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1.
PLoS Genet ; 18(4): e1009638, 2022 04.
Artigo em Inglês | MEDLINE | ID: mdl-35377872

RESUMO

Neurogenesis in the adult hippocampus contributes to learning and memory in the healthy brain but is dysregulated in metabolic and neurodegenerative diseases. The molecular relationships between neural stem cell activity, adult neurogenesis, and global metabolism are largely unknown. Here we applied unbiased systems genetics methods to quantify genetic covariation among adult neurogenesis and metabolic phenotypes in peripheral tissues of a genetically diverse family of rat strains, derived from a cross between the spontaneously hypertensive (SHR/OlaIpcv) strain and Brown Norway (BN-Lx/Cub). The HXB/BXH family is a very well established model to dissect genetic variants that modulate metabolic and cardiovascular diseases and we have accumulated deep phenome and transcriptome data in a FAIR-compliant resource for systematic and integrative analyses. Here we measured rates of precursor cell proliferation, survival of new neurons, and gene expression in the hippocampus of the entire HXB/BXH family, including both parents. These data were combined with published metabolic phenotypes to detect a neurometabolic quantitative trait locus (QTL) for serum glucose and neuronal survival on Chromosome 16: 62.1-66.3 Mb. We subsequently fine-mapped the key phenotype to a locus that includes the Telo2-interacting protein 2 gene (Tti2)-a chaperone that modulates the activity and stability of PIKK kinases. To verify the hypothesis that differences in neurogenesis and glucose levels are caused by a polymorphism in Tti2, we generated a targeted frameshift mutation on the SHR/OlaIpcv background. Heterozygous SHR-Tti2+/- mutants had lower rates of hippocampal neurogenesis and hallmarks of dysglycemia compared to wild-type littermates. Our findings highlight Tti2 as a causal genetic link between glucose metabolism and structural brain plasticity. In humans, more than 800 genomic variants are linked to TTI2 expression, seven of which have associations to protein and blood stem cell factor concentrations, blood pressure and frontotemporal dementia.


Assuntos
Glucose , Neurogênese , Animais , Humanos , Ratos , Glucose/genética , Glucose/metabolismo , Hipocampo/metabolismo , Neurogênese/genética , Fenótipo , Ratos Endogâmicos BN , Ratos Endogâmicos SHR
2.
Nature ; 553(7686): 106-110, 2018 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-29300013

RESUMO

Class B G-protein-coupled receptors (GPCRs), which consist of an extracellular domain (ECD) and a transmembrane domain (TMD), respond to secretin peptides to play a key part in hormonal homeostasis, and are important therapeutic targets for a variety of diseases. Previous work has suggested that peptide ligands bind to class B GPCRs according to a two-domain binding model, in which the C-terminal region of the peptide targets the ECD and the N-terminal region of the peptide binds to the TMD binding pocket. Recently, three structures of class B GPCRs in complex with peptide ligands have been solved. These structures provide essential insights into peptide ligand recognition by class B GPCRs. However, owing to resolution limitations, the specific molecular interactions for peptide binding to class B GPCRs remain ambiguous. Moreover, these previously solved structures have different ECD conformations relative to the TMD, which introduces questions regarding inter-domain conformational flexibility and the changes required for receptor activation. Here we report the 3.0 Å-resolution crystal structure of the full-length human glucagon receptor (GCGR) in complex with a glucagon analogue and partial agonist, NNC1702. This structure provides molecular details of the interactions between GCGR and the peptide ligand. It reveals a marked change in the relative orientation between the ECD and TMD of GCGR compared to the previously solved structure of the inactive GCGR-NNC0640-mAb1 complex. Notably, the stalk region and the first extracellular loop undergo major conformational changes in secondary structure during peptide binding, forming key interactions with the peptide. We further propose a dual-binding-site trigger model for GCGR activation-which requires conformational changes of the stalk, first extracellular loop and TMD-that extends our understanding of the previously established two-domain peptide-binding model of class B GPCRs.


Assuntos
Glucagon/análogos & derivados , Receptores de Glucagon/química , Receptores de Glucagon/metabolismo , Cristalografia por Raios X , Agonismo Parcial de Drogas , Humanos , Ligantes , Modelos Moleculares , Ligação Proteica , Conformação Proteica
3.
Environ Sci Technol ; 2023 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-36608262

RESUMO

The distributed consensus mechanism is the backbone of the rapidly developing blockchain network. Blockchain platforms consume vast amounts of electricity based on the current consensus mechanism of Proof-of-Work (PoW). Here, we point out a different consensus mechanism named Proof-of-Stake (PoS) that can eliminate the extensive energy consumption of the current PoW-based blockchain. We comprehensively elucidate the current and projected energy consumption and carbon footprint of the PoW- and PoS-based Bitcoin and Ethereum blockchain platforms. The model of energy consumption of PoS-based Ethereum blockchain can lead the way toward the prediction of other PoS-based blockchain technologies in the future. With the widespread adoption of blockchain technology, if the current PoW mechanism continues to be employed, the carbon footprint of Bitcoin and Ethereum will push the global temperature above 1.5 °C in this century. However, a PoS-based blockchain can reduce the carbon footprint by 99% compared to the PoW mechanism. The small amount of carbon footprint from PoS-based blockchain could make blockchain an attractive technology in a carbon-constrained future. The study sheds light on the urgency of developing the PoS mechanism to solve the current sustainability problem of blockchain.

4.
Phys Chem Chem Phys ; 25(20): 13877-13891, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37183599

RESUMO

CO2 capture by primary or secondary amines has been a topic of great research interests for a century because of its industrial importance. Interest has grown even more, because of the need to eliminate CO2 emissions that lead to global warming. Experimental evidence shows that CO2 sorption by primary or secondary amines is accompanied by co-absorption of H2O. A quantitative analysis of such CO2-H2O co-absorption behavior is important for practical process design and theoretical understanding. Even though there is almost an experimental consensus that water enhances CO2 uptake capacity, an analytical model to explain this phenomenon is not well established. Instead, some empirical models such as the Toth model are used to describe the isotherm without accounting for the presence of water. Recently, we have demonstrated that the isotherm equation of CO2 sorption into strong-base anion exchange materials with quaternary ammonium can be derived from that of strong-base aqueous alkaline solutions by correcting for the drastic change in the water activity and by including an appropriate parameterization of the water activity terms. In this paper, we generalize this model from quaternary ammonium to primary, secondary and tertiary amines either in solutions or as functional groups in polymer resins. For primary, secondary and tertiary amines, the isotherm equation can be derived by extending that of a weak-base aqueous alkaline solution such as aqueous ammonia. The model has been validated using experimental data on CO2 sorption for aqueous ammonia from the literature. This general model even includes quaternary ammonium as a special limit. Hence, this general model offers a platform that can treat the isotherms of solid amines, aqueous amines and aqueous alkaline solutions in a unified manner.

5.
Am J Physiol Cell Physiol ; 322(6): C1260-C1269, 2022 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-35442827

RESUMO

Exocrine glands in the submucosa of the proximal duodenum secrete alkaline fluid containing mucus to protect the intestinal mucosa from acidic stomach contents. These glands, known as Brunner's glands, express high glucagon-like peptide 1 receptor (GLP-1R) levels. Previous studies have suggested that activation of the GLP-1R induces expression of barrier protective genes in Brunner's glands. Still, the lack of a viable in vitro culture of Brunner's glands has hampered additional studies of the functional consequences of GLP-1R activation. In this study, we established a procedure to isolate and culture cells derived from murine Brunner's glands. The isolated glandular cells retained functional GLP-1R expression in culture, making this in vitro system suitable for the study of GLP-1R activation. We found that cells derived from the Brunner's glands of mice pretreated with semaglutide contained significantly more mucus compared with Brunner's glands from vehicle-treated mice. Our data suggest a protective intestinal response upon semaglutide treatment, but further studies are required to leverage the full potential of cultured Brunner's gland cells.


Assuntos
Glândulas Duodenais , Receptor do Peptídeo Semelhante ao Glucagon 1 , Animais , Glândulas Duodenais/química , Glândulas Duodenais/metabolismo , Técnicas de Cultura de Células , Duodeno/metabolismo , Receptor do Peptídeo Semelhante ao Glucagon 1/análise , Receptor do Peptídeo Semelhante ao Glucagon 1/genética , Receptor do Peptídeo Semelhante ao Glucagon 1/metabolismo , Mucosa Intestinal/metabolismo , Masculino , Camundongos , Muco
6.
Phys Chem Chem Phys ; 24(24): 14763-14771, 2022 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-35678464

RESUMO

Moisture-controlled sorption of CO2, the basis for moisture-swing CO2 capture from air, is a novel phenomenon observed in strong-base anion exchange materials. Prior research has shown that Langmuir isotherms provide an approximate fit to moisture-controlled CO2 sorption isotherm data. However, this fit still lacks a governing equation derived from an analytic model. In this paper, we derive an analytic form for an isotherm equation from a bottom-up approach, starting with a fundamental theory for an alkali liquid. In the range of interest relevant to CO2 capture from air, an isotherm equation for an alkali liquid reduces to a simple analytic form with a single parameter, Keq. In the limit Keq ≫ 1, a 2nd order approximation simplifies to a Langmuir isotherm that, however, deviates from experimental data. The isotherm theory for an alkali liquid has been generalized to a strong-base anion exchange material. In a strong-base anion exchange material, water concentration inside a sorbent, [H2O], is not large enough to be regarded as constant, which allows us to extend Keq to Keq(AEM)eff = Keq(AEM) × [H2O]-n according to the law of mass action. The final isotherm formula has been validated by experimental data from the literature. For a moisture-controlled CO2 sorbent, Keq(AEM)eff varies significantly with moisture content of the sorbent. Depending on moisture level, the observed Keq(AEM)eff in a specific sorbent ranges from a few times to a few thousand times the value of Keq of a 2 mol L-1 alkali liquid.

7.
Phys Chem Chem Phys ; 24(35): 21061-21077, 2022 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-36017678

RESUMO

The understanding of the sorption/desorption kinetics is essential for practical applications of moisture-controlled CO2 sorption. We introduce an analytic model of the kinetics of moisture-controlled CO2 sorption and its interpretation in two limiting cases. In one case, chemical reaction kinetics on pore surfaces dominates, in the other case, diffusive transport through the sorbent defines the kinetics. We show that reaction kinetics, which is dominant in the first case, can be expressed as a linear combination of 1st and 2nd order kinetics in agreement with the static isotherm equation derived and validated in a previous paper. The interior transport kinetics can be described by non-linear diffusion equations. By combining all carbon species into a single equation, we can eliminate - in certain limits - the source terms associated with chemical reactions. In this case, the governing equation is . For a sorbent in a form of a flat sheet or a membrane, one can maintain the same functional form of a diffusion equation by introducing a generalized effective diffusivity DM that combines contributions from both surface chemical reaction kinetics and interior diffusive transport kinetics. Experimental data of transient CO2 flux in a preconditioned commercial anion exchange membrane fit well to the 1st order model as long as very dry states are avoided, validating the theory. The observed DM for a preconditioned commercial anion exchange membrane ranges from 6.6 × 10-14 to 7.1 × 10-14 m2 s-1 at 35 °C. These small values compared to typical ionic diffusivities imply a very slow kinetics, which will be the largest issue that needs to be addressed for practical application. The collected transient CO2 flux data are used to predict the magnitude of a continuous CO2 pumping flux in an active membrane that transports CO2 against a CO2 concentration gradient. The pumped CO2 flux is supported by water flux due to a water concentration gradient.

8.
Eur J Immunol ; 50(3): 445-458, 2020 03.
Artigo em Inglês | MEDLINE | ID: mdl-31722123

RESUMO

TNF-blockade has shown clear therapeutic value in rheumatoid arthritis and other immune-mediated inflammatory diseases, however its mechanism of action is not fully elucidated. We investigated the effects of TNF-blockade on CD4+ T cell activation, maturation, and proliferation, and assessed whether TNF-inhibitors confer regulatory potential to CD4+ T cells. CyTOF and flow cytometry analysis revealed that in vitro treatment of human CD4+ T cells with the anti-TNF monoclonal antibody adalimumab promoted IL-10 expression in CD4+ T cells, whilst decreasing cellular activation. In line with this, analysis of gene expression profiling datasets of anti-TNF-treated IL-17 or IFN-γ-producing CD4+ T cells revealed changes in multiple pathways associated with cell cycle and proliferation. Kinetics experiments showed that anti-TNF treatment led to delayed, rather than impaired T-cell activation and maturation. Whilst anti-TNF-treated CD4+ T cells displayed some hyporesponsiveness upon restimulation, they did not acquire enhanced capacity to suppress T-cell responses or modulate monocyte phenotype. These cells however displayed a reduced ability to induce IL-6 and IL-8 production by synovial fibroblasts. Together, these data indicate that anti-TNF treatment delays human CD4+ T-cell activation, maturation, and proliferation, and this reduced activation state may impair their ability to activate stromal cells.


Assuntos
Adalimumab/farmacologia , Anti-Inflamatórios/farmacologia , Linfócitos T CD4-Positivos/efeitos dos fármacos , Diferenciação Celular/efeitos dos fármacos , Ativação Linfocitária/efeitos dos fármacos , Linfócitos T CD4-Positivos/imunologia , Diferenciação Celular/imunologia , Proliferação de Células/efeitos dos fármacos , Células Cultivadas , Anergia Clonal/efeitos dos fármacos , Anergia Clonal/imunologia , Humanos , Ativação Linfocitária/imunologia , Fenótipo , Fator de Necrose Tumoral alfa/antagonistas & inibidores
9.
Glob Chang Biol ; 26(6): 3336-3355, 2020 06.
Artigo em Inglês | MEDLINE | ID: mdl-32012402

RESUMO

Changes in rainfall amounts and patterns have been observed and are expected to continue in the near future with potentially significant ecological and societal consequences. Modelling vegetation responses to changes in rainfall is thus crucial to project water and carbon cycles in the future. In this study, we present the results of a new model-data intercomparison project, where we tested the ability of 10 terrestrial biosphere models to reproduce the observed sensitivity of ecosystem productivity to rainfall changes at 10 sites across the globe, in nine of which, rainfall exclusion and/or irrigation experiments had been performed. The key results are as follows: (a) Inter-model variation is generally large and model agreement varies with timescales. In severely water-limited sites, models only agree on the interannual variability of evapotranspiration and to a smaller extent on gross primary productivity. In more mesic sites, model agreement for both water and carbon fluxes is typically higher on fine (daily-monthly) timescales and reduces on longer (seasonal-annual) scales. (b) Models on average overestimate the relationship between ecosystem productivity and mean rainfall amounts across sites (in space) and have a low capacity in reproducing the temporal (interannual) sensitivity of vegetation productivity to annual rainfall at a given site, even though observation uncertainty is comparable to inter-model variability. (c) Most models reproduced the sign of the observed patterns in productivity changes in rainfall manipulation experiments but had a low capacity in reproducing the observed magnitude of productivity changes. Models better reproduced the observed productivity responses due to rainfall exclusion than addition. (d) All models attribute ecosystem productivity changes to the intensity of vegetation stress and peak leaf area, whereas the impact of the change in growing season length is negligible. The relative contribution of the peak leaf area and vegetation stress intensity was highly variable among models.


Assuntos
Ciclo do Carbono , Ecossistema , Folhas de Planta , Estações do Ano , Água
10.
Environ Sci Technol ; 54(8): 5102-5111, 2020 04 21.
Artigo em Inglês | MEDLINE | ID: mdl-32212696

RESUMO

This analysis investigates the cost of carbon capture from the US natural gas-fired electricity generating fleet comparing two technologies: postcombustion capture and direct air capture (DAC). Many of the existing natural gas combined cycle (NGCC) units are suitable for postcombustion capture. We estimated the cost of postcombustion retrofits and investigated the most important unit characteristics contributing to this cost. Units larger than 400 MW, younger than 14 years, more efficient than 45%, and with a utilization (capacity factor) higher than 0.5 were found to be the most promising for retrofit. Counterintuitively, DAC (which is usually not considered for point-source capture) may be cheaper in addressing emissions from nonretrofittable NGCC units. DAC can also address the residual emissions from retrofitted units. Moreover, the economic challenges of postcombustion capture for small natural gas-fired units with low utilization, such as gas turbines, make DAC look favorable for these units. After considering the cost of postcombustion capture for the entire natural gas-related emissions and incorporating the impact of learning-by-doing for both carbon capture technologies, our results show that DAC is the cheaper capture solution for at least 1/3 of all emissions.


Assuntos
Gás Natural , Centrais Elétricas , Dióxido de Carbono/análise , Carvão Mineral , Eletricidade
11.
Angew Chem Int Ed Engl ; 59(18): 6984-7006, 2020 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-31379037

RESUMO

The urgency to address global climate change induced by greenhouse gas emissions is increasing. In particular, the rise in atmospheric CO2 levels is generating alarm. Technologies to remove CO2 from ambient air, or "direct air capture" (DAC), have recently demonstrated that they can contribute to "negative carbon emission." Recent advances in surface chemistry and material synthesis have resulted in new generations of CO2 sorbents, which may drive the future of DAC and its large-scale deployment. This Review describes major types of sorbents designed to capture CO2 from ambient air and they are categorized by the sorption mechanism: physisorption, chemisorption, and moisture-swing sorption.

12.
Internist (Berl) ; 60(4): 339-344, 2019 04.
Artigo em Alemão | MEDLINE | ID: mdl-30506152

RESUMO

BACKGROUND: Miniaturization has not only driven microelectronics and generated new unforeseen options but has also dramatically changed sensors and analytics. DEVELOPMENTS: The Lab on a Chip (LOC) technology enables laboratory processes to run fully automated in canals in the micrometre range. The biggest challenge for LOC is to keep production costs low despite miniaturization and application-specific design. If this is achieved medical laboratory analyses can usually be carried out faster and with less hands on time. This explains why LOCs are already integrated into many laboratory instruments and why point-of-care testing (POCT) can no longer be imagined without it. New markers, such as in liquid biopsies and measurement techniques, such as Raman spectroscopy and mass spectroscopy, create further potentials that will enable faster and more specific laboratory analyses to be made using LOC technology. CONCLUSION: The LOC technology has the potential of changing the medical practice especially in cases when the central laboratory is not available or is unable to provide results fast enough.


Assuntos
Dispositivos Lab-On-A-Chip , Técnicas Analíticas Microfluídicas/instrumentação , Testes Imediatos , Telemedicina , Humanos
13.
Eur J Immunol ; 47(1): 193-205, 2017 01.
Artigo em Inglês | MEDLINE | ID: mdl-27718235

RESUMO

The cytoplasmic tail of CD45 (ct-CD45) is proteolytically cleaved and released upon activation of human phagocytes. It acts on T cells as an inhibitory, cytokine-like factor in vitro. Here, we show that ct-CD45 is abundant in human peripheral blood plasma from healthy adults compared with plasma derived from umbilical cord blood and plasma from patients with rheumatoid arthritis or systemic lupus erythematosus. Plasma depleted of ct-CD45 enhanced T-cell proliferation, while addition of exogenous ct-CD45 protein inhibited proliferation and reduced cytokine production of human T lymphocytes in response to TCR signaling. Inhibition of T-cell proliferation by ct-CD45 was overcome by costimulation via CD28. T-cell activation in the presence of ct-CD45 was associated with an upregulation of the quiescence factors Schlafen family member 12 (SLFN12) and Krueppel-like factor 2 (KLF2) as well as of the cyclin-dependent kinase (CDK) inhibitor p27kip1. In contrast, positive regulators of the cell cycle such as cyclin D2 and D3 as well as CDK2 and CDK4 were found to be downregulated in response to ct-CD45. In summary, we demonstrate that ct-CD45 is present in human plasma and sets the threshold of T-cell activation.


Assuntos
Ciclo Celular , Antígenos Comuns de Leucócito/sangue , Domínios Proteicos , Linfócitos T/imunologia , Linfócitos T/metabolismo , Adulto , Idoso , Artrite Reumatoide/genética , Artrite Reumatoide/imunologia , Artrite Reumatoide/metabolismo , Biomarcadores , Ciclo Celular/genética , Ciclo Celular/imunologia , Feminino , Perfilação da Expressão Gênica , Regulação da Expressão Gênica , Humanos , Imunomodulação , Imunofenotipagem , Antígenos Comuns de Leucócito/química , Lúpus Eritematoso Sistêmico/genética , Lúpus Eritematoso Sistêmico/imunologia , Lúpus Eritematoso Sistêmico/metabolismo , Ativação Linfocitária/imunologia , Masculino , Pessoa de Meia-Idade , Fenótipo , Subpopulações de Linfócitos T/imunologia , Subpopulações de Linfócitos T/metabolismo
14.
J Chem Phys ; 149(16): 164708, 2018 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-30384735

RESUMO

Ion hydration is a fundamental process in many natural phenomena. This paper presents a quantitative analysis, based on atomistic modeling, of the behavior of ions and the impact of hydration in a novel CO2 sorbent. We explore moisture-driven CO2 sorbents focusing on diffusion of ions and the structure of ion hydration complexes forming inside water-laden resin structures. We show that the stability of the carbonate ion is reduced as the water content of the resin is lowered. As the hydration cloud of the carbonate ion shrinks, it becomes energetically favorable to split a remaining water molecule and form a bicarbonate ion plus a hydroxide ion. These two ions bind less water than a single, doubly charged carbonate ion. As a result, under relatively dry conditions, more OH- ions are available to capture CO2 than in the presence of high humidity. Local concentrations of dissolved inorganic carbon and water determine chemical equilibria. Reaction kinetics is then driven to a large extent by diffusion rates that allow water and anions to move through the resin structure. Understanding the basic mechanics of chemical equilibria and transport may help us to rationally design next-generation efficient moisture-driven CO2 sorbents.

15.
J Autoimmun ; 79: 53-62, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28118944

RESUMO

Monocytes and macrophages are key mediators of inflammation in rheumatoid arthritis (RA). Their persistence at the inflammatory site is likely to contribute to immunopathology. We sought to characterise one mechanism by which persistence may be achieved: resistance to apoptosis and the role of mir-155 in this process. CD14+ monocytes from peripheral blood (PBM) and synovial fluid (SFM) of RA patients were found to be resistant to spontaneous apoptosis relative to PBM from healthy control (HC) individuals. RA SFM were also resistant to anti-Fas-mediated apoptosis and displayed a gene expression profile distinct from HC and RA PBM populations. Gene expression profiling analysis revealed that the differentially expressed genes in RA SFM vs. PBM were enriched for apoptosis-related genes and showed increased expression of the mir-155 precursor BIC. Following identification of potential mir-155 target transcripts by bioinformatic methods, we show increased levels of mature mir-155 expression in RA PBM and SFM vs. HC PBM and a corresponding decrease in SFM of two predicted mir-155-target mRNAs, apoptosis mediators CASP10 and APAF1. Using miR mimics, we demonstrate that mir-155 over-expression in healthy CD14+ cells conferred resistance to spontaneous apoptosis, but not Fas-induced death in these cells, and resulted in increased production of cytokines and chemokines. Collectively our data indicate that CD14+ cells from patients with RA show enhanced resistance to apoptosis, and suggest that an increase in mir-155 may partially contribute to this phenotype.


Assuntos
Apoptose/genética , Artrite Reumatoide/genética , Artrite Reumatoide/imunologia , MicroRNAs/genética , Monócitos/imunologia , Monócitos/metabolismo , Artrite Reumatoide/metabolismo , Biomarcadores , Estudos de Casos e Controles , Sobrevivência Celular/genética , Biologia Computacional/métodos , Citocinas/metabolismo , Perfilação da Expressão Gênica , Regulação da Expressão Gênica , Ontologia Genética , Humanos , Imunofenotipagem , Mediadores da Inflamação/metabolismo , Receptores de Lipopolissacarídeos/metabolismo , Fenótipo , Interferência de RNA , Receptor fas/metabolismo
16.
Environ Sci Technol ; 51(2): 1024-1034, 2017 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-27935700

RESUMO

Most carbon capture and storage (CCS) envisions capturing CO2 from flue gas. Direct air capture (DAC) of CO2 has hitherto been deemed unviable because of the higher energy associated with capture at low atmospheric concentrations. We present a Life Cycle Assessment of coal-fired electricity generation that compares monoethanolamine (MEA)-based postcombustion capture (PCC) of CO2 with distributed, humidity-swing-based direct air capture (HS-DAC). Given suitable temperature, humidity, wind, and water availability, HS-DAC can be largely passive. Comparing energy requirements of HS-DAC and MEA-PCC, we find that the parasitic load of HS-DAC is less than twice that of MEA-PCC (60-72 kJ/mol versus 33-46 kJ/mol, respectively). We also compare other environmental impacts as a function of net greenhouse gas (GHG) mitigation: To achieve the same 73% mitigation as MEA-PCC, HS-DAC would increase nine other environmental impacts by on average 38%, whereas MEA-PCC would increase them by 31%. Powering distributed HS-DAC with photovoltaics (instead of coal) while including recapture of all background GHG, reduces this increase to 18%, hypothetically enabling coal-based electricity with net-zero life-cycle GHG. We conclude that, in suitable geographies, HS-DAC can complement MEA-PCC to enable CO2 capture independent of time and location of emissions and recapture background GHG from fossil-based electricity beyond flue stack emissions.


Assuntos
Carvão Mineral , Etanolamina , Eletricidade , Umidade , Centrais Elétricas
17.
Phys Chem Chem Phys ; 19(40): 27435-27441, 2017 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-28975183

RESUMO

The hydration of ions in nanoscale hydrated clusters is ubiquitous and essential in many physical and chemical processes. Here we show that the hydrolysis reaction is strongly affected by relative humidity. The hydrolysis of CO32- with n = 1-8 water molecules is investigated using an ab initio method. For n = 1-5 water molecules, all the reactants follow a stepwise pathway to the transition state. For n = 6-8 water molecules, all the reactants undergo a direct proton transfer to the transition state with overall lower activation free energy. The activation free energy of the reaction is dramatically reduced from 10.4 to 2.4 kcal mol-1 as the number of water molecules increases from 1 to 6. Meanwhile, the degree of hydrolysis of CO32- is significantly increased compared to the bulk water solution scenario. Incomplete hydration shells facilitate the hydrolysis of CO32- with few water molecules to be not only thermodynamically favorable but also kinetically favorable. We showed that the chemical kinetics is not likely to constrain the speed of CO2 air capture driven by the humidity-swing. Instead, the pore-diffusion of ions is expected to be the time-limiting step in the humidity driven CO2 air capture. The effect of humidity on the speed of CO2 air capture was studied by conducting a CO2 absorption experiment using IER with a high ratio of CO32- to H2O molecules. Our result is able to provide valuable insights into designing efficient CO2 air-capture sorbents.

18.
Glob Chang Biol ; 22(7): 2370-9, 2016 07.
Artigo em Inglês | MEDLINE | ID: mdl-27109012

RESUMO

Whether species can respond evolutionarily to current climate change is crucial for the persistence of many species. Yet, very few studies have examined genetic responses to climate change in manipulated experiments carried out in natural field conditions. We examined the evolutionary response to climate change in a common annelid worm using a controlled replicated experiment where climatic conditions were manipulated in a natural setting. Analyzing the transcribed genome of 15 local populations, we found that about 12% of the genetic polymorphisms exhibit differences in allele frequencies associated to changes in soil temperature and soil moisture. This shows an evolutionary response to realistic climate change happening over short-time scale, and calls for incorporating evolution into models predicting future response of species to climate change. It also shows that designed climate change experiments coupled with genome sequencing offer great potential to test for the occurrence (or lack) of an evolutionary response.


Assuntos
Evolução Biológica , Mudança Climática , Invertebrados/genética , Solo , Animais , Clima , Frequência do Gene , Polimorfismo Genético , Temperatura
19.
Chemistry ; 22(51): 18326-18330, 2016 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-27762459

RESUMO

A great deal of information exists concerning the hydration of ions in bulk water. Much less noticeable, but equally ubiquitous is the hydration of ions holding on to several water molecules in nanoscopic pores or in natural air at low relative humidity. Such hydration of ions with a high ratio of ions to water molecules (up to 1:1) are essential in determining the energetics of many physical and chemical systems. Herein, we present a quantitative analysis of the energetics of ion hydration in nanopores based on molecular modeling of a series of basic salts associated with different numbers of water molecules. The results show that the degree of hydrolysis of basic salts in the presence of a few water molecules is significantly different from that in bulk water. The reduced availability of water molecules promotes the hydrolysis of divalent and trivalent basic ions (S2- , CO32- , SO32- , HPO42- , SO42- , PO43- ), which produces lower valent ions (HS- , HCO3- , HSO3- , H2 PO4- , HSO4- , HPO42- ) and OH- ions. However, reducing the availability of water inhibits the hydrolysis of monovalent basic ions (CN- , HS- ). This finding sheds some light on a vast number of chemical processes in the atmosphere and on solid porous surfaces. The discovery has wide potential applications including designing efficient absorbents for acidic gases.

20.
Angew Chem Int Ed Engl ; 55(12): 4026-9, 2016 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-26914978

RESUMO

Water confined in nanoscopic pores is essential in determining the energetics of many physical and chemical systems. Herein, we report a recently discovered unconventional, reversible chemical reaction driven by water quantities in nanopores. The reduction of the number of water molecules present in the pore space promotes the hydrolysis of CO3(2-) to HCO3(-) and OH(-). This phenomenon led to a nano-structured CO2 sorbent that binds CO2 spontaneously in ambient air when the surrounding is dry, while releasing it when exposed to moisture. The underlying mechanism is elucidated theoretically by computational modeling and verified by experiments. The free energy of CO3 (2-) hydrolysis in nanopores reduces with a decrease of water availability. This promotes the formation of OH(-), which has a high affinity to CO2 . The effect is not limited to carbonate/bicarbonate, but is extendable to a series of ions. Humidity-driven sorption opens a new approach to gas separation technology.

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