Impacts of elevated atmospheric ozone on peatland below-ground DOC characteristics

Rising concentrations of tropospheric ozone are having detrimental impacts on the growth of crop and forest species and some studies have reported inhibition of the allocation of carbon below ground. The effects of ozone on peatland ecosystems have received relatively little attention, despite their importance within the global carbon cycle. During this study, cores from a Welsh minerotrophic fen and ombrotrophic bog were exposed to four ambient/ elevated ozone concentration regimes representing current and predicted 2050 profiles. A large and significant reduction in the concentration of porewater dissolved organic carbon (DOC) was recorded in the fen cores exposed to the elevated ozone concentrations (up to −55%), with a concurrent shift to a higher molecularweight of the remaining soil carbon. No effects of ozone on DOC concentrations or characteristics were recorded for the bog cores. The data suggest higher ozone sensitivity of plants growing in the fen-type peatland, that the impacts on the vegetation may affect soil carbon characteristics through a reduction in root exudates and that theremay have been a shift in the source of substrate DOC for microbial consumption from vegetation exudates to native soil carbon. Theremay also have been a direct effect of ozone molecules reacting with soil organic matter after being transported into the soil through the aerenchyma tissue of the overlying vegetation. These qualitative changes in the soil carbon in response to elevated ozone may have important implications for carbon cycling in peatland ecosystems, and therefore climate change

Gold-Catalyzed Direct Arylation

Gently Coupled Linked aryl rings are found in a broad range of commercial chemical products. Currently, the most versatile synthetic route to this motif involves cross-coupling of one ring with a halide substituent to another ring with a boron or metal-based substituent. Recent research has focused on eliminating the need for one or both of these activating substituents, but for the most part, the emerging methods have required high temperatures and high concentrations of one coupling partner. Ball et al. (p. 1644 ) now present a gold catalyst that can couple silyl-activated arenes to unactivated arenes in comparable concentrations at room temperature. </jats:p

<i>In Situ </i>Studies of Arylboronic Acids/Esters and R₃SiCF₃ Reagents: Kinetics, Speciation, and Dysfunction at the Carbanion–Ate Interface

[Image: see text] Reagent instability reduces the efficiency of chemical processes, and while much effort is devoted to reaction optimization, less attention is paid to the mechanistic causes of reagent decomposition. Indeed, the response is often to simply use an excess of the reagent. Two reaction classes with ubiquitous examples of this are the Suzuki–Miyaura cross-coupling of boronic acids/esters and the transfer of CF(3) or CF(2) from the Ruppert–Prakash reagent, TMSCF(3). This Account describes some of the overarching features of our mechanistic investigations into their decomposition. In the first section we summarize how specific examples of (hetero)arylboronic acids can decompose via aqueous protodeboronation processes: Ar–B(OH)(2) + H(2)O → ArH + B(OH)(3). Key to the analysis was the development of a kinetic model in which pH controls boron speciation and heterocycle protonation states. This method revealed six different protodeboronation pathways, including self-catalysis when the pH is close to the pK(a) of the boronic acid, and protodeboronation via a transient aryl anionoid pathway for highly electron-deficient arenes. The degree of “protection” of boronic acids by diol-esterification is shown to be very dependent on the diol identity, with six-membered ring esters resulting in faster protodeboronation than the parent boronic acid. In the second section of the Account we describe (19)F NMR spectroscopic analysis of the kinetics of the reaction of TMSCF(3) with ketones, fluoroarenes, and alkenes. Processes initiated by substoichiometric “TBAT” ([Ph(3)SiF(2)][Bu(4)N]) involve anionic chain reactions in which low concentrations of [CF(3)](−) are rapidly and reversibly liberated from a siliconate reservoir, [TMS(CF(3))(2)][Bu(4)N]. Increased TMSCF(3) concentrations reduce the [CF(3)](−) concentration and thus inhibit the rates of CF(3) transfer. Computation and kinetics reveal that the TMSCF(3) intermolecularly abstracts fluoride from [CF(3)](−) to generate the CF(2), in what would otherwise be an endergonic α-fluoride elimination. Starting from [CF(3)](−) and CF(2), a cascade involving perfluoroalkene homologation results in the generation of a hindered perfluorocarbanion, [C(11)F(23)](−), and inhibition. The generation of CF(2) from TMSCF(3) is much more efficiently mediated by NaI, and in contrast to TBAT, the process undergoes autoacceleration. The process involves NaI-mediated α-fluoride elimination from [CF(3)][Na] to generate CF(2) and a [NaI·NaF] chain carrier. Chain-branching, by [(CF(2))(3)I][Na] generated in situ (CF(2) + TFE + NaI), causes autoacceleration. Alkenes that efficiently capture CF(2) attenuate the chain-branching, suppress autoacceleration, and lead to less rapid difluorocyclopropanation. The Account also highlights how a collaborative approach to experiment and computation enables mechanistic insight for control of processes

Effect of work:rest ratio on cycling performance following sprint interval training: A randomised control trial

Sprint interval training (SIT) has been shown to improve performance measures in a range of individuals, and it is understood that different responses can be elicited from different training protocols. However, consideration of changes in work: rest ratios could offer important insight into optimising training programmes. The purpose of this study was to investigate the effect of three different work: rest ratios on exercise performance. Thirty-six male and female participants were randomly allocated to one of three training groups, or a non-training control group. Training consisted of 10x6 second ‘all-out’ sprints on a cycle ergometer, with a 1:8, 1:10 or 1:12 work: rest ratio. Performance data, including peak power output, performance decrement, and 10km time trial performance data were collected before and after 2-weeks of SIT. There were significant (p ≤ 0.05) improvements in all parameters for the training groups, but no changes in the control condition. Peak power increased by 57.2W, 50.7W and 53.7W in the 1:8, 1:10 and 1:12 groups respectively, with no significant differences in response between conditions. Time trial performance improved significantly in all three training conditions (29.4s, 8.7s, and 25.1s in the 1:8, 1:10 and 1:12 groups), while worsening in the control group. All training conditions resulted in significant improvements in performance, but there were no significant differences in improvement for any of the groups. Any of the three stated work: rest ratios would be appropriate for use with athletes and allow some level of personal preference for those interested in using the protocol

Quantum Process Tomography of the Quantum Fourier Transform

The results of quantum process tomography on a three-qubit nuclear magnetic resonance quantum information processor are presented, and shown to be consistent with a detailed model of the system-plus-apparatus used for the experiments. The quantum operation studied was the quantum Fourier transform, which is important in several quantum algorithms and poses a rigorous test for the precision of our recently-developed strongly modulating control fields. The results were analyzed in an attempt to decompose the implementation errors into coherent (overall systematic), incoherent (microscopically deterministic), and decoherent (microscopically random) components. This analysis yielded a superoperator consisting of a unitary part that was strongly correlated with the theoretically expected unitary superoperator of the quantum Fourier transform, an overall attenuation consistent with decoherence, and a residual portion that was not completely positive - although complete positivity is required for any quantum operation. By comparison with the results of computer simulations, the lack of complete positivity was shown to be largely a consequence of the incoherent errors during the quantum process tomography procedure. These simulations further showed that coherent, incoherent, and decoherent errors can often be identified by their distinctive effects on the spectrum of the overall superoperator. The gate fidelity of the experimentally determined superoperator was 0.64, while the correlation coefficient between experimentally determined superoperator and the simulated superoperator was 0.79; most of the discrepancies with the simulations could be explained by the cummulative effect of small errors in the single qubit gates.Comment: 26 pages, 17 figures, four tables; in press, Journal of Chemical Physic

Self-control tames the coupling of reactive radicals

Highly reactive or unstable chemical reagents are challenging to prepare, store, and safely handle, so chemists frequently generate them in situ from convenient precursors. In an ideal case, the rate of release of the reagent would be matched to the rate of its “capture” in the desired chemical reaction, thereby preventing the reagent from accumulating and minimizing any opportunity for decomposition. However, this synchronization is rarely achieved or even attempted: The rate of release is usually dictated by the conditions of the reaction (1), rather than being regulated by capture of the reagent. In this issue, Tellis et al. (2) on page 433 and Zuo et al. (3) on page 437 independently report the use of iridium photocatalysis (4, 5) to supply highly reactive radical coupling partners (R⋅) to a nickel-catalyzed carbon-carbon bond-forming process (see the figure). Intriguingly, the two points of contact between the iridium and nickel cycles enforce autoregulated release of the radical, ensuring its efficient capture by nickel rather than its decomposition via other pathways

The Oral-Vascular-Pulmonary Infection Route:a Pathogenic Mechanism Linking Oral Health Status to Acute and Post-Acute COVID-19

Purpose of Review: In recent years, much attention has focused on the role of poor oral health in the development or worsening of systemic diseases, including COVID-19. The mouth is an important site of cellular infection early in the disease course of COVID-19. We review how oral pathology, and specifically viral infection within the oral cavity, may mediate the disease severity and duration of COVID-19. In particular, the previously reported model of SARS-CoV-2 vascular delivery from the mouth to the lungs via the bloodstream is revisited.Recent Findings: We previously proposed that an oral-vascular-pulmonary route of infection could facilitate severe lung disease in COVID-19. This pathway could also explain the vital link between periodontitis and COVID-19 severity, including higher mortality risk. This model of pathogenesis is reconsidered in light of recent findings regarding the involvement of the mouth as a viral reservoir, and pathological processes in the blood, pulmonary vasculature, and elsewhere in the body. Oral dysbiosis in COVID-19 and the effect of oral hygiene in mitigating disease severity are discussed. The evidence for viral persistence in the mouth and intravascular viral passage from the mouth to the rest of the body via blood is also discussed in the context of post-acute COVID (long COVID).Summary: High viral load in the mouth and poor oral health status are associated with COVID-19 disease severity, increasing the risk of death. Pathophysiological links between viral activity in the mouth, oral health status, and disease outcome in the lungs and blood provide a rationale for further evaluation of the oral-vascular-systemic pathway in patients with acute COVID-19 and long COVID. The potential benefits of oral hygiene protocols and periodontal procedures in COVID-19 also warrant further investigation

The Oral-Vascular-Pulmonary Infection Route:a Pathogenic Mechanism Linking Oral Health Status to Acute and Post-Acute COVID-19

Purpose of Review: In recent years, much attention has focused on the role of poor oral health in the development or worsening of systemic diseases, including COVID-19. The mouth is an important site of cellular infection early in the disease course of COVID-19. We review how oral pathology, and specifically viral infection within the oral cavity, may mediate the disease severity and duration of COVID-19. In particular, the previously reported model of SARS-CoV-2 vascular delivery from the mouth to the lungs via the bloodstream is revisited.Recent Findings: We previously proposed that an oral-vascular-pulmonary route of infection could facilitate severe lung disease in COVID-19. This pathway could also explain the vital link between periodontitis and COVID-19 severity, including higher mortality risk. This model of pathogenesis is reconsidered in light of recent findings regarding the involvement of the mouth as a viral reservoir, and pathological processes in the blood, pulmonary vasculature, and elsewhere in the body. Oral dysbiosis in COVID-19 and the effect of oral hygiene in mitigating disease severity are discussed. The evidence for viral persistence in the mouth and intravascular viral passage from the mouth to the rest of the body via blood is also discussed in the context of post-acute COVID (long COVID).Summary: High viral load in the mouth and poor oral health status are associated with COVID-19 disease severity, increasing the risk of death. Pathophysiological links between viral activity in the mouth, oral health status, and disease outcome in the lungs and blood provide a rationale for further evaluation of the oral-vascular-systemic pathway in patients with acute COVID-19 and long COVID. The potential benefits of oral hygiene protocols and periodontal procedures in COVID-19 also warrant further investigation

Expansion of the ligand knowledge base for chelating P,P-donor ligands (LKB-PP)

[Image: see text] We have expanded the ligand knowledge base for bidentate P,P- and P,N-donor ligands (LKB-PP, Organometallics2008, 27, 1372–1383) by 208 ligands and introduced an additional steric descriptor (nHe(8)). This expanded knowledge base now captures information on 334 bidentate ligands and has been processed with principal component analysis (PCA) of the descriptors to produce a detailed map of bidentate ligand space, which better captures ligand variation and has been used for the analysis of ligand properties