Efficient absorption of CO2 by protic-ionic-liquid based deep eutectic solvents.

Carbon capture, utilization, and storage (CCUS) are among the key technologies to achieve large-scale carbon emission reduction globally. Deep eutectic solvents (DESs) are considered as designable solvents, which has attracted intensive attention for CO2 capture. Here, a series of binary DESs are synthesized through one-step mixing with the starting materials of protic ionic liquid (PIL) and amine. The eutectic behavior was investigated by measuring the melting point of PILs and amine. The saturated vapor of these DESs and industrial MDEA solution were measured and compared. These DESs are investigated to have high absorption capacity (0.1 g·g-1 at 1.0 bar and 25ºC), superior apparent absorption rate constant (0.381 min-1 vs 0.012 min-1 of MDEA-30%H2O), moderate interaction with CO2 (the enthalpy change is as low as -34.8 kJ·mol-1). The absorption mechanism is also investigated by NMR analysis. Eight absorption/desorption regeneration experiments are carried out to show their reversibility. Considering the advantages, including convenience of synthesis, large absorption capacity, fast absorption rate, and moderate interaction energy as well as good regeneration, these DESs are believed to be as potential CO2 absorbent in practical applications.

Recurrence and malignant transformation of laryngeal leukoplakia treated with CO2 laser: A systematic review and meta-analysis.

BACKGROUND: Laryngeal leukoplakia (LL) is a white lesion with high potential of recurrence and malignant transformation. Currently, CO2 laser has become the primary surgical treatment for LL, and the recurrence and malignant transformation rates after treatment vary widely. OBJECTIVE: We performed a systematic review and meta-analysis dedicated to evaluating the rates of recurrence and malignant transformation of LL lesions treated with CO2 laser and exploring relevant risk factors for recurrence or malignant transformation. METHODS: Literature searches were conducted on ProQuest, PubMed, Web of Science, Ovid Medline, Embase, and Cochrane databases. Some articles identified through hand searching were included. RESULTS: A total of 14 articles and 1462 patients were included in this review. Pooled results showed that the overall recurrence rate was 15%, and the malignant transformation rate was 3%. Subgroup analysis showed that the dysplasia grade was not a significant risk factor for the recurrence and malignant transformation of LL (P > .05). CONCLUSIONS: The results of this systematic review and meta-analysis suggest that the CO2 laser is a safe and effective surgical instrument for the excision of LL, which yields low rates of recurrence and malignant transformation. The risk factors relevant to recurrence or malignant transformation remain unclear and require further investigation.

Anesthesia experience in an adult Silver-Russell syndrome: a case report.

BACKGROUND: There are no reports of anesthesia use in adult patients with Silver-Russell syndrome (SRS). Here, we report our experience with anesthesia in an adult patient with SRS complicated by chronic respiratory failure. CASE PRESENTATION: A 33-year-old woman was clinically diagnosed with SRS. She had severe chronic respiratory failure, complicated by superior mesenteric artery syndrome. Percutaneous gastrostomy was scheduled for nutritional management under epidural anesthesia; however, soon after esophagogastroduodenoscopy was started, she lost consciousness and spontaneous respiration. The patient was urgently intubated and converted to general anesthesia. The end-tidal carbon dioxide tension was > 90 mmHg at intubation. CONCLUSIONS: Adult SRS patients with chronic respiratory failure have a risk of CO2 narcosis. SRS also requires preparation for difficult airway management during the perioperative period.

Spontaneous α-C-H Carboxylation of Ketones by Gaseous CO2 at the Air-water Interface of Aqueous Microdroplets.

We present a catalyst-free route for the reduction of carbon dioxide integrated with the formation of a carbon-carbon bond at the air/water interface of negatively charged aqueous microdroplets, at ambient temperature. The reactions proceed through carbanion generation at the α-carbon of a ketone followed by nucleophilic addition to CO2. Online mass spectrometry reveals that the product is an α-ketoacid. Several factors, such as the concentration of the reagents, pressure of CO2 gas, and distance traveled by the droplets, control the kinetics of the reaction. Theoretical calculations suggest that water in the microdroplets facilitates this unusual chemistry. Furthermore, such a microdroplet strategy has been extended to seven different ketones. This work demonstrates a green pathway for the reduction of CO2 to useful carboxylated organic products.

Parkinson's disease cerebrovascular reactivity pattern: A feasibility study.

A mounting body of research points to cerebrovascular dysfunction as a fundamental element in the pathophysiology of Parkinson's disease (PD). In the current feasibility study, blood-oxygen-level-dependent (BOLD) MRI was used to measure cerebrovascular reactivity (CVR) in response to hypercapnia in 26 PD patients and 16 healthy controls (HC), and aimed to find a multivariate pattern specific to PD. Whole-brain maps of CVR amplitude (i.e., magnitude of response to CO2) and latency (i.e., time to reach maximum amplitude) were computed, which were further analyzed using scaled sub-profile model principal component analysis (SSM-PCA) with leave-one-out cross-validation. A meaningful pattern based on CVR latency was identified, which was named the PD CVR pattern (PD-CVRP). This pattern was characterized by relatively increased latency in basal ganglia, sensorimotor cortex, supplementary motor area, thalamus and visual cortex, as well as decreased latency in the cerebral white matter, relative to HC. There were no significant associations with clinical measures, though sample size may have limited our ability to detect significant associations. In summary, the PD-CVRP highlights the importance of cerebrovascular dysfunction in PD, and may be a potential biomarker for future clinical research and practice.

Influence of Iron Substitution and Solution Composition on Brucite Carbonation.

Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH)2] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO2. Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na2SO4, and Na4SiO4). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe10IIIO14(OH)2] and layered double hydroxides {e.g., pyroaurite [Mg6Fe2III(OH)16CO3·4H2O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO3·3H2O) and dypingite [Mg5(CO3)4(OH)2·âˆ¼5H2O], as well as chukanovite [Fe2IICO3(OH)2] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride- and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO2·nH2O and Fe-Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

The effect of hypertension on cerebrovascular carbon dioxide reactivity in atrial fibrillation patients.

Atrial fibrillation (AF) and hypertension (HTN) are both associated with impaired cerebrovascular carbon dioxide reactivity (CVRCO2), an indicator of cerebral vasodilatory reserve. We hypothesised that CVRCO2 would be lower in patients with both AF and HTN (AF + HTN) compared to normotensive AF patients, due to an additive effect of AF and HTN on CVRCO2. Forty AF (68 ± 9 years) and fifty-seven AF + HTN (68 ± 8 years) patients underwent transcranial Doppler ultrasound measurement of middle cerebral artery blood velocity (MCA Vm) during stepped increases and decreases in end-tidal carbon dioxide (PETCO2). A cerebrovascular conductance index (CVCi) was calculated as the ratio of MCA Vm and mean arterial pressure (MAP). CVRCO2 was determined from the linear slope for MCA Vm and MCA CVCi vs PETCO2. Baseline MAP was higher in AF + HTN than AF (107 ± 9 vs. 98 ± 9 mmHg, respectively; p < 0.001), while MCA Vm was not different (AF + HTN:49.6 [44.1-69.0]; AF:51.7 [45.2-63.3] cm.s-1; p = 0.075), and CVCi was lower in AF + HTN (0.46 [0.42-0.57] vs. 0.54 [0.44-0.63] cm.s-1.mmHg-1; p < 0.001). MCA Vm CVRCO2 was not different (AF + HTN: 1.70 [1.47-2.19]; AF 1.74 [1.54-2.52] cm/s/mmHg-2; p = 0.221), while CVCi CVRCO2 was 13% lower in AF + HTN (0.013 ± 0.004 vs 0.015 ± 0.005 cm.s-1.mmHg-1; p = 0.047). Our results demonstrate blunted cerebral vasodilatory reserve (determined as MCA CVCi CVRCO2) in AF + HTN compared to AF alone. This may implicate HTN as a driver of further cerebrovascular dysfunction in AF that may be important for the development of AF-related cerebrovascular events and downstream cognitive decline. We demonstrated reduced cerebrovascular CO2 responsiveness in atrial fibrillation with hypertension (AF+HTN) vs. atrial fibrillation (AF). Furthermore, AF per se (as opposed to normal sinus rhythm) predicts reduced cerebrovascular CO2 responsiveness. Our findings suggest additional cerebrovascular dysfunction in AF+HTN vs. AF.

Hypocapnia is associated with increased in-hospital mortality and 1 year mortality in acute heart failure patients.

AIMS: Both hypercapnia and hypocapnia are common in patients with acute heart failure (AHF), but the association between partial pressure of arterial carbon dioxide (PaCO2) and AHF prognosis remains unclear. The objective of this study was to investigate the connection between PaCO2 within 24 h after admission to the intensive care unit (ICU) and mortality during hospitalization and at 1 year in AHF patients. METHODS AND RESULTS: AHF patients were enrolled from the Medical Information Mart for Intensive Care IV database. The patients were divided into three groups by PaCO2 values of <35, 35-45, and >45 mmHg. The primary outcome was to investigate the connection between PaCO2 and in-hospital mortality and 1 year mortality in AHF patients. The secondary outcome was to assess the prediction value of PaCO2 in predicting in-hospital mortality and 1 year mortality in AHF patients. A total of 2374 patients were included in this study, including 457 patients in the PaCO2 < 35 mmHg group, 1072 patients in the PaCO2 = 35-45 mmHg group, and 845 patients in the PaCO2 > 45 mmHg group. The in-hospital mortality was 19.5%, and the 1 year mortality was 23.9% in the PaCO2 < 35 mmHg group. Multivariate logistic regression analysis showed that the PaCO2 < 35 mmHg group was associated with an increased risk of in-hospital mortality [hazard ratio (HR) 1.398, 95% confidence interval (CI) 1.039-1.882, P = 0.027] and 1 year mortality (HR 1.327, 95% CI 1.020-1.728, P = 0.035) than the PaCO2 = 35-45 mmHg group. The PaCO2 > 45 mmHg group was associated with an increased risk of in-hospital mortality (HR 1.387, 95% CI 1.050-1.832, P = 0.021); the 1 year mortality showed no significant difference (HR 1.286, 95% CI 0.995-1.662, P = 0.055) compared with the PaCO2 = 35-45 mmHg group. The Kaplan-Meier survival curves showed that the PaCO2 < 35 mmHg group had a significantly lower 1 year survival rate. The area under the receiver operating characteristic curve for predicting in-hospital mortality was 0.591 (95% CI 0.526-0.656), and the 1 year mortality was 0.566 (95% CI 0.505-0.627) in the PaCO2 < 35 mmHg group. CONCLUSIONS: In AHF patients, hypocapnia within 24 h after admission to the ICU was associated with increased in-hospital mortality and 1 year mortality. However, the increase in 1 year mortality may be influenced by hospitalization mortality. Hypercapnia was associated with increased in-hospital mortality.

The Tandem Nitrate and CO2 Reduction for Urea Electrosynthesis: Role of Surface N-Intermediates in CO2 Capture and Activation.

Electrochemical reduction of CO2 and nitrate offers a promising avenue to produce valuable chemicals through the using of greenhouse gas and nitrogen-containing wastewater. However, the generally proposed reaction pathway of concurrent CO2 and nitrate reduction for urea synthesis requires the catalysts to be both efficient in both CO2 and nitrate reduction, thus narrowing the selection range of suitable catalysts. Herein, we demonstrate a distinct mechanism in urea synthesis, a tandem NO3- and CO2 reduction, in which the surface amino species generated by nitrate reduction play the role to capture free CO2 and subsequent initiate its activation. When using the TiO2 electrocatalyst derived from MIL-125-NH2, it intrinsically exhibits low activity in aqueous CO2 reduction, however, in the presence of both nitrate and CO2, this catalyst achieves an excellent urea yield rate of 43.37 mmolï½¥g-1ï½¥h-1 and a Faradaic efficiency of 48.88% at -0.9 V vs. RHE in a flow cell. Even at a low CO2 level of 15%, the Faradaic efficiency of urea synthesis remains robust at 42.33%. The tandem reduction procedure was further confirmed by in-situ spectroscopies and theoretical calculations. This research provides new insights into the selection and design of electrocatalysts for urea synthesis.

Effect of Casein Phosphopeptide-Amorphous Calcium Phosphate, Proanthocyanidin, Carbon Dioxide Laser Remineralization on the Bond Integrity of Composite Restoration Bonded to Caries Affected Dentin.

Objective: Assessment of different remineralizing pretreatment casein phosphopeptide-amorphous calcium phosphate (CPP-ACP), proanthocyanidin (PA), carbon dioxide laser (CO2), eggshell solution (ES) on the shear bond strength (SBS) of resin composite bonded to remineralized carious-affected dentin (CAD). Materials and methods: Eighty human molars were collected with occlusal caries that extended about halfway into the dentin. Using a water-cooled, low-speed cutting saw, a flat, mid-coronal dentin surface was exposed. CAD was differentiated from healthy dentin. Based on the remineralizing agent used on the CAD surface, the teeth were arbitrarily allocated into five groups (n = 10). Group 1: no remineralizing agent, Group 2: CPP-ACP, Group 3: 6.5% PA solution, Group 4: CO2 laser, and Group 5: ES solution. All samples were bonded to composite and light cured and thermocycled. SBS and failure mode analysis were performed using universal testing and stereomicroscope 40 × . Using SPSS, SBS, and failure mode data were analyzed using analysis of variance and Tukey's honesty significant difference (HSD) test Results: Group 3 (6.5% PA solution; 15.59 ± 1.44 MPa) samples established the maximum bond integrity. Nevertheless, Group 1 (No remineralizing agent; 11.19 ± 1.21 MPa) exhibited the minimum outcome of bond strength. Intergroup comparison analysis showed that Group 1 (No remineralizing agent), Group 2 (CPP-ACP), and Group 4 (CO2 laser) established comparable values of bond strength (p > 0.05). Likewise, Group 3 (6.5% PA solution) and Group 5 (EA solution) also revealed equivalent bond integrity (p > 0.05). Conclusions: PA and ES are considered potential remineralizing agents used for caries-affected dentin surfaces in improving bond integrity to composite resin. However, further studies are advocated to extrapolate the findings of this study.

Utilization of used textiles for solid recovered fuel production.

One of the current important issues is the management of used textiles. One method is recycling, but the processes are characterized by a high environmental burden and the products obtained are of lower quality. Used textiles can be successfully used to produce SRF (solid recovered fuels). This type of fuel is standardized by ISO 21640:2021. In the paper, an analysis of used textiles made from fibers of different origins was performed. These were acrylic, cotton, linen, polyester, wool, and viscose. A proximate and ultimate analysis of the investigated samples was performed, including mercury and chlorine content. The alternative fuel produced from used textiles will be characterized by acceptable parameters for consumers: a lower heating value at 20 MJ/kg (class 1-3 SRF), mercury content below 0.9 µg Hg/MJ (class 1 SRF), and a chlorine content below 0.2% (class 1 SRF). However, the very high sulfur content in wool (3.0-3.6%) and the high nitrogen content in acrylic may limit its use for power generation. The use of alternative fuel derived from used textiles may allow 3% of the coal consumed to be substituted in 2030. The reduction in carbon dioxide emissions from the substitution of coal with an alternative fuel derived from used textiles will depend on their composition. For natural and man-made cellulosic fibers, the emission factor can be assumed as for plant biomass, making their use for SRF production preferable. For synthetic fibers, the emission factor was estimated at the level of 102 and 82 gCO2/MJ for polyester and acrylic, respectively.

Evaluating the efficacy of a standardized 4 mL/kg fluid bolus technique in critically ill patients with elevated PvaCO2: secondary analysis of two prospective studies.

Background: Limiting the fluid bolus (FB) volume may attenuate side effects, including hemodilution and increased filling pressures, but it may also reduce hemodynamic responsiveness. The minimum volume to create hemodynamic effects is considered to be 4 mL/kg. In critically ill patients, the hemodynamic effects of FB with this volume have not been adequately investigated and compared to higher quantities. We hypothesized that a standardized FB approach using 4 mL/kg has comparable hemodynamic and metabolic effects to the common practice of physician-determined FB in critically ill patients. Methods: We conducted post hoc analysis of two trials in non-selected critically ill patients with central venous-to-arterial CO2 tension (PvaCO2) >6 mmHg and no acute bleeding. All patients received crystalloids either at a physician-determined volume and rate or at 4 mL/kg pump-administered at 1.2 L/h. Cardiac index (CI) was calculated with transthoracic echocardiogram, and arterial and venous blood gas samples were assessed before and after FB. Endpoints were changes in CI and oxygen delivery (DO2) >15%. Results: A total of 47 patients were eligible for the study, 15 of whom received physician-determined FB and 32 of whom received standardized FB. Patients in the physician-determined FB group received 16 (12-19) mL/kg at a fluid rate of 1.5 (1.5-1.9) L/h, compared to 4.1 (3.7-4.4) mL/kg at a fluid rate of 1.2 (1.2-1.2) L/h (p < 0.01) in the standardized FB group. The difference in CI elevations between the two groups was not statistically significant (8.8% [-0.1-19.9%] vs. 8.4% [0.3-23.2%], p = 0.76). Compared to physician-determined FB, the standardized FB technique had similar probabilities of increasing CI or DO2 by >15% (odds ratios: 1.3 [95% CI: 0.37-5.18], p = 0.66 and 1.83 [95% CI: 0.49-7.85], p = 0.38). Conclusion: A standardized FB protocol (4 mL/kg at 1.2 L/h) effectively reduced the volume of fluid administered to critically ill patients without compromising hemodynamic or metabolic effects.

Venoarterial Partial Pressure of Carbon Dioxide Difference: Let's Trend It!

How to cite this article: Ravisankar NR. Venoarterial Partial Pressure of Carbon Dioxide Difference: Let's Trend It! Indian J Crit Care Med 2024;28(4):323-325.

Relationship between maternal arterial and foetal cord carbon dioxide tension and neonatal outcome in critically ill pregnant women at delivery.

Background and Aims: No studies have evaluated the relationship between maternal arterial partial pressure of carbon dioxide (mPaCO2) and umbilical cord venous partial pressure of carbon dioxide (PCO2) in critically ill pregnant women at delivery. Based on the studies in healthy pregnant women, an mPaCO2 target of ≤50 mmHg is a suggested threshold during mechanical ventilation in critically ill parturients. We evaluated the relationship between mPaCO2 and neonatal cord gases in critically ill parturients at delivery as the primary objective. The relationship between mPaCO2 and APGAR scores at delivery was also analysed as a secondary objective. Methods: Maternal and neonatal cord gas data at delivery and APGAR scores were obtained by a retrospective chart review of 25 consecutive parturients with severe respiratory compromise who were delivered during mechanical ventilation. Linear regression was used to assess the relationship between mPaCO2 and umbilical artery and vein PCO2 and between mPaCO2 and APGAR scores at 1 and 5 min. Results: There was a positive correlation between mPaCO2 and neonatal cord venous PCO2 (P = 0.013). Foetal venous PCO2 exceeded predelivery mPaCO2 by 17.5 (7.5) mmHg. There was an inverse relationship between mPaCO2 and neonatal APGAR scores at 1 and 5 min (P = 0.006 and P = 0.007, respectively). Conclusion: Foetal cord venous PCO2 can be predicted if mPaCO2 values are known. Unlike in healthy pregnant women, there was an inverse relationship between rising mPaCO2 levels and neonatal APGAR scores in critically ill pregnant women who had several associated compounding factors.

Synthesis of Cobalt-Based Nanoparticles as Catalysts for Methanol Synthesis from CO2 Hydrogenation.

The increasing emission of carbon dioxide into the atmosphere has urged the scientific community to investigate alternatives to alleviate such emissions, being that they are the principal contributor to the greenhouse gas effect. One major alternative is carbon capture and utilization (CCU) toward the production of value-added chemicals using diverse technologies. This work aims at the study of the catalytic potential of different cobalt-derived nanoparticles for methanol synthesis from carbon dioxide hydrogenation. Thanks to its abundance and cost efficacy, cobalt can serve as an economical catalyst compared to noble metal-based catalysts. In this work, we present a systematic comparison among different cobalt and cobalt oxide nanocomposites in terms of their efficiency as catalysts for carbon dioxide hydrogenation to methanol as well as how different supports, zeolites, MnO2, and CeO2, can enhance their catalytic capacity. The oxygen vacancies in the cerium oxide act as carbon dioxide adsorption and activation sites, which facilitates a higher methanol production yield.

Liposomes, transfersomes and niosomes: production methods and their applications in the vaccinal field.

One of the most effective strategies to fight viruses and handle health diseases is vaccination. Recent studies and current applications are moving on antigen, DNA and RNA-based vaccines to overcome the limitations related to the conventional vaccination strategies, such as low safety, necessity of multiple injection, and side effects. However, due to the instability of pristine antigen, RNA and DNA molecules, the use of nanocarriers is required. Among the different nanocarriers proposed for vaccinal applications, three types of nanovesicles were selected and analysed in this review: liposomes, transfersomes and niosomes. PubMed, Scopus and Google Scholar databases were used for searching recent papers on the most frequently used conventional and innovative methods of production of these nanovesicles. Weaknesses and limitations of conventional methods (i.e., multiple post-processing, solvent residue, batch-mode processes) can be overcome using innovative methods, in particular, the ones assisted by supercritical carbon dioxide. SuperSomes process emerged as a promising production technique of solvent-free nanovesicles, since it can be easily scaled-up, works in continuous-mode, and does not require further post-processing steps to obtain the desired products. As a result of the literature analysis, supercritical carbon dioxide assisted methods attracted a lot of interest for nanovesicles production in the vaccinal field. However, despite their numerous advantages, supercritical processes require further studies for the production of liposomes, transfersomes and niosomes with the aim of reaching well-defined technologies suitable for industrial applications and mass production of vaccines.

Technical innovation, renewable energy consumption, and CO2 emissions in the USA: a cross-quantile approach.

This study investigates whether technological innovation and the consumption of renewable energy tend to reduce the emissions of CO2 in the USA by analyzing datasets from January 2010 to May 2022. The main contribution to this study is that we applied a cross-quantile approach, which possesses several strengths compared to other methods used for directional predictability. The empirical results of this research can be concluded as three points: (1) both the consumption of renewable energy and technological innovation significantly and negatively impacted the emissions of CO2 in the short run (i.e., 1 month) across high quantiles, which gradually diminished over time (i.e., 3 months, 12 months, and 24 months), implying that technological innovation and the consumption of renewable energy possess a short-lived effect on CO2 emissions, respectively; (2) this relationship remains significant for causal links spanning 1 and 3 months and 1 and 2 years when the consumption of renewable energy and technological innovation are treated as control variables respectively; (3) a recursive cross-quantilogram was constructed to support further our findings, which showed that the consumption of renewable energy and technological innovation tend to negatively impact the emissions of CO2 across all quantiles. These results imply that an increase in the consumption of renewable energy and technological innovation can curb CO2 emissions in the USA; these effects tend to be more lasting when technological innovation and the consumption of renewable energy are combined. Therefore, future policies focused on curbing the emissions of CO2 should pay attention to the combined effect, which is the promotion of technological innovation and the exploitation of renewable energy sources in the USA.

Unusually large microporous HKUST-1 via polyethylene glycol-templated synthesis: enhanced CO2 uptake with high selectivity over CH4 and N2.

Porous solids with highly microporous structures for effective carbon dioxide uptake and separation from mixed gases are highly desirable. Here we present the use of polyethylene glycol (20,000 g/mol) as a soft template for the simple and rapid synthesis of a highly microporous Cu-BTC (denoted as HKUST-1). The polyethylene glycol-templated HKUST-1 obtained at room temperature in 10 min exhibited a very high Brunauer-Emmett-Teller (BET) surface area of 1904 m2/g, pore volume of 0.87 cm3/g, and average micropore size of 0.84 nm. However, conventional HKUST-1 exhibits a BET surface area of 700-1700 m2/g confirming the advantages of using this method. X-ray powder diffraction and electron microscopy analysis confirm the formation of highly crystalline and uniform octahedral particles with sizes ranging from 100 nm to 120 µm. Adsorption isotherms recorded at temperatures between 273 and 353 K and pressures up to 40 bar revealed a more favorable adsorption capacity of HKUST-1 for CO2 vs. CH4 and N2 (708 mg (CO2)/g, 214 mg (CH4)/g and 177 mg (N2)/g at 298 K and 40 bar). The Langmuir, isotherm model, and isosteric heats of adsorption were evaluated. The CO2 interaction at PEG-templated HKUST-1 is physical, exothermic, and spontaneous with DH° = - 6.52 kJ/mol, DS° = - 13.72 J/mol, and DG° = - 2.43 kJ/mol at 298 K at 40 bar. The selectivities in equimolar mixtures were determined as 53 and 24, respectively, for CO2 over N2 and CH4. CO2 adsorption-desorption tests reveal high adsorbent reusability. The cost-effective and quickly prepared PEG-templated HKUST-1 demonstrates high efficacy as a gas adsorbent, particularly in selectively capturing CO2.

Fine-Scale Spatial Variability of Greenhouse Gas Emissions From a Subantarctic Peatland Bog.

Peatlands are recognized as crucial greenhouse gas sources and sinks and have been extensively studied. Their emissions exhibit high spatial heterogeneity when measured on site using flux chambers. However, the mechanism by which this spatial variability behaves on a very fine scale remains unclear. This study investigates the fine-scale spatial variability of greenhouse gas emissions from a subantarctic Sphagnum peatland bog. Using a recently developed skirt chamber, methane emissions and ecosystem respiration (as carbon dioxide) were measured at a submeter scale resolution, at five specific 3 × 3 m plots, which were examined across the site throughout a single campaign during the Austral summer season. The results indicated that methane fluxes were significantly less homogeneously distributed compared with ecosystem respiration. Furthermore, we established that the spatial variation scale, i.e., the minimum spatial domain over which notable changes in methane emissions and ecosystem respiration occur, was <0.56 m2. Factors such as ground height relative to the water table and vegetation coverage were analyzed. It was observed that Tetroncium magellanicum exhibited a notable correlation with higher methane fluxes, likely because of the aerenchymatous nature of this species, facilitating gas transport. This study advances understanding of gas exchange patterns in peatlands but also emphasizes the need for further efforts for characterizing spatial dynamics at a very fine scale for precise greenhouse gas budget assessment.

Fine-tuning covalent organic frameworks for structure-activity correlation via adsorption and catalytic studies.

In applications utilizing Covalent Organic Frameworks (COFs) for adsorption, the interplay between crystallinity (vis-à-vis surface area) and active sites still remains ambiguous. To address this, the present study introduces three isoreticular COFs-COP-N18 (covalent organic polymer with short-range order), COF-N18 (COF having long-range order), and COF-N27 (semicrystalline COF with pyridyl heteroatoms)-to explore this duality. Through systematic variations in structural order, pore volume, and pore-wall nitrogen content, we aim to establish a structure-activity relationship (SAR) for these COFs via adsorption and catalysis, using CO2 and I2 as probes. Our investigation highlights the positive influence of crystallinity, surface area, and pore volume in adsorption as well as catalysis. However, the presence of heteroatoms manifests complex behavior in CO2 adsorption and CO2 cycloaddition reactions with epoxides. COF-N18 and COF-N27 showed comparable CO2 uptake capacities at different temperatures (273, 293, and 313 K) and ∼1 bar pressure. Additionally, CO2 cycloaddition reactions were performed with substrates possessing different polarities (epichlorohydrin, 1,2-epoxydodecane) to elucidate the role of COF surface polarity. Further investigation into iodine adsorption was performed to understand the impact of COF structural features on the modes of adsorption and adsorption kinetics. Improvements in COF-crystallinity results in faster average iodine uptake rate at 80% (K80% = 1.79 g/h) by COF-N18. Whereas, heteroatom doping slows down iodine adsorption kinetics (0.35 g/h) by prolonging the adsorption process up to 72 h. Overall, this study advances our understanding of COFs as adsorbents and catalysts, providing key insights into their SAR while emphasizing structural fine-tuning as a key factor for impactful environmental applications.