Influence of Modified Bio-Coals on Carbonization and Bio-Coke Reactivity

Substitution of coal in coking coal blend with bio-coal is a potential way to reduce fossil CO2 emissions from iron and steelmaking. The current study aims to explore possible means to counteract negative influence from bio-coal in cokemaking. Washing and kaolin coating of bio-coals were conducted to remove or bind part of the compounds in the bio-coal ash that catalyzes the gasification of coke with CO2. To further explore how the increase in coke reactivity is related to more reactive carbon in bio-coal or catalytic oxides in bio-coal ash, ash was produced from a corresponding amount of bio-coal and added to the coking coal blend for carbonization. The reaction behavior of coals and bio-coals under carbonization conditions was studied in a thermogravimetric analyzer equipped with a mass spectrometer during carbonization. The impact of the bio-coal addition on the fluidity of the coking coal blend was studied in optical dilatometer tests for coking coal blends with and without the addition of bio-coal or bio-coal ash. The result shows that the washing of bio-coal will result in lower or even negative dilatation. The washing of bio-coals containing a higher amount of catalytic components will reduce the negative effect on bio-coke reactivity, especially with acetic acid washing when the start of gasification temperature is less lowered. The addition of bio-coal coated with 5% kaolin do not significantly lower the dilatation-relative reference coking coal blend. The reactivity of bio-cokes containing bio-coal coated with kaolin-containing potassium oxide was higher in comparison to bio-coke containing the original bio-coal. The addition of ash from 5% of torrefied bio-coals has a moderate effect on lowering the start of gasification temperature, which indicates that the reactive carbon originating from bio-coal has a larger impact.

Construction of poly-N-heterocyclic scaffolds via the controlled reactivity of Cu-allenylidene intermediates

Controlling the sequence of the three consecutive reactive carbon centres of Cu-allenylidene remains a challenge. One of the impressive achievements in this area is the Cu-catalyzed annulation of 4-ethynyl benzoxazinanones, which are transformed into zwitterionic Cu-stabilized allenylidenes that are trapped by interceptors to provide the annulation products. In principle, the reaction proceeds via a preferential γ-attack, while annulation reactions via an α- or β-attack are infrequent. Herein, we describe a method for controlling the annulation mode, by the manipulation of a CF3 or CH3 substituent, to make it proceed via either a γ-attack or an α- or β-attack. The annulation of CF3-substituted substrates with sulfamate-imines furnished densely functionalized N-heterocycles with excellent enantioselectivity via a cascade of an internal β-attack and an external α-attack. CH3-variants were transformed into different heterocycles that possess a spiral skeleton, via a cascade of an internal β-attack and a hydride α-migration followed by a Diels−Alder reaction.

Net carbon sink of China was overestimated by more than 35%

As a carbon source/sink of atmospheric carbon dioxide, the net regional carbon budget (NRCB) of terrestrial ecosystems is very important to effect global warming, especially China with the largest emissions at present. However, the carbon consumption is difficult to measure accurately, which is caused by the emissions of CH4 and CO, the utilization of agriculture, forestry and grass, and the emissions from rivers and other physical processes, such as forest fires. Therefore, the spatial patterns and driving factors of NRCB are not clear. Here, we used multi-source data to estimate the NRCB of 31 provincial administrative divisions of China and to develop NRCB datasets from 2000 to 2018. We found that the average of NRCB was 669 TgC yr−1, and it significantly decreased at a rate of 2.56 TgC yr−1. The relative contribution rates of fluxes of emissions from anthropogenic (FEAD), reactive carbon and creature ingestion (FERCCI), autotrophic respiration (Ra), heterotrophic respiration (Rh) and natural disturbances (FEND) were 35.17%, 26.09%, 19.68%, 17.38% and 1.68% respectively. In addition, NRCB datasets of the different administrative regions of China were mapped. These datasets will provide support for China's carbon neutrality and the study of the global carbon cycle.

Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Organophosphorus compounds have numerous useful applications, from versatile ligands and nucleophiles in the case of trivalent organophosphorus species to therapeutics, agrochemicals and material additives for pentavalent species. Although phosphorus chemistry is a fairly mature field, the construction of C–P(V) bonds relies heavily on either prefunctionalized substrates such as alkyl or aryl halides, or requires previously oxidized bonds such as C=N or C=O, leading to potential sustainability issues when looking at the overall synthetic route. In light of the recent advances in photochemistry, using photons as a reagent can provide better alternatives for phosphorylations by unlocking radical mechanisms and providing interesting redox pathways. This review will showcase the different photomediated phosphorylation procedures available for converting C–H bonds into C–P(V) bonds.1 Introduction1.1 Organophosphorus Compounds1.2 Phosphorylation: Construction of C–P(V) Bonds1.3 Photochemistry as an Alternative to Classical Phosphorylations2 Ionic Mechanisms Involving Nucleophilic Additions3 Mechanisms Involving Radical Intermediates3.1 Mechanisms Involving Reactive Carbon Radicals3.2 Mechanisms Involving Phosphorus Radicals3.2.1 Photoredox: Direct Creation of Phosphorus Radicals3.2.2 Photoredox: Indirect Creation of Phosphorus Radicals3.2.3 Dual Catalysis3.3 Photolytic Cleavage4 Conclusion and Outlook

Attribution of ground-level ozone to anthropogenic and natural sources of nitrogen oxides and reactive carbon in a global chemical transport model

We perform a source attribution for tropospheric and ground-level ozone using a novel technique that accounts separately for the contributions of the two chemically distinct emitted precursors (reactive carbon and oxides of nitrogen) to the chemical production of ozone in the troposphere. By tagging anthropogenic emissions of these precursors according to the geographical region from which they are emitted, we determine source–receptor relationships for ground-level ozone. Our methodology reproduces earlier results obtained via other techniques for ozone source attribution, and it also delivers additional information about the modelled processes responsible for the intercontinental transport of ozone, which is especially strong during the spring months. The current generation of chemical transport models used to support international negotiations aimed at reducing the intercontinental transport of ozone shows especially strong inter-model differences in simulated springtime ozone. Current models also simulate a large range of different responses of surface ozone to methane, which is one of the major precursors of ground-level ozone. Using our novel source attribution technique, we show that emissions of NOx (oxides of nitrogen) from international shipping over the high seas play a disproportionately strong role in our model system regarding the hemispheric-scale response of surface ozone to changes in methane, as well as to the springtime maximum in intercontinental transport of ozone and its precursors. We recommend a renewed focus on the improvement of the representation of the chemistry of ship NOx emissions in current-generation models. We demonstrate the utility of ozone source attribution as a powerful model diagnostic tool and recommend that similar source attribution techniques become a standard part of future model intercomparison studies.

A Ligand-Directed Approach to Activity-Based Sensing: Developing Palladacycle Fluorescent Probes that Enable Endogenous Carbon Monoxide Detection

Carbon monoxide (CO) is an emerging gasotransmitter and reactive carbon species with broad anti-inflammatory, cytoprotective, and neurotransmitter functions along with therapeutic potential for the treatment of cardiovascular diseases. The study of CO chemistry in biology and medicine relative to other prominent gasotransmitters such as NO and H2S remains challenging, in large part due to limitations in available tools for the direct visualization of this transient and freely diffusing small molecule in complex living systems. Here we report a ligand-directed activity-based sensing (ABS) approach to CO detection through palladium-mediated carbonylation chemistry. Specifically, the design and synthesis of a series of ABS probes with systematic alterations in the palladium-ligand environment (e.g., sp3-S, sp3-N, sp2-N) establish structureactivity relationships for palladacycles to confer selective reactivity with CO under physiological conditions. These fundamental studies led to the development of an optimized probe, termed Carbon Monoxide Probe-3 Ester Pyridine (COP3E-Py), which enables imaging of CO release in live cell and brain settings, including monitoring of endogenous CO production that triggers presynaptic dopamine release in fly brains. This work provides a unique tool for studying CO in living systems and establishes the utility of a synthetic methods approach to activity-based sensing using principles of organometallic chemistry

A Ligand-Directed Approach to Activity-Based Sensing: Developing Palladacycle Fluorescent Probes that Enable Endogenous Carbon Monoxide Detection

Carbon monoxide (CO) is an emerging gasotransmitter and reactive carbon species with broad anti-inflammatory, cytoprotective, and neurotransmitter functions along with therapeutic potential for the treatment of cardiovascular diseases. The study of CO chemistry in biology and medicine relative to other prominent gasotransmitters such as NO and H2S remains challenging, in large part due to limitations in available tools for the direct visualization of this transient and freely diffusing small molecule in complex living systems. Here we report a ligand-directed activity-based sensing (ABS) approach to CO detection through palladium-mediated carbonylation chemistry. Specifically, the design and synthesis of a series of ABS probes with systematic alterations in the palladium-ligand environment (e.g., sp3-S, sp3-N, sp2-N) establish structureactivity relationships for palladacycles to confer selective reactivity with CO under physiological conditions. These fundamental studies led to the development of an optimized probe, termed Carbon Monoxide Probe-3 Ester Pyridine (COP3E-Py), which enables imaging of CO release in live cell and brain settings, including monitoring of endogenous CO production that triggers presynaptic dopamine release in fly brains. This work provides a unique tool for studying CO in living systems and establishes the utility of a synthetic methods approach to activity-based sensing using principles of organometallic chemistry

Minisci C-H Alkylation of Heteroarenes Enabled by Dual Photoredox/bromide Catalysis in Micellar Solutions

Microstructured aqueous solutions were employed to engage non-activated alkyl bromides in the visible-light-promoted C‑H functionalization of heteroarenes. The reactive carbon-centered alkyl radicals were generated by merging the photoredox approach, bromide anion co-catalysis and spatial pre-aggregation of reacting species in the mixture. The presented methodology allowed obtaining alkylated heteroarenes without stoichiometric radical-promoters, in acid-free conditions and using blue LEDs as the light source.

Minisci C-H Alkylation of Heteroarenes Enabled by Dual Photoredox/bromide Catalysis in Micellar Solutions

Microstructured aqueous solutions were employed to engage non-activated alkyl bromides in the visible-light-promoted C‑H functionalization of heteroarenes. The reactive carbon-centered alkyl radicals were generated by merging the photoredox approach, bromide anion co-catalysis and spatial pre-aggregation of reacting species in the mixture. The presented methodology allowed obtaining alkylated heteroarenes without stoichiometric radical-promoters, in acid-free conditions and using blue LEDs as the light source.