Atmospheric Carbon Monoxide Research Articles

Analyzing the Interactions between Environmental Parameters and Cardiovascular Diseases Using Random Forest and SHAP Algorithms.

Cardiovascular diseases (CVD) remain the predominant global cause of mortality, with both low and high temperatures increasing CVD-related mortalities. Climate change impacts human health directly through temperature fluctuations and indirectly via factors like disease vectors. Elevated and reduced temperatures have been linked to increases in CVD-related hospitalizations and mortality, with various studies worldwide confirming the significant health implications of temperature variations and air pollution on cardiovascular outcomes. A database of daily Emergency Room admissions at the Giovanni XIII Polyclinic in Bari (Southern Italy) was developed, spanning from 2013 to 2019, including weather and air quality data. A Random Forest (RF) supervised machine learning model was used to simulate the trend of hospital admissions for CVD. The Seasonal and Trend decomposition using Loess (STL) decomposition model separated the trend component, while cross-validation techniques were employed to prevent overfitting. Model performance was assessed using specific metrics and error analysis. Additionally, the SHapley Additive exPlanations (SHAP) method, a feature importance technique within the eXplainable Artificial Intelligence (XAI) framework, was used to identify the feature importance. An of 0.97 and a Mean Absolute Error of 0.36 admissions were achieved by the model. Atmospheric pressure, minimum temperature, and carbon monoxide were found to collectively contribute about 74% to the model's predictive power, with atmospheric pressure being the dominant factor at 37%. This research underscores the significant influence of weather-climate variables on cardiovascular diseases. The identified key climate factors provide a practical framework for policymakers and healthcare professionals to mitigate the adverse effects of climate change on CVD and devise preventive strategies.

Southern Hemisphere atmospheric history of carbon monoxide over the late Holocene reconstructed from multiple Antarctic ice archives

Abstract. Carbon monoxide (CO) is a naturally occurring atmospheric trace gas, a regulated pollutant, and one of the main components determining the oxidative capacity of the atmosphere. Evaluating climate–chemistry models under different conditions than today and constraining past CO sources requires a reliable record of atmospheric CO mixing ratios ([CO]) that includes data since preindustrial times. Here, we report the first continuous record of atmospheric [CO] for Southern Hemisphere (SH) high latitudes over the past 3 millennia. Our continuous record is a composite of three high-resolution Antarctic ice core gas records and firn air measurements from seven Antarctic locations. The ice core gas [CO] records were measured by continuous flow analysis (CFA), using an optical feedback cavity-enhanced absorption spectrometer (OF-CEAS), achieving excellent external precision (2.8–8.8 ppb; 2σ) and consistently low blanks (ranging from 4.1±1.2 to 7.4±1.4 ppb), thus enabling paleo-atmospheric interpretations. Six new firn air [CO] Antarctic datasets collected between 1993 and 2016 CE at the DE08-2, DSSW19K, DSSW20K, South Pole, Aurora Basin North (ABN), and Lock-In sites (and one previously published firn CO dataset at Berkner) were used to reconstruct the atmospheric history of CO from ∼1897 CE, using inverse modeling that incorporates the influence of gas transport in firn. Excellent consistency was observed between the youngest ice core gas [CO] and the [CO] from the base of the firn and between the recent firn [CO] and atmospheric [CO] measurements at Mawson station (eastern Antarctica), yielding a consistent and contiguous record of CO across these different archives. Our Antarctic [CO] record is relatively stable from −835 to 1500 CE, with mixing ratios within a 30–45 ppb range (2σ). There is a ∼5 ppb decrease in [CO] to a minimum at around 1700 CE during the Little Ice Age. CO mixing ratios then increase over time to reach a maximum of ∼54 ppb by ∼1985 CE. Most of the industrial period [CO] growth occurred between about 1940 to 1985 CE, after which there was an overall [CO] decrease, as observed in Greenland firn air and later at atmospheric monitoring sites and attributed partly to reduced CO emissions from combustion sources. Our Antarctic ice core gas CO observations differ from previously published records in two key aspects. First, our mixing ratios are significantly lower than reported previously, suggesting that previous studies underestimated blank contributions. Second, our new CO record does not show a maximum in the late 1800s. The absence of a [CO] peak around the turn of the century argues against there being a peak in Southern Hemisphere biomass burning at this time, which is in agreement with (i) other paleofire proxies such as ethane or acetylene and (ii) conclusions reached by paleofire modeling. The combined ice core and firn air [CO] history, spanning −835 to 1992 CE, extended to the present by the Mawson atmospheric record, provides a useful benchmark for future atmospheric chemistry modeling studies.

Clearing the air: unraveling past and guiding future research in atmospheric chemosynthesis.

Atmospheric chemosynthesis is a recently proposed form of chemoautotrophic microbial primary production. The proposed process relies on the oxidation of trace concentrations of hydrogen (≤530 ppbv), carbon monoxide (≤90 ppbv), and methane (≤1,870 ppbv) gases using high-affinity enzymes. Atmospheric hydrogen and carbon monoxide oxidation have been primarily linked to microbial growth in desert surface soils scarce in liquid water and organic nutrients, and low in photosynthetic communities. It is well established that the oxidation of trace hydrogen and carbon monoxide gases widely supports the persistence of microbial communities in a diminished metabolic state, with the former potentially providing a reliable source of metabolic water. Microbial atmospheric methane oxidation also occurs in oligotrophic desert soils and is widespread throughout copiotrophic environments, with established links to microbial growth. Despite these findings, the direct link between trace gas oxidation and carbon fixation remains disputable. Here, we review the supporting evidence, outlining major gaps in our understanding of this phenomenon, and propose approaches to validate atmospheric chemosynthesis as a primary production process. We also explore the implications of this minimalistic survival strategy in terms of nutrient cycling, climate change, aerobiology, and astrobiology.

Prediction of atmospheric carbon monoxide concentration utilizing different machine learning algorithms: A case study in Kuala Lumpur, Malaysia

Insidious toxin carbon monoxide (CO) can imitate a wide range of different disease states. Clinicians have, and will continue to have, serious concerns about the impact of CO imbalances on the human body. Carbon monoxide concentration has been exceeding the allowable levels in Malaysia. Owing to this, the main objective of this research is to propose a carbon monoxide (CO) prediction model based on machine learning techniques. Three years of historical data were used as input to develop the proposed models to predict carbon monoxide concentrations on a 12-hour and 24-hour basis. Four different machine learning technique models were used for the prediction which are Decision Tree (DT), Random Forest (RF), Support Vector Machine (SVM), and Automated Neural Network – Multi-Layer Perceptron (ANN-MLP). The input parameters used are wind speed, humidity, Ozone (O3), Nitric oxide (NOx), Sulfur dioxide (SO2), and Nitrogen Dioxide (NO2). For each location, in this study, the uncertainty of the models utilized has been implemented to ensure the robustness of the performance. Furthermore, Taylor Diagram has been constructed to distinguish the performance of each model. The results indicate that ANN-MLP outperformed the all-other models involved in this study and showed efficiency in predicting Carbone monoxide concentration. By using ANN-MLP, the highest determination coefficient R2 were achieved which are 0.7190, 0.8914 and 0.7441 for the first station (S1), second station (S2) and the third station (S3) respectively by using 24-hour dataset. Meanwhile, by using a 12-hour dataset, 0.7490 for S1, 0.8942 for S2 and 0.8127 for S3. The uncertainty analysis of the ANN-MLP has 0.99 of confidence level and the lowest d-factor achieved, at S2 by using 12-hour dataset, is 0.000250455. These results ensure the effectiveness and robustness of ANN-MLP to predict carbon monoxide in the tropospheric layer. Code availabilityNot applicable.

The Transient Outgassed Atmosphere of 55 Cancri e

T​​​​​​he enigmatic nature of 55 Cancri e has defied theoretical explanation. Any explanation needs to account for the observed variability of its secondary eclipse depth, which is at times consistent with zero in the visible/optical range of wavelengths—a phenomenon that does not occur with its also variable infrared eclipses. Yet despite this variability, its transit depth remains somewhat constant in time and is inconsistent with opaque material filling its Hill sphere. The current study explores the possibility of a thin, transient, secondary atmosphere on 55 Cancri e that is sourced by geochemical outgassing. Its transient nature derives from the inability of outgassing to be balanced by atmospheric escape. As the outgassed atmosphere escapes and is replenished, it rapidly adjusts to radiative equilibrium and the temperature fluctuations cause the infrared eclipse depths to vary. Atmospheres of pure carbon dioxide or carbon monoxide produce sufficient Rayleigh scattering to explain the observed optical/visible eclipse depths, which vanish in the absence of an atmosphere and the presence of a dark rocky surface. Atmospheres of pure methane are ruled out, because they produce insufficient Rayleigh scattering. Upcoming observations by the James Webb Space Telescope will potentially allow the atmospheric temperature and surface pressure, as well as the surface temperature, to be measured.

Exposure levels for carbon monoxide in nuclear submarine atmosphere

This work proposes exposure limits for carbon monoxide in the nuclear submarine environment. Linear and non-linear forms of the Coburn-Foster-Kane equation were used to evaluate carbon monoxide exposure for an environment with low oxygen content, different exposure times and crew physical activity levels. We evaluated the 90-day Continuous Exposure Guidance Level, 24-h and 1-h Emergency Exposure Guidance Levels and 10-day and 24-h Submarine Escape Action Levels. The results showed that the concentration of carbon monoxide in the environment must not exceed 9 ppm for the 90-day Continuous Exposure Guidance Level, 35 ppm for the 24-h Emergency Exposure Guidance Level, 90 ppm 1-h Emergency Exposure Guidance Level, 60 ppm for the 10-day Submarine Escape Action Level and 80 ppm for the 24-h Submarine Escape Action Level. Comparing these values with those established by the National Research Council for the United States Navy, the limits proposed by this work are verified to be lower, which may indicate a risk to the health of the crew. They also show the impact of the crew's level of physical activity on the formation of carboxyhemoglobin.

Getting insight into the CO tolerance over Co-modified MnSm/Ti catalyst for NH3-SCR of NOx at low temperature: Experiments and DFT studies

The existence of carbon monoxide (CO) in industrial boilers flue gas can suppress the performance of the selective catalytic reduction with NH3 (NH3-SCR) for NOx removal at low temperatures over the Mn-based catalyst, and the related mechanism is needed to be revealed for improving the NH3-SCR performance. In this work, the effects of CO on the NH3-SCR performance over MnSm/Ti catalyst were studied, and the CO tolerance of the catalyst with cobalt (Co) modification at low temperatures was evaluated. The DFT calculations were performed to reveal the mechanism for the modification of Co over the MnSm/Ti catalyst. The NOx conversion for MnSm/Ti catalyst decreased by 15.2%-21.4% at 150–300 ℃ due to the presence of CO in the NH3-SCR reaction atmosphere. After introducing Co into MnSm/Ti catalyst, the NOx conversion for MnSmCo/Ti catalyst only decreased by 8.9%-13.8% at 150–300 ℃ with the presence of CO. It was evidenced that the CO tolerance of the MnSm/Ti catalyst was enhanced with the Co modification. The characterizations of catalysts revealed that the adsorptions of NH3 and NO over the MnSm/Ti catalyst were inhibited by the presence of CO in the mixed atmosphere. Furthermore, the presence of CO in the flue gas resulted in the formation of carbonates, bicarbonates, and bridging formate on the surface of the MnSm/Ti catalysts, which would cause a decrease in the content of Mn4+ and Oα on the surface of the catalyst surface. Introducing Co into MnSm/Ti catalyst could enhance the adsorption of NH3 by forming more Lewis acid sites over the MnSmCo/Ti catalyst. The contents of Mn4+ and Oα over MnSmCo/Ti catalyst were increased via the strong electronic interaction between Co ions and Mn ions. DFT calculations proved that the adsorption of CO over the catalyst was suppressed by the modification of Co with the change of the adsorption energy of CO from −167.25 kJ/mol to −53.82 kJ/mol. Additionally, the Co modification facilitated the decomposition of the carbonate formed over the catalyst with the energy barrier of related reactions decreasing from 214.67 kJ/mol to 24.45 kJ/mol, thus improving the CO tolerance of the catalyst.

Multicomponent Reaction: Pd/Cu-Catalyzed Borocarbonylation of Aryldiazonium Salts with Aliphatic Terminal Alkynes to gem-Bis(boryl) Ketones.

We report the development of Pd/Cu-catalyzed selective 2,1-borocarbonylation reactions of aliphatic terminal alkynes with aryldiazonium salts and B2 Pin2 to prepare gem-bis(boryl) ketones in one-pot. A series of corresponding products are obtained with good to excellent yields under a carbon monoxide atmosphere (10 bar). In addition, wide functional-group tolerance can be observed. Preliminary mechanistic studies reveal that ethyl acetate serves as a proton source in the reaction.

Spatial heterogeneity in global atmospheric CO during the COVID–19 lockdown: Implications for global and regional air quality policies

The COVID–19 lockdown (LD) provided a unique opportunity to examine the changes in regional and global air quality. Changes in the atmospheric carbon monoxide (CO) during LD warrant a thorough analysis as CO is a major air pollutant that affects human health, ecosystem and climate. Our analysis reveals a decrease of 5–10% in the CO column during LD (April–May 2020) compared to the pre-lockdown (PreLD, March 2020) periods in regions with high anthropogenic activity, such as East China (EC), Indo-Gangetic Plain (IGP), North America, parts of Europe and Russia. However, this reduction did not occur in the regions of frequent and intense wildfires and agricultural waste burning (AWB). We find high heterogeneity in the CO column distributions, from regional to city scales during the LD period. To determine the sources of CO emissions during LD, we examined the ratios of nitrogen dioxide (NO2), sulfur dioxide (SO2) to CO for major cities in the world. This facilitated the identification of contributions from different sources; including vehicles, industries and biomass burning during LD. The comparison between CO levels during the LD and PreLD periods indicates a notable reduction in the global tropospheric CO, but no significant change in the stratosphere. It is found that CO emissions decreased during LD in the hotspot regions, but rebounded after the LD restrictions were lifted. This study, therefore, highlights the importance of policy decisions and their implementations in the global and regional scales to improve the air quality, and thus to protect public health and environment.

Palladium‐Catalyzed Hydroaminocarbonylation of Olefins with Aliphatic Amines without Additives

AbstractPalladium‐catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct‐1‐ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N‐nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo‐, regio‐ and enantioselectivities was also studied. Plausible explanation was given for the additive‐free hydroaminocarbonylation reaction.

Structural transition of VSe2 on Au(1 1 1) induced by high sensitivity to CO gas

Carbon monoxide (CO) is one of the well-studied reactants in many chemical catalytic reactions, and it is important to deeply understand the adsorption behavior as well as chemical reactivity of CO on a solid surface with regards to adsorption/desorption kinetics. Therefore, it is of great interest to study the process of CO adsorption and further catalytic reaction on one of the transition metal dichalcogenides, namely Vanadium diselenide (VSe2) because of its excellent catalytic activities. Herein, based on in-situ scanning tunneling microscopy (STM) study and density functional theory (DFT) calculations, we systematically investigated the absorption effect under different CO pressures. At relatively low pressure of CO (about 1x10-8 mbar), a few CO molecules adsorb on VSe2 and lead to the desorption of the top-Se atoms resulting in point defects. With the rise of pressure, the amount of absorbed CO increases, and the underlying V atoms also desorb due to the interaction of CO, finally leading to the structural transition of the whole VSe2. One thing to note is that, during the experiment CO atmosphere was injected as a continuous flow and some STM images were taken at the same time expressing the dynamic behavior of CO adsorption on VSe2, which has scarcely been in other static systems like UHV-STM.

Seasonal, interannual and long-term changes in the middle atmospheric carbon monoxide in the tropics

Middle atmospheric carbon monoxide (CO) has been considered as a dynamical tracer to study the transport in the stratosphere and mesosphere because of its long lifetime. However, most trend studies of CO are limited to troposphere and the Upper Troposphere Lower Stratosphere (UTLS). Here, we investigate the seasonal, annual and long-term changes of CO in the tropical (30° N–30° S) middle atmosphere (20–80 km) for the period of 2005–2021. CO shows a semi-annual oscillation in the higher altitudes of both stratosphere and mesosphere. The response of solar cycle to CO increases with altitude and is largest in the mesosphere. On the other hand, Quasi Biennial Oscillation (QBO) response to CO change is highest in the lower stratosphere. The CO trends are statistically insignificant at all altitudes, although they are positive in the height range 20–25 km and 32–40 km, at about 0.01–0.035/yr, depending on altitude. The observed changes in the middle atmospheric CO in the tropics are well reproduced by the Whole Atmospheric Chemical Climate Model (WACCM). Therefore, this study provides new insights on the long-term changes in the tropical middle atmospheric CO and its connection to dynamics of the region.

Diurnal carbon monoxide observed from a geostationary infrared hyperspectral sounder: first result from GIIRS on board FengYun-4B

Abstract. The Geostationary Interferometric Infrared Sounder (GIIRS) on board FengYun-4 series satellites is the world's first geostationary hyperspectral infrared sounder. With hyperspectral measurement collected from a geostationary orbit covering the carbon monoxide (CO) absorption window around 2150 cm−1, GIIRS provides a unique opportunity for monitoring the diurnal variabilities of atmospheric CO over eastern Asia. In this study, we develop the FengYun Geostationary satellite Atmospheric Infrared Retrieval (FY-GeoAIR) algorithm to retrieve the CO profiles using observations from GIIRS on board FY-4B, which was launched in June 2021, and provide CO maps at a spatial resolution of 12 km and a temporal resolution of 2 h. The performance of the algorithm is first evaluated by conducting retrieval experiments using simulated synthetic spectra. The result shows that the GIIRS data provide significant information for constraining CO profiles. The degree of freedom for signal (DOFS) and retrieval error are both highly correlated with thermal contrast (TC), the temperature difference between the surface and the lower atmosphere. Retrieval results from 1 month of GIIRS spectra in July 2022 show that the DOFS for the majority is between 0.8 and 1.5 for the CO total column and between 0 and 0.8 for the bottom three layers ranging from the surface to 3 km a.s.l. Consistent with CO retrievals from low-Earth-orbit (LEO) infrared sounders, the largest observation sensitivity, as quantified by the averaging kernel (AK), is in the free troposphere at around 3–6 km. The diurnal changes in DOFS and vertical sensitivity of observation are primarily driven by the diurnal TC variabilities. Finally, we compare the CO total columns between GIIRS and Infrared Atmospheric Sounding Interferometer (IASI) and find that the two datasets show good consistency in capturing the spatial and temporal variabilities. This study demonstrates that the GIIRS retrievals are able to reproduce the temporal variability of CO total columns over eastern Asia in the daytime in July. Nevertheless, the retrievals have low detectivity in the nighttime due to their weak sensitivity to the ground level CO changes limited by low information content. Model assimilation that takes into account the retrieved diurnal CO profiles and the associated vertical sensitivity will have potential in improving local and global air quality and climate research over eastern Asia.

Effect of Transition Metals Addition on the Nickel Oxide Catalyst toward Reduction Behaviour in Carbon Monoxide Atmosphere

The chemical reduction progression behaviour of transition metals (Mo, Zr, W, Ce, and Co) doped on NiO was studied using temperature programmed reduction (TPR) analysis. A wet impregnation method was applied to synthesise the doped NiO series catalysts. The reduction progress of the catalysts was attained by using a reductant gas at the concentration of 40% v/v CO/N2. X-ray diffraction (XRD) was employed to determine the composition of the reduced phases. Undoped NiO was reduced at 384℃ to obtain a cubic phase of NiO. It was observed that Ce/NiO exhibited the lowest reduction temperature of 370℃ among all catalysts. This phenomenon might be due to a higher surface area of Ce/NiO compared to undoped NiO, which facilitated a faster reduction reaction. The rest of the doped NiO series catalysts (Co/NiO, Mo/NiO, W/NiO and Zr/NiO) demonstrated a higher reduction temperature compared to undoped NiO. New peaks in the XRD pattern were observed only for the reduced catalysts of Mo/NiO and W/NiO, which were associated with monoclinic MoO2 and WO2.72 phases, respectively. The formation of new compounds or more stable nickel alloys led to a slower reduction reaction than undoped NiO. Therefore, Ce/NiO was the most efficient catalyst in promoting the formation of Ni under the CO atmosphere.

Study on liquefaction characteristics of lignite in CO atmosphere

This article investigated the interaction mechanism between carbon monoxide (CO) and lignite organic matter in lignite liquefaction systems. The study found that a CO atmosphere can facilitate lignite conversion, but its hydrogen supply capacity is poor, resulting in lower liquefaction effects compared to an H2 atmosphere. Increasing the initial reaction pressure and CO content can enhance the conversion of lignite to low molecular compounds. In-situ studies on lignite pyrolysis in CO and N2 atmospheres show that CO plays an effective role in promoting the fracture of multiple hydrogen bonds present in lignite, which is linked to the water-gas shift reaction that CO takes part. Additionally, CO can also facilitate the breaking of oxygen-containing ether bonds in lignite, thereby eliminating oxygen and producing CO2 in the gaseous phase. Density functional theory (DFT) calculations demonstrate that CO reacts with the group after the ether bond breaks, which reduces the formation energy of the product and promotes the ether bond breaking. In summary, CO in syngas may benefit the breaking of ether and hydrogen bonds in lignite during liquefaction, thus promoting lignite conversion.

Carbon monoxide (CO) cycling in the Fram Strait, Arctic Ocean

Abstract. Carbon monoxide (CO) influences the radiative budget and oxidative capacity of the atmosphere over the Arctic Ocean, which is a source of atmospheric CO. Yet, oceanic CO cycling is understudied in this area, particularly in light of the ongoing rapid environmental changes. We present results from incubation experiments conducted in the Fram Strait in August–September 2019 under different environmental conditions: while lower pH did not affect CO production (GPCO) or consumption (kCO) rates, enhanced GPCO and kCO were positively correlated with coloured dissolved organic matter (CDOM) and dissolved nitrate concentrations, respectively, suggesting microbial CO uptake under oligotrophic conditions to be a driving factor for variability in CO surface concentrations. Both production and consumption of CO will likely increase in the future, but it is unknown which process will dominate. Our results will help to improve models predicting future CO concentrations and emissions and their effects on the radiative budget and the oxidative capacity of the Arctic atmosphere.

Rising surface ozone due to anthropogenic activities and its impact on COVID-19 related deaths in Delhi, India

The rapidity and global spread of the COVID-19 pandemic have left several vital questions in the research community requiring coordinated investigation and unique perspectives to explore the relationship between the spread of disease and air quality. Previous studies have focused mainly on the relation of particulate matter concentration with COVID-19-related mortalities. In contrast, surficial ozone has not been given much attention as surface ozone is a primary air pollutant and directly impacts the respiratory system of humans. Hence, we analyzed the relationship between surface ozone pollution and COVID-19-related mortalities. In this study, we have analyzed the variability of various atmospheric pollutants (particulate matter (PM2.5 and PM10), Nitrogen dioxide (NO2), Carbon monoxide (CO), and Ozone) in the National Capital Region (NCR) of India during 2020–2021 using station data and investigated the relationship of the air-quality parameters with the COVID-19 related deaths. In northern parts of India, the concentration of particulate matter (PM2.5 and PM10), Nitrogen dioxide (NO2), Carbon monoxide (CO), and Ozone remain high during the pre- and post-monsoon seasons due to dust loading and crop residue burning (after winter wheat in April & summer rice in November). The westerly wind brings the polluted airmass from western and northwestern parts to Delhi and National Capital Region during April–June and October–November, and meteorological conditions help raise the concentration of these pollutants. Due to long solar hours and high CO concentrations, the ozone concentration is higher from April to June and September. While comparing major air quality parameters with COVID-19-related deaths, we found a good relationship between surface ozone and COVID-19 mortality in Delhi. We also observed a time lag relationship between ozone concentration and mortality in Delhi, so the exposure to Ozone in a large population of Delhi may have augmented the rise of COVID-19-related deaths. The analysis suggested that ozone has a significant relationship with COVID-19 related mortality in Delhi in comparison to other parameters.

One-pot synthesis of hyperbranched polymers via visible light regulated switchable catalysis

Switchable catalysis promises exceptional efficiency in synthesizing polymers with ever-increasing structural complexity. However, current achievements in such attempts are limited to constructing linear block copolymers. Here we report a visible light regulated switchable catalytic system capable of synthesizing hyperbranched polymers in a one-pot/two-stage procedure with commercial glycidyl acrylate (GA) as a heterofunctional monomer. Using (salen)CoIIICl (1) as the catalyst, the ring-opening reaction under a carbon monoxide atmosphere occurs with high regioselectivity (>99% at the methylene position), providing an alkoxycarbonyl cobalt acrylate intermediate (2a) during the first stage. Upon exposure to light, the reaction enters the second stage, wherein 2a serves as a polymerizable initiator for organometallic-mediated radical self-condensing vinyl polymerization (OMR-SCVP). Given the organocobalt chain-end functionality of the resulting hyperbranched poly(glycidyl acrylate) (hb-PGA), a further chain extension process gives access to a core-shell copolymer with brush-on-hyperbranched arm architecture. Notably, the post-modification with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords a metal-free hb-PGA that simultaneously improves the toughness and glass transition temperature of epoxy thermosets, while maintaining their storage modulus.

Rapid decline of carbon monoxide emissions in the Fenwei Plain in China during the three-year Action Plan on defending the blue sky

The Fenwei Plain is one of China's most polluted regions, with poor atmospheric dispersion conditions and an outdated energy structure. After implementing multiple policies in recent years, significant reductions in air pollutant concentrations were observed. In this study, based on the Lagrangian-Bayesian inversion framework FLEXINVERT, we constructed a variable resolution inversion system focusing on the Fenwei Plain and inferred the carbon monoxide (CO) emissions using in-situ atmospheric CO observations from April 2014 to March 2020. We analyzed the spatiotemporal variations of the CO emissions and discussed their causes, especially the effect of the “Three-year Action Plan on Defending the Blue Sky” (TAPDBS). Before the policy, CO emissions temporarily increased, and the overall decrease in CO emissions per unit of Gross Domestic Product (GDP) slowed down. When the policy was implemented, CO emission fluxes declined sharply, with an average drop of 28%, accompanied by an even higher 37% decrease of CO emission per GDP. The reasons for the decline in CO emissions in Shanxi, Shaanxi and Henan are diverse. The decrease in energy intensity is the reason for CO emission reduction in Shannxi and Henan province but not in Shanxi province. This research fills the gap in emission information in recent years and confirms that TAPDBS has brought a breakthrough in both economic development and air quality protection in the Fenwei Plain.

Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons.

Under an atmosphere of carbon monoxide (CO), a (phosphino)diazomethyl anion salt [[P]-CN2 ][K(18-C-6)(THF)] (1) ([P]=[(CH2 )(NDipp)]2 P; 18-C-6=18-crown-6; Dipp=2,6-diisopropylphenyl) undergoes a facile N2 /CO exchange reaction giving the (phosphino)ketenyl anion salt [[P]-CCO][K(18-C-6)] (2). Oxidation of 2 with elemental Se affords the (selenophosphoryl)ketenyl anion salt [P](Se)-CCO][K(18-C-6)] (3). These ketenyl anions feature a strongly bent geometry at the P-bound carbon and this carbon atom is highly nucleophilic. The electronic structure of the ketenyl anion [[P]-CCO]- of 2 is examined by theoretical studies. Reactivity investigations demonstrate 2 as a versatile synthon for derivatives of ketene, enolate, acrylate and acrylimidate moieties.