Fluorescent responsive chlorophyllide-hydrogel for carbon dioxide detection

The reactions between cis-Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2) (1) or cis-Fe(PP3)H2 (PP3 = P(CH2CH2PMe2)3) (2) and carbon dioxide (CO2), carbon disulfide (CS2), and carbonyl sulfide (COS) are investigated. At 300 K, additions of CO2 (1 atm), CS2 (2 equiv), and COS (1 atm) to 1 result in the formation of a stable transformato hydride, trans-Fe(dmpe)2(OCHO)H (3a), a trans-dithioformato hydride, trans-Fe(dmpe)2(SCHS)H (4a), and a trans-thioformato hydride, trans-Fe(dmpe)2(SCHO)H (5a), respectively. When CS2 and COS are added to cis-Fe(dmpe)2H2 at 195 K, a cis-dithioformato hydride, 4b, and a cis-thioformato hydride, 5b, respectively, are observed as the initially formed products, but there is no evidence of the corresponding cis-formato hydride upon addition of CO2 to cis-Fe(dmpe)2H2. Additions of excess CO2, CS2, and COS to 1 at lower temperatures (195-240 K) result in the formation of a trans-bis(formate), trans-Fe(dmpe)2(OCHO)2 (3b), a trans-bis(dithioformate), trans-Fe(dmpe)2(SCHS)2 (4c), and a cis-bis(thioformate), cis-Fe(dmpe)2(SCHO)2 (5c), respectively. trans-Fe(dmpe)2(SCHO)2 (5d) is prepared by the addition of excess COS at 300 K. Additions of CO2 (1 atm), CS2 (0.75 equiv), and COS (1 atm) to 2 at 300 K result in the formation of a thermally stable, geometrically constrained cis-formato hydride, cis-Fe(PP3)(OCHO)H (6a), a cis-dithioformato hydride, cis-Fe(PP3)(SCHS)H (7a), and a cis-thioformato hydride, cis-Fe(PP3)(SCHO)H (8a), respectively. Additions of excess CO2 and COS to 2 yield a cis-bis(formate), cis-Fe(PP3)(OCHO)2 (6b), and a thermally stable cis-bis(thioformate), cis-Fe(PP3)(SCHO)2 (8b), respectively. All complexes are characterized by multinuclear NMR spectroscopy, with IR spectroscopy and elemental analyses confirming structures of thermally stable complexes where possible. Complexes 3b and 5a are also characterized by X-ray crystallography.

Boosting CO2 Conversion with Terminal Alkynes by Molecular Architecture of Graphene Oxide-Supported Ag Nanoparticles

N-carboxymethanofuran (carbamate) formation from unprotonated methanofuran (MFR) and CO2 is the first reaction in the reduction of CO2 to methane in methanogenic archaea. The reaction proceeds spontaneously. We address here the question whether the rate of spontaneous carbamate formation is high enough to account for the observed rate of methanogenesis from CO2. The rates of carbamate formation (v1) and cleavage (v2) were determined under equilibrium conditions via 2D proton exchange NMR spectroscopy (EXSY). At pH 7.0 and 300 K the second order rate constant k1* of carbamate formation from 'MFR'(MFR + MFRH+) and 'CO2' (CO2 + H2CO3 + HCO3-+ CO32-) was found to be 7 M-1.s-1 (v1 = k1* ['MFR'] ['CO2']) while the pseudo first order rate constant k2* of carbamate cleavage was 12 s-1 (v2 = k2* [carbamate]). The equilibrium constant K* = k1*/k2* = [carbamate]/['MFR']['CO2'] was 0.6 M-1 at pH 7.0 corresponding to a free energy change DeltaG degrees ' of + 1.3 kJ.mol-1. The pH and temperature dependence of k1*, of k2* and of K* were determined. From the second order rate constant k1* it was calculated that under physiological conditions the rate of spontaneous carbamate formation is of the same order as the maximal rate of methane formation and as the rate of spontaneous CO2 formation from HCO3- in methanogenic archaea, the latter being important as CO2 is mainly present as HCO3- which has to be converted to CO2 before it can react with MFR. An enzyme catalyzed carbamate formation thus appears not to be required for methanogenesis from CO2. Consistent with this conclusion is our finding that the rate of carbamate formation was not enhanced by cell extracts of Methanosarcina barkeri and Methanobacterium thermoautotrophicum or by purified formylmethanofuran dehydrogenase which catalyzes the reduction of N-carboxymethanofuran to N-formylmethanofuran. From the concentrations of 'CO2' and of 'MFR' determined by 1D-NMR spectroscopy and the pKa of H2CO3 and of MFRH+ the concentrations of CO2 and of MFR were obtained, allowing to calculate k1 (v1 = k1 [MFR] [CO2]). The second order rate constant k1 was found to be approximately 1000 M-1 x s-1 at 300 K and pH values between 7.0 and 8. 0 which is in the order of k1 values determined for other carbamate forming reactions by stopped flow.

Biogas is mainly consisted of methane and carbon dioxide in the presence of other contaminants. The biogas purification by adsorption using metal-organic frameworks is getting attention due to the low-cost operation and high-efficiency process. Co-gallate was predicted to give a promising performance in CO2 and CH4 adsorption. However, the behaviours of CO2 and CH4 adsorption on Co-gallate are not well-explained. Therefore, this work is to synthesize Co-gallate and its performance was discussed in terms of adsorbed amount of CO2 and CH4. The experimental CO2 and CH4 pure adsorption isotherms were then fitted with equilibrium isotherm and kinetic models to describe the adsorption behaviours. Co-gallate offered a greater CO2 adsorption capacity than CH4 due to a stronger adsorbent-adsorbate interaction. The experimental pure adsorption isotherms were best fitted with Toth model compared to Langmuir, Freundlich and Sips models according to the values. Toth model described the CO2 adsorption was multilayer and heterogeneous. Thermodynamic property suggested the CO2 and CH4 adsorption were classified as exothermic process and physisorption. For kinetic models, pseudo-first order model brought the highest goodness-of-fit in terms of rate of adsorption compared to pseudo-second order and Elovich models. Pseudo-first order model reflects the adsorption rate is proportional to the number of vacant sites. It confirmed CO2 adsorption was more favourable than CH4, at lower temperature condition. In this work, the equilibrium isotherm and kinetic models were employed to select the best-fitted model in explaining the adsorption behaviours. Therefore, these behaviours of CO2 and CH4 adsorption on Co-gallate are useful in designing the future practical operation of CO2/CH4 gas adsorption.

Capnography: Clinical Aspects.

An Integration Strategy to Develop Dual-State Luminophores with Tunable Spectra, Large Stokes Shift, and Activatable Fluorescence for High-Contrast Imaging

The unusual uptake behavior and preferential adsorption of CO(2) over N(2) are investigated in a flexible metal-organic framework system, Zn(2)(bdc)(2)(bpee), where bpdc = 4,4'-biphenyl dicarboxylate and bpee = 1,2-bis(4-pyridyl)ethylene, using Raman and IR spectroscopy. The results indicate that the interaction of CO(2) with the framework induces a twisting of one of its ligands, which is possible because of the type of connectivity of the carboxylate end group of the ligand to the metal center and the specific interaction of CO(2) with the framework. The flexibility of the bpee pillars allows the structure to respond to the twisting, fostering the adsorption of more CO(2). DFT calculations support the qualitative picture derived from the experimental analysis. The adsorption sites at higher loading have been identified using a modified van der Waals-Density Functional Theory method, showing that the more energetically favorable positions for the CO(2) molecules are closer to the C═C bond of the bpee and the C-C bond of the bpdc ligands instead of the benzene and pyridine rings of these ligands. These findings are consistent with changes observed using Raman spectroscopy, which is useful for detecting both specific guest-host interactions and structural changes in the framework.

Nitrogen–Carbon Bond Formation from N₂ and CO₂ Promoted by a Hafnocene Dinitrogen Complex Yields a Substituted Hydrazine

Industrialization over the past two centuries has resulted in a continuous rise in global CO2 emissions. These emissions are changing ecosystems and livelihoods. Therefore, methods are needed to capture these emissions from point sources and possibly from our atmosphere. Though the amount of CO2 is rising, it is challenging to capture directly from air because its concentration in air is extremely low, 0.04%. In this study, amines installed inside metal-organic frameworks (MOFs) are investigated for the adsorption of CO2, including at low concentrations. The amines used are polyamidoamine dendrimers that contain many primary amines. Chemically reversible adsorption of CO2 via carbamate formation was observed, as was enhanced uptake of carbon dioxide, likely via dendrimer-amide-based physisorption. Limiting factors in this initial study are comparatively low dendrimer loadings and slow kinetics for carbon dioxide uptake and release, even at 80 °C.

The detailed information on the surface structure and binding sites of oxide nanomaterials is crucial to understand the adsorption and catalytic processes and thus the key to develop better materials for related applications. However, experimental methods to reveal this information remain scarce. Here we show that 17O solid-state nuclear magnetic resonance (NMR) spectroscopy can be used to identify specific surface sites active for CO2 adsorption on MgO nanosheets. Two 3-coordinated bare surface oxygen sites, resonating at 39 and 42 ppm, are observed, but only the latter is involved in CO2 adsorption. Double resonance NMR and density functional theory (DFT) calculations results prove that the difference between the two species is the close proximity to H, and CO2 does not bind to the oxygen ions with a shorter O···H distance of approx. 3.0 Å. Extensions of this approach to explore adsorption processes on other oxide materials can be readily envisaged.

The interaction between amines and CO2 offers a possible route for the catalytic activation of CO2. In situ infrared spectroscopy was used to study the interaction of CO2 with amine-grafted SBA-15. We employed three different types of amine-grafted SBA-15 surfaces to quantify the effect distinct tethered amine moieties have on the chemistry of CO2 interacting with amine-grafted SBA-15. When the SBA-15 surface has a low density of amines and is “capped” to mitigate against interactions with surface-bound moieties, no new chemical species are observed on exposure to carbon dioxide. An ionic carbamate and a surface-bound carbamate are observed on the other SBA-15 surfaces on exposure to CO2. The formation of carbamates decreases the bond order of the carbon oxygen bond of the carbon dioxide molecule. The role of the different amine moieties and the surface silanol groups in the formation of the carbamates is discussed. Our results suggest that controlling the local environment around surface-grafted amines, which could be achieved by the use of suitably engineered surface environments, could facilitate the adsorption and activation of CO2.

Excimer Formation of Perylene Bisimide Dyes within Stacking-Restrained Folda-Dimers: Insight into Anomalous Temperature Responsive Dual Fluorescence

Effect of pressure on the short-range structure and speciation of carbon in alkali silicate and aluminosilicate glasses and melts at high pressure up to 8 GPa: 13C, 27Al, 17O and 29Si solid-state NMR study

Limits to Paris compatibility of CO2 capture and utilization

In aqueous solution, 2-methylpiperine (2-MP) has been proposed as a phase-separating amine for carbon-capture applications, whose carbamate is considered to be unstable due to steric hindrance. This paper demonstrates, for the first time, that the carbamate can be synthesized as the salt of the 2-methylpiperidinium cation (2-MPH+) and the 2-methylpiperidine- N-carboxylate anion (2-MPCOO-) by adding carbon dioxide gas to anhydrous liquid 2-MP at CO2/amine ratios α > 0.32 to yield well-defined prismatic crystals. Raman spectra have been measured for anhydrous liquid 2-MP and aqueous solutions of 2-MP and 2-MPH+Cl- at 298 K. The spectra of anhydrous liquid 2-MP, containing dissolved CO2 at lower CO2/amine ratios,. clearly showed the presence of 2-MPH+ and several unidentified bands that were attributed to the carbamate, 2-MPCOO-. Quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory yielded simulated Raman spectra consistent with the experimental spectra. The spectra show the methyl group of both liquid and aqueous 2-MP and that of aqueous 2-MPH+Cl- to be in the equatorial position. The crystal structure shows the same conformations in the solid state and confirms that Raman spectroscopy can be used to determine the conformation of 2-MP species in the liquid state and aqueous solutions.