by metal-organic chemical vapor deposition from a single source precursor. FeMnP exhibits high electrocatalytic activity toward both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Utilizing FeMnP/GNF as both the anode and the cathode for overall water splitting, a current density of 10 mA cm−2 is achieved at a cell voltage of as low as 1.55 V with excellent stability. Complementary density functional theory (DFT) calculations suggest that facets exposing both Fe and Mn sites are necessary to achieve high HER activity. The present work provides a facile strategy for fabricating highly efficient electrocatalysts from earth-abundant materials for overall water splitting

Risk Factors for Heart Failure Among Pan-European Childhood Cancer Survivors: A PanCareSurFup and ProCardio Cohort and Nested Case-Control Study.

PURPOSE Heart failure (HF) is a potentially life-threatening complication of treatment for childhood cancer. We evaluated the risk and risk factors for HF in a large European study of long-term survivors. Little is known of the effects of low doses of treatment, which is needed to improve current treatment protocols and surveillance guidelines. METHODS This study includes the PanCareSurFup and ProCardio cohort of ≥ 5-year childhood cancer survivors diagnosed between 1940 and 2009 in seven European countries (N = 42,361). We calculated the cumulative incidence of HF and conducted a nested case-control study to evaluate detailed treatment-related risk factors. RESULTS The cumulative incidence of HF was 2% (95% CI, 1.7 to 2.2) by age 50 years. The case-control study (n = 1,000) showed that survivors who received a mean heart radiation therapy (RT) dose of 5 to < 15 Gy have an increased risk of HF (odds ratio, 5.5; 95% CI, 2.5 to 12.3), when compared with no heart RT. The risk associated with doses 5 to < 15 Gy increased with exposure of a larger heart volume. In addition, the HF risk increased in a linear fashion with higher mean heart RT doses. Regarding total cumulative anthracycline dose, survivors who received ≥ 100 mg/m2 had a substantially increased risk of HF and survivors treated with a lower dose showed no significantly increased risk of HF. The dose-response relationship appeared quadratic with higher anthracycline doses. CONCLUSION Survivors who received a mean heart RT dose of ≥ 5 Gy have an increased risk of HF. The risk associated with RT increases with larger volumes exposed. Survivors treated with < 100 mg/m2 total cumulative anthracycline dose have no significantly increased risk of HF. These new findings might have consequences for new treatment protocols for children with cancer and for cardiomyopathy surveillance guidelines

Risk of subsequent primary lymphoma in a cohort of 69,460 five-year survivors of childhood and adolescent cancer in Europe: The PanCareSurFup study.

BACKGROUND Survivors of Hodgkin lymphoma (HL) are at risk of developing non-Hodgkin lymphoma (NHL) after treatment; however, the risks of developing subsequent primary lymphomas (SPLs), including HL and NHL, after different types of childhood cancer are unknown. The authors quantified the risk of SPLs using the largest cohort of childhood cancer survivors worldwide. METHODS The Pan-European Network for Care of Survivors After Childhood and Adolescent Cancer (PanCare) Survivor Care and Follow-Up Studies (PanCareSurFup) cohort includes 69,460 five-year survivors of childhood cancer, diagnosed during 1940 through 2008, from 12 European countries. Risks of SPLs were quantified by standardized incidence ratios (SIRs) and relative risks (RRs) using multivariable Poisson regression. RESULTS Overall, 140 SPLs, including 104 NHLs and 36 HLs, were identified. Survivors were at 60% increased risk of an SPL compared with the general population (SIR, 1.6; 95% confidence interval [CI], 1.4-1.9). Survivors were twice as likely to develop NHL (SIR, 2.3; 95% CI, 1.9-2.8), with the greatest risks among survivors of HL (SIR, 7.1; 95% CI, 5.1-10.0), Wilms tumor (SIR, 3.1; 95% CI, 1.7-5.7), leukemia (SIR, 2.8; 95% CI, 1.8-4.4), and bone sarcoma (SIR, 2.7; 95% CI, 1.4-5.4). Treatment with chemotherapy for any cancer doubled the RR of NHL (RR, 2.1; 95% CI, 1.2-3.9), but treatment with radiotherapy did not (RR, 1.2; 95% CI, 0.7-2.0). Survivors were at similar risk of developing a subsequent HL as the general population (SIR, 1.1; 95% CI, 0.8-1.5). CONCLUSIONS In addition to HL, the authors show here for the first time that survivors of Wilms tumor, leukemia, and bone sarcoma are at risk of NHL. Survivors and health care professionals should be aware of the risk of NHL in these survivors and in any survivors treated with chemotherapy

Risk of subsequent gliomas and meningiomas among 69,460 5-year survivors of childhood and adolescent cancer in Europe:the PanCareSurFup study

BACKGROUND: Childhood cancer survivors are at risk of subsequent gliomas and meningiomas, but the risks beyond age 40 years are uncertain. We quantified these risks in the largest ever cohort.METHODS: Using data from 69,460 5-year childhood cancer survivors (diagnosed 1940-2008), across Europe, standardized incidence ratios (SIRs) and cumulative incidence were calculated.RESULTS: In total, 279 glioma and 761 meningioma were identified. CNS tumour (SIR: 16.2, 95% CI: 13.7, 19.2) and leukaemia (SIR: 11.2, 95% CI: 8.8, 14.2) survivors were at greatest risk of glioma. The SIR for CNS tumour survivors was still 4.3-fold after age 50 (95% CI: 1.9, 9.6), and for leukaemia survivors still 10.2-fold after age 40 (95% CI: 4.9, 21.4). Following cranial radiotherapy (CRT), the cumulative incidence of a glioma in CNS tumour survivors was 2.7%, 3.7% and 5.0% by ages 40, 50 and 60, respectively, whilst for leukaemia this was 1.2% and 1.7% by ages 40 and 50. The cumulative incidence of a meningioma after CRT in CNS tumour survivors doubled from 5.9% to 12.5% between ages 40 and 60, and in leukaemia survivors increased from 5.8% to 10.2% between ages 40 and 50.DISCUSSION: Clinicians following up survivors should be aware that the substantial risks of meningioma and glioma following CRT are sustained beyond age 40 and be vigilant for symptoms.</p

Magnetocapacitance effect and magnetoelectric coupling in type-II multiferroic HoFeWO6

We have investigated the multiferroicity and magnetoelectric (ME) coupling in HoFeWO6. With a noncentrosymmetric polar structure (space group Pna21) at room temperature, this compound shows an onset of electric polarization with an antiferromagnetic ordering at the Néel temperature (TN ) of 17.8 K. The magnetic properties of the polycrystalline samples were studied by DC and AC magnetization and heat capacity measurements. The metamagnetic behavior at low temperatures was found to be directly related to the dielectric properties of the compound. In particular, field-dependent measurements of capacitance show a magnetocapacitance (MC) effect with double-hysteresis loop behavior in direct correspondence with the magnetization. Our x-ray diffraction results show the Pna21 structure down to 8 K and suggest the absence of a structural phase transition across TN . Soft x-ray absorption spectroscopy and soft x-ray magnetic circular dichroism (XMCD) measurements at the Fe L2,3 and Ho M4,5 edges revealed the oxidation state of Fe and Ho cations to be 3+. Fe L2,3 XMCD further shows that Fe3+ cations are antiferromagnetically ordered in a noncollinear fashion with spins arranged 90◦ with respect to each other. Our findings show that HoFeWO6 is a type-II multiferroic exhibiting a MC effect. The observed MC effect and the change in polarization by the magnetic field, as well as their direct correspondence with magnetization, further support the strong ME coupling in this compound.The work at University of Houston (UH) is supported by U. S. Air Force Office of Scientific Research Grants FA9550-15-1-0236 and FA9550-20-1-0068, the T. L. L. Temple Foundation, the John J. and Rebecca Moores Endowment, and the State of Texas through the Texas Center for Superconductivity at the University of Houston. The XRD patterns were collected at the National Synchrotron Radiation Research Center at Taiwan. The synchrotron XAS/XMCD experiments were performed at the BOREAS beamline of the ALBA Synchrotron Light Facility in collaboration with ALBA staff. Computational resources were provided by the Extreme Science and Engineering Discovery Environment (XSEDE) [55] supported by the National Science Foundation (ACI-1548562) and the National Energy Research Scientific Computing (NERSC) Center, a DOE Office of Science User Facility supported by the Office of Science, U. S. Department of Energy, under Contract No. DE-AC02-05CH11231. Additional support for this work was provided through resources of the uHPC cluster managed by UH and acquired through NSF Award 1531814. The authors acknowledge the use of the Maxwell/Opuntia/Sabine Cluster and the advanced support from the Research Computing Data Core at UH. The work at National Sun Yat-Sen University was partially supported by the Ministry of Science and Technology of Taiwan under Grant No. MOST 109-2112-M-110-019.Peer reviewe

The PanCareSurFup consortium:research and guidelines to improve lives for survivors of childhood cancer

Background: Second malignant neoplasms and cardiotoxicity are among the most serious and frequent adverse health outcomes experienced by childhood and adolescent cancer survivors (CCSs) and contribute significantly to their increased risk of premature mortality. Owing to differences in health-care systems, language and culture across the continent, Europe has had limited success in establishing multi-country collaborations needed to assemble the numbers of survivors required to clarify the health issues arising after successful cancer treatment. PanCareSurFup (PCSF) is the first pan-European project to evaluate some of the serious long-term health risks faced by survivors. This article sets out the overall rationale, methods and preliminary results of PCSF. Methods: The PCSF consortium pooled data from 13 cancer registries and hospitals in 12 European countries to evaluate subsequent primary malignancies, cardiac disease and late mortality in survivors diagnosed between ages 0 and 20 years. In addition, PCSF integrated radiation dosimetry to sites of second malignancies and to the heart, developed evidence-based guidelines for long-term care and for transition services, and disseminated results to survivors and the public. Results: We identified 115,596 individuals diagnosed with cancer, of whom 83,333 were 5-year survivors and diagnosed from 1940 to 2011. This single data set forms the basis for cohort analyses of subsequent malignancies, cardiac disease and late mortality and case–control studies of subsequent malignancies and cardiac disease in 5-year survivors. Conclusions: PCSF delivered specific estimates of risk and comprehensive guidelines to help survivors and care-givers. The expected benefit is to provide every European CCS with improved access to care and better long-term health

Late cardiac events after childhood cancer: Methodological aspects of the pan-european study pancaresurfup

Background and Aim Childhood cancer survivors are at high risk of long-Termadverse effects of cancer and its treatment, including cardiac events. The pan-European PanCareSurFup study determined the incidence and risk factors for cardiac events among childhood cancer survivors. The aim of this article is to describe the methodology of the cardiac cohort and nested case-control study within PanCareSurFup. Methods Eight data providers in Europe participating in PanCareSurFup identified and validated symptomatic cardiac events in their cohorts of childhood cancer survivors. Data onsymptomatic heart failure, ischemia, pericarditis, valvular disease and arrhythmia were collected and graded according to the Criteria for Adverse Events. Detailed treatment data, data on potential confounders, lifestyle related risk factors and general health problems were collected. Results The PanCareSurFup cardiac cohort consisted of 59,915 5-year childhood cancer survivors with malignancies diagnosed between 1940 and 2009 and classified according to the International Classification of Childhood Cancer 3. Different strategies were used to identify cardiac events such as record linkage to population/ hospital or regional based databases, and patient-And general practitioner-based questionnaires. Conclusion The cardiac study of the European collaborative research project PanCareSurFup will provide the largest cohort of 5-year childhood cancer survivors with systematically ascertained and validated data on symptomatic cardiac events. The result of this study can provide information to minimize the burden of cardiac events in childhood cancer survivors by tailoring the follow-up of childhood cancer survivors at high risk of cardiac adverse events, transferring this knowledge into evidence-based clinical practice guidelines and providing a platformfor future research studies in childhood cancer patients. © 2016 Feijen et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited

Risk of subsequent primary oral cancer in a cohort of 69,460 5-year survivors of childhood and adolescent cancer in Europe: the PanCareSurFup study

Background Survivors of childhood cancer are at risk of subsequent primary malignant neoplasms (SPNs), but the risk for rarer types of SPNs, such as oral cancer, is uncertain. Previous studies included few oral SPNs, hence large-scale cohorts are required to identify groups at risks. Methods The PanCareSurFup cohort includes 69,460 5-year survivors of childhood cancer across Europe. Risks of oral SPNs were defined by standardised incidence ratios (SIRs), absolute excess risks and cumulative incidence. Results One hundred and forty-five oral SPNs (64 salivary gland, 38 tongue, 20 pharynx, 2 lip, and 21 other) were ascertained among 143 survivors. Survivors were at 5-fold risk of an oral SPN (95% CI: 4.4-5.6). Survivors of leukaemia were at greatest risk (SIR = 19.2; 95% CI: 14.6-25.2) followed by bone sarcoma (SIR = 6.4, 95% CI: 3.7-11.0), Hodgkin lymphoma (SIR = 6.2, 95% CI: 3.9-9.9) and soft-tissue sarcoma (SIR = 5.0, 95% CI: 3.0-8.5). Survivors treated with radiotherapy were at 33-fold risk of salivary gland SPNs (95% CI: 25.3-44.5), particularly Hodgkin lymphoma (SIR = 66.2, 95% CI: 43.6-100.5) and leukaemia (SIR = 50.5, 95% CI: 36.1-70.7) survivors. Survivors treated with chemotherapy had a substantially increased risk of a tongue SPN (SIR = 15.9, 95% CI: 10.6-23.7). Conclusions Previous radiotherapy increases the risk of salivary gland SPNs considerably, while chemotherapy increases the risk of tongue SPNs substantially. Awareness of these risks among both health-care professionals and survivors could play a crucial role in detecting oral SPNs early.</p