•Review of environmental redox classifications.•Calibration of commonly used elemental proxies to redox facies.•Analysis of proxies from modern Black Sea, Saanich Inlet, and California Margin.•Use of ...compound covariation of redox proxies to identify key redox thresholds.•No universal proxy values: calibration necessary for each depositional system under study.
Existing redox classifications and the calibrations of elemental proxies to modern environmental redox scales are in need of re-evaluation. Here, we review environmental redox classifications, commonly used elemental redox proxies, and their intercalibration, and we propose a novel approach to improve the calibration of such proxies, using datasets from the modern Black Sea, Saanich Inlet, and California Margin as examples. Our approach is based on recognition of compound covariation patterns among pairs of elemental redox proxies within a redox framework based on three key thresholds: (1) the Re4+/Re3− couple near the suboxidized/subreduced boundary of the suboxic zone, (2) the U6+/U4+ couple in the middle of the subreduced zone, and (3) the SO42−/H2S couple at the suboxic/euxinic boundary. Within this framework, it is possible to determine the relative timing of onset and the degree of enrichment of other elemental redox proxies. Our analysis demonstrates that, even though some elements exhibit limited enrichment within the suboxic zone, the bulk of authigenic enrichment of the redox-sensitive elements considered in this study occurs within the euxinic zone. One important finding of our study is that the threshold value associated with a given elemental proxy can vary considerably between depositional systems. For this reason, it is inadvisable to transfer published threshold values (i.e., from earlier paleoredox studies) to completely different formations, and redox proxies must be internally calibrated for each individual paleodepositional system under investigation.
Following the severe acute respiratory syndrome coronavirus (SARS‐CoV) and Middle East respiratory syndrome coronavirus (MERS‐CoV), another highly pathogenic coronavirus named SARS‐CoV‐2 (previously ...known as 2019‐nCoV) emerged in December 2019 in Wuhan, China, and rapidly spreads around the world. This virus shares highly homological sequence with SARS‐CoV, and causes acute, highly lethal pneumonia coronavirus disease 2019 (COVID‐19) with clinical symptoms similar to those reported for SARS‐CoV and MERS‐CoV. The most characteristic symptom of patients with COVID‐19 is respiratory distress, and most of the patients admitted to the intensive care could not breathe spontaneously. Additionally, some patients with COVID‐19 also showed neurologic signs, such as headache, nausea, and vomiting. Increasing evidence shows that coronaviruses are not always confined to the respiratory tract and that they may also invade the central nervous system inducing neurological diseases. The infection of SARS‐CoV has been reported in the brains from both patients and experimental animals, where the brainstem was heavily infected. Furthermore, some coronaviruses have been demonstrated able to spread via a synapse‐connected route to the medullary cardiorespiratory center from the mechanoreceptors and chemoreceptors in the lung and lower respiratory airways. Considering the high similarity between SARS‐CoV and SARS‐CoV2, it remains to make clear whether the potential invasion of SARS‐CoV2 is partially responsible for the acute respiratory failure of patients with COVID‐19. Awareness of this may have a guiding significance for the prevention and treatment of the SARS‐CoV‐2‐induced respiratory failure.
Research Highlights
SARS‐CoV2 causes epidemic pneumonia characterized by acute respiratory distress.
This novel coronavirus is similar to SARS‐CoV in sequence, pathogenesis, and cellular entry.
Some coronaviruses can invade brainstem via a synapse‐connected route from the lung and airways.
The potential invasion of SARS‐CoV2 may be one reason for the acute respiratory failure.
Awareness of this will have guiding significance for the prevention and treatment.
Conventional approaches for Pd‐catalyzed ring‐opening cross‐couplings of gem‐difluorocyclopropanes with nucleophiles predominantly deliver the β‐fluoroalkene scaffolds (linear selectivity). Herein, ...we report a cooperative strategy that can completely switch the reaction selectivity to give the alkylated α‐fluoroalkene skeletons (branched selectivity). The unique reactivity of hydrazones that enables analogous inner‐sphere 3,3′‐reductive elimination driven by denitrogenation, as well as the assistance of steric‐embedded N‐heterocyclic carbene ligand, are the key to switch the regioselectivity. A wide range of hydrazones derived from naturally abundant aryl and alkyl aldehydes are well applicable, and various gem‐difluorocyclopropanes, including modified pharmaceutical and biological molecules, can be efficiently functionalized with high value alkylated α‐fluorinated alkene motifs under mild conditions.
A highly effective Pd‐catalyzed defluorinative alkylation of gem‐difluorocyclopropane with branched selectivity was achieved by using a cooperative strategy that integrated the unique trifunctional character of hydrazones with Pd/NHC catalysis.
Modern alkyne chemistry Trost, Barry M; Li, Chao-Jun
2014., 2014, 2015, 2014-10-09, 2014-10-08
eBook
A comprehensive and up-to-date overview of alkyne chemistry, taking into account the progress made over the last two decades. The experienced editors are renowned world leaders in the field, while ...the list of contributors reads like a "Who's Who" of synthetic organic chemistry. The result is a valuable reference not only for organic chemists at universities and in the chemical industry, but also for biologists and material scientists involved in the modern synthesis of organic compounds and materials.
Abstract
Hydrogen atom abstraction (HAT) from C(
sp
3
)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction ...designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report a photo-induced and chemical oxidant-free cross-dehydrogenative coupling (CDC) between alkanes and heteroarenes using catalytic chloride and cobalt catalyst. Couplings of strong C(
sp
3
)–H bond-containing substrates and complex heteroarenes, have been achieved with satisfactory yields. This dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst to enable the hydrogen evolution for catalytic turnover. The practical value of this protocol was demonstrated by the gram-scale synthesis of alkylated heteroarene with merely 3 equiv. alkane loading.
Despite their impressive capacity to access diverse functional groups and to synthesize structurally complex molecules, the majority of the organic reactions suffers from harsh conditions, low atom ...economy, and hazardous waste production. The goal of our research is geared towards developing efficient methods to minimize the adverse environmental impact and contributing to chemical sustainability. Herein, we illustrate three distinct green approaches, studying the novel reactivities with environmentally innocuous reagents to improve the synthetic efficiency, utilization of natural feedstocks, and employment of green energy to facilitate various important chemical transformations. From this perspective article, we hope to provide an overview of green synthetic chemistry and inspire the expansion of the field in the future.
Green synthesis and catalysis play key roles in future chemical sustainability. Various examples drawn from our lab are used to discuss potential chemistry tools to convert resources prevalent in nature more efficiently into valuable products. Display omitted
The first example of homogeneous copper‐catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous ...conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.
Without ‘Fehl ’: The first example of homogeneous copper‐catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.
PDF
