The influence of reaction conditions on the oxidation of cyclohexane via the in-situ production of H2O2

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), both key materials in the production of Nylon. Herein we demonstrate that through the in-situ production of H2O2 supported AuPd nanoparticles catalyse the formation of KA oil under conditions where activity is limited when using molecular O2, with no loss in catalytic activity observed upon re-use. The effect of key reaction parameters, including reaction temperature, catalyst mass and H2:O2 ratio are evaluated

IntCal09 and Marine09 radiocarbon age calibration curves, 0-50,000yeats cal BP

The IntCal04 and Marine04 radiocarbon calibration curves have been updated from 12 cal kBP (cal kBP is here defined as thousands of calibrated years before AD 1950), and extended to 50 cal kBP, utilizing newly available data sets that meet the IntCal Working Group criteria for pristine corals and other carbonates and for quantification of uncertainty in both the 14C and calendar timescales as established in 2002. No change was made to the curves from 0–12 cal kBP. The curves were constructed using a Markov chain Monte Carlo (MCMC) implementation of the random walk model used for IntCal04 and Marine04. The new curves were ratified at the 20th International Radiocarbon Conference in June 2009 and are available in the Supplemental Material at www.radiocarbon.org

A comparative study of palladium-gold and palladium-tin catalysts in the direct synthesis of H2O2

Herein we evaluate the promotive effect of Au and Sn incorporation into supported Pd nanoparticles for the direct synthesis of H2O2 from molecular H2 and O2. The introduction of both secondary metal modifiers was found to result in a significant enhancement in catalytic performance, although, in the case of the PdSn system, it was identified that relatively large quantities of the secondary metal were required to rival the activity observed over optimal Au-containing formulations, with the 0.25%Pd-2.25%Sn/TiO2 catalyst offering comparable H2O2 synthesis rates to the optimised 0.25%Pd-0.25%Au/TiO2 formulation. The introduction of Sn was found to considerably improve Pd dispersion, correlating with an improvement in selective H2 utilisation. Notably, the optimal PdSn catalyst identified in this work achieves superior H2O2 selectivities compared to the PdAu analogue and is able to rival the performance of state-of-the-art materials

IntCal09 and Marine09 radiocarbon age calibration curves, 0-50,000 years cal BP

The IntCal04 and Marine04 radiocarbon calibration curves have been updated from 12 cal kBP (cal kBP is here defined as thousands of calibrated years before AD 1950), and extended to 50 cal kBP, utilizing newly available data sets that meet the IntCal Working Group criteria for pristine corals and other carbonates and for quantification of uncertainty in both the 14C and calendar timescales as established in 2002. No change was made to the curves from 0-12 cal kBP. The curves were constructed using a Markov chain Monte Carlo (MCMC) implementation of the random walk model used for IntCal04 and Marine04. The new curves were ratified at the 20th International Radiocarbon Conference in June 2009 and are available in the Supplemental Material at www.radiocarbon.org.Additional co-authors: TJ Heaton, AG Hogg, KA Hughen, KF Kaiser, B Kromer, SW Manning, RW Reimer, DA Richards, JR Southon, S Talamo, CSM Turney, J van der Plicht, CE Weyhenmeye

The selective oxidation of cyclohexane via In-situ H2O2 production over supported Pd-based catalysts

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), key materials in the production of Nylon. The in-situ route has the potential to overcome the significant economic and environmental concerns associated with the use of commercial H2O2, while also allowing for the use of far lower reaction temperatures than those typical of the purely aerobic route to KA oil. Herein we demonstrate the efficacy of a series of bi-functional Pd-based catalysts, which offer appreciable concentrations of KA oil, under conditions where limited activity is observed using O2 alone. In particular the introduction of V into a supported Pd catalyst is seen to improve KA oil concentration by an order of magnitude, compared to the Pd-only analogue. In particular we ascribe this improvement in catalytic performance to the development of Pd domains of mixed oxidation state upon V incorporation as evidenced through X-ray photoelectron spectroscopy

IntCal04 terrestrial radiocarbon age calibration, 0-26 cal kyr BP

Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2004. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 46 (2004): 1029-1058.A new calibration curve for the conversion of radiocarbon ages to calibrated (cal) ages has been constructed and internationally ratified to replace IntCal98, which extended from 0–24 cal kyr BP (Before Present, 0 cal BP = AD 1950). The new calibration data set for terrestrial samples extends from 0–26 cal kyr BP, but with much higher resolution beyond 11.4 cal kyr BP than IntCal98. Dendrochronologically-dated tree-ring samples cover the period from 0–12.4 cal kyr BP. Beyond the end of the tree rings, data from marine records (corals and foraminifera) are converted to the atmospheric equivalent with a site-specific marine reservoir correction to provide terrestrial calibration from 12.4–26.0 cal kyr BP. A substantial enhancement relative to IntCal98 is the introduction of a coherent statistical approach based on a random walk model, which takes into account the uncertainty in both the calendar age and the 14C age to calculate the underlying calibration curve (Buck and Blackwell, this issue). The tree-ring data sets, sources of uncertainty, and regional offsets are discussed here. The marine data sets and calibration curve for marine samples from the surface mixed layer (Marine04) are discussed in brief, but details are presented in Hughen et al. (this issue a). We do not make a recommendation for calibration beyond 26 cal kyr BP at this time; however, potential calibration data sets are compared in another paper (van der Plicht et al., this issue)

Thiol-based chemical probes exhibit antiviral activity against SARS-CoV-2 via allosteric disulfide disruption in the spike glycoprotein

The development of small-molecules targeting different components of SARS-CoV-2 is a key strategy to complement antibody-based treatments and vaccination campaigns in managing the COVID-19 pandemic. Here, we show that two thiol-based chemical probes that act as reducing agents, P2119 and P2165, inhibit infection by human coronaviruses, including SARS-CoV-2, and decrease the binding of spike glycoprotein to its receptor, the angiotensin-converting enzyme 2 (ACE2). Proteomics and reactive cysteine profiling link the antiviral activity to the reduction of key disulfides, specifically by disruption of the Cys379–Cys432 and Cys391–Cys525 pairs distal to the receptor binding motif in the receptor binding domain (RBD) of the spike glycoprotein. Computational analyses provide insight into conformation changes that occur when these disulfides break or form, consistent with an allosteric role, and indicate that P2119/P2165 target a conserved hydrophobic binding pocket in the RBD with the benzyl thiol-reducing moiety pointed directly toward Cys432. These collective findings establish the vulnerability of human coronaviruses to thiol-based chemical probes and lay the groundwork for developing compounds of this class, as a strategy to inhibit the SARS-CoV-2 infection by shifting the spike glycoprotein redox scaffold