Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 3.406
Filtrar
Más filtros

Intervalo de año de publicación
1.
Immunity ; 51(3): 443-450.e4, 2019 09 17.
Artículo en Inglés | MEDLINE | ID: mdl-31422870

RESUMEN

The presence of gallstones (cholelithiasis) is a highly prevalent and severe disease and one of the leading causes of hospital admissions worldwide. Due to its substantial health impact, we investigated the biological mechanisms that lead to the formation and growth of gallstones. We show that gallstone assembly essentially requires neutrophil extracellular traps (NETs). We found consistent evidence for the presence of NETs in human and murine gallstones and describe an immune-mediated process requiring activation of the innate immune system for the formation and growth of gallstones. Targeting NET formation via inhibition of peptidyl arginine deiminase type 4 or abrogation of reactive oxygen species (ROS) production, as well as damping of neutrophils by metoprolol, effectively inhibit gallstone formation in vivo. Our results show that after the physicochemical process of crystal formation, NETs foster their assembly into larger aggregates and finally gallstones. These insights provide a feasible therapeutic concept to prevent cholelithiasis in patients at risk.


Asunto(s)
Trampas Extracelulares/inmunología , Cálculos Biliares/inmunología , Neutrófilos/inmunología , Animales , Femenino , Humanos , Inmunidad Innata/inmunología , Masculino , Ratones , Ratones Endogámicos BALB C , Ratones Endogámicos C57BL , Especies Reactivas de Oxígeno/inmunología
2.
Proc Natl Acad Sci U S A ; 121(42): e2321342121, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39374395

RESUMEN

Carbonate minerals are of particular interest in paleoenvironmental research as they are an integral part of the carbon and water cycles, both of which are relevant to habitability. Given that these cycles are less constrained on Mars than they are on Earth, the identification of carbonates has been a point of emphasis for rover missions. Here, we present carbon (δ13C) and oxygen (δ18O) isotope data from four carbonates encountered by the Curiosity rover within the Gale crater. The carbon isotope values range from 72 ± 2‰ to 110 ± 3‰ Vienna Pee Dee Belemnite while the oxygen isotope values span from 59 ± 4‰ to 91 ± 4‰ Vienna Standard Mean Ocean Water (1 SE uncertainties). Notably, these values are isotopically heavy (13C- and 18O-enriched) relative to nearly every other Martian material. The extreme isotopic difference between the carbonates and other carbon- and oxygen-rich reservoirs on Mars cannot be reconciled by standard equilibrium carbonate-CO2 fractionation, thus requiring an alternative process during or prior to carbonate formation. This paper explores two processes capable of contributing to the isotopic enrichments: 1) evaporative-driven Rayleigh distillation and 2) kinetic isotope effects related to cryogenic precipitation. In isolation, each process cannot reproduce the observed carbonate isotope values; however, a combination of these processes represents the most likely source for the extreme isotopic enrichments.

3.
Proc Natl Acad Sci U S A ; 120(15): e2213987120, 2023 04 11.
Artículo en Inglés | MEDLINE | ID: mdl-37011196

RESUMEN

The dinosaur-bird transition involved several anatomical, biomechanical, and physiological modifications of the theropod bauplan. Non-avian maniraptoran theropods, such as Troodon, are key to better understand changes in thermophysiology and reproduction occurring during this transition. Here, we applied dual clumped isotope (Δ47 and Δ48) thermometry, a technique that resolves mineralization temperature and other nonthermal information recorded in carbonates, to eggshells from Troodon, modern reptiles, and modern birds. Troodon eggshells show variable temperatures, namely 42 and 29 ± 2 °C, supporting the hypothesis of an endothermic thermophysiology with a heterothermic strategy for this extinct taxon. Dual clumped isotope data also reveal physiological differences in the reproductive systems between Troodon, reptiles, and birds. Troodon and modern reptiles mineralize their eggshells indistinguishable from dual clumped isotope equilibrium, while birds precipitate eggshells characterized by a positive disequilibrium offset in Δ48. Analyses of inorganic calcites suggest that the observed disequilibrium pattern in birds is linked to an amorphous calcium carbonate (ACC) precursor, a carbonate phase known to accelerate eggshell formation in birds. Lack of disequilibrium patterns in reptile and Troodon eggshells implies these vertebrates had not acquired the fast, ACC-based eggshell calcification process characteristic of birds. Observation that Troodon retained a slow reptile-like calcification suggests that it possessed two functional ovaries and was limited in the number of eggs it could produce; thus its large clutches would have been laid by several females. Dual clumped isotope analysis of eggshells of extinct vertebrates sheds light on physiological information otherwise inaccessible in the fossil record.


Asunto(s)
Cáscara de Huevo , Reptiles , Animales , Femenino , Carbonato de Calcio , Isótopos
4.
Proc Natl Acad Sci U S A ; 120(45): e2306627120, 2023 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-37917794

RESUMEN

The elemental composition of coral skeletons provides important information for palaeoceanographic reconstructions and coral biomineralization. Partition of anions and their stable isotopes in coral skeleton enables the reconstruction of past seawater carbonate chemistry, paleo-CO2, and past climates. Here, we investigated the partition of B, S, As, Br, I, and Mo into the skeletons of two corals, Acropora cervicornis and Pocillopora damicornis, as a function of calcium and carbonate concentrations.* Anion-to-calcium ratio in the corals (An/CaCoral) were correlated with the equivalent ratios in the culturing seawater (An/CO32-SW). Negative intercepts of these relationships suggest a higher CO32- concentration in the coral extracellular calcifying fluid (ECF) relative to seawater, from which the skeleton precipitates. The enrichment factor of CO32- at the ECF was 2.5 for A. cervicornis and 1.9 for P. damicornis, consistent with their relative calcification rates. The CO32-ECF concentrations thus calculated are similar to those proposed by previous studies based on B/Ca coupled with δ11B, as well as by direct measurements using microsensors and fluorescent dyes. Rayleigh fractionation modeling demonstrates a uniform Ca utilization at various CaSW concentrations, providing further evidence that coral calcification occurs directly from a semiclosed seawater reservoir as reported previously. The partition coefficients reported in this study for B, S, As, Br, I, and Mo open up wide possibilities for past ocean chemistry reconstructions based on Br having long residence time (~160 Ma) in the ocean. Other elements like S, Mo, B, as well as pCO2 may also be calculated based on these elements in fossil coral.


Asunto(s)
Antozoos , Calcinosis , Animales , Antozoos/metabolismo , Calcio/metabolismo , Biomineralización , Carbonato de Calcio/química , Concentración de Iones de Hidrógeno , Carbonatos/química , Agua de Mar/química , Calcificación Fisiológica , Arrecifes de Coral
5.
Proc Natl Acad Sci U S A ; 119(45): e2212616119, 2022 Nov 08.
Artículo en Inglés | MEDLINE | ID: mdl-36322756

RESUMEN

Some mollusc shells are formed from an amorphous calcium carbonate (ACC) compound, which further transforms into a crystalline material. The transformation mechanism is not fully understood but is however crucial to develop bioinspired synthetic biomineralization strategies or accurate marine biomineral proxies for geoscience. The difficulty arises from the simultaneous presence of crystalline and amorphous compounds in the shell, which complicates the selective experimental characterization of the amorphous fraction. Here, we use nanobeam X-ray total scattering together with an approach to separate crystalline and amorphous scattering contributions to obtain the spatially resolved atomic pair distribution function (PDF). We resolve three distinct amorphous calcium carbonate compounds, present in the shell of Pinctada margaritifera and attributed to: interprismatic periostracum, young mineralizing units, and mature mineralizing units. From this, we extract accurate bond parameters by reverse Monte Carlo (RMC) modeling of the PDF. This shows that the three amorphous compounds differ mostly in their Ca-O nearest-neighbor atom pair distance. Further characterization with conventional spectroscopic techniques unveils the presence of Mg in the shell and shows Mg-calcite in the final, crystallized shell. In line with recent literature, we propose that the amorphous-to-crystal transition is mediated by the presence of Mg. The transition occurs through the decomposition of the initial Mg-rich precursor into a second Mg-poor ACC compound before forming a crystal.


Asunto(s)
Pinctada , Animales , Carbonato de Calcio/química , Moluscos , Rayos X
6.
Proc Natl Acad Sci U S A ; 119(41): e2208750119, 2022 Oct 11.
Artículo en Inglés | MEDLINE | ID: mdl-36191218

RESUMEN

A basic requirement for solid oxide fuel cells (SOFCs) is the sintering of electrolyte into a dense impermeable membrane to prevent the mixing of fuel and oxygen for a sufficiently high open-circuit voltage (OCV). However, herein, we demonstrate a different type of fuel cell, a carbonate-superstructured solid fuel cell (CSSFC), in which in situ generation of superstructured carbonate in the porous samarium-doped ceria layer creates a unique electrolyte with ultrahigh ionic conductivity of 0.17 S⋅cm-1 at 550 °C. The CSSFC achieves unprecedented high OCVs (1.051 V at 500 °C and 1.041 V at 550 °C) with methane fuel. Furthermore, the CSSFC exhibits a high peak power density of 215 mW⋅cm-2 with dry methane fuel at 550 °C, which is higher than all reported values of electrolyte-supported SOFCs. This provides a different approach for the development of efficient solid fuel cells.

7.
J Struct Biol ; 216(3): 108106, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38871094

RESUMEN

Osteosarcoma (OS) is the most common malignant primary bone tumor in humans and occurs in various subtypes. Tumor formation happens through malignant osteoblasts producing immature bone. In the present paper we studied two different subtypes of osteosarcoma, from one individual with conventional OS with massive sclerosis and one individual with parosteal OS, based on a multimodal approach including small angle x-ray scattering (SAXS), wide angle x-ray diffraction (WAXS), backscattered electron imaging (BEI) and Raman spectroscopy. It was found that both tumors showed reduced mineral particle sizes and degree of orientation of the collagen-mineral composite in the affected areas, alongside with a decreased crystallinity. Distinct differences between the tumor material from the two individuals were found in the degree of mineralization. Further differences were observed in the carbonate to phosphate ratio, which is related to the degree of carbonate substitution in bone mineral and indicative of the turnover rate. The contraction of the c-axis of the bone mineral crystals proved to be a further, very sensitive parameter, potentially indicative of malignancy.


Asunto(s)
Osteosarcoma , Dispersión del Ángulo Pequeño , Espectrometría Raman , Difracción de Rayos X , Humanos , Osteosarcoma/patología , Osteosarcoma/metabolismo , Difracción de Rayos X/métodos , Espectrometría Raman/métodos , Neoplasias Óseas/patología , Esclerosis/patología , Huesos/patología , Masculino , Femenino
8.
J Comput Chem ; 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39286905

RESUMEN

An impact of an electronic structure or force field method, gas-phase thermodynamic correction, and continuum solvation model on organic carbonate clusters (S)n conformational and binding energies is explored. None of the tested force field (GFN-FF, GAFF, MMFF94) and standard semiempirical methods (PM3, AM1, RM1, PM6, PM6-D3, PM6-D3H4, PM7) can reproduce reference RI-SCS-MP2 conformational energies. Tight-binding GFNn-xTB methods provide more realistic conformational energies which are accurate enough to discard the least stable conformers. The effect of thermodynamic correction is moderate and can be ignored if the gas phase conformational stability ranking is a goal. The influence of continuum solvation is stronger, especially if reinforced with the Gibbs free energy thermodynamic correction, and results in the reduced spread of conformational energies. The cluster formation binding energies strongly depend on a particular approach to vibrational thermochemistry with the difference between traditional harmonic and modified scaled rigid - harmonic oscillator approximations reaching 10 kcal mol-1.

9.
Small ; : e2403661, 2024 Jul 12.
Artículo en Inglés | MEDLINE | ID: mdl-38994824

RESUMEN

Efficient conversion of biomass wastes into valuable chemicals has been regarded as a sustainable approach for green and circular economy. Herein, a highly efficient catalytic conversion of glycerol (Gly) into glycerol carbonate (GlyC) by carbonylation with the commercially available urea is presented using low-cost transition metal single atoms supported on zinc oxide quantum dots (M1-ZnO QDs) as a catalyst without using any solvent. A facile one-step wet chemical synthesis allows various types of metal single atoms to simultaneously dope and introduce Lewis-acid defects in the ZnO QD structure. It is found that doping with a trace amount of isolated metal atoms greatly boosts the catalytic activity with Gly conversion of 90.7%, GlyC selectivity of 100.0%, and GlyC yield of 90.6%. Congruential results from both Density Functional Theory (DFT) and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) studies reveal that the superior catalytic performance can be attributed to the enriched Lewis acid sites that endow optimal adsorption, formation of the intermediate for coupling between urea and Gly, and desorption of GlyC. Moreover, the tiny size of ZnO QDs efficiently promotes the accessibility of these active sites to the reactants.

10.
Small ; : e2404260, 2024 Aug 06.
Artículo en Inglés | MEDLINE | ID: mdl-39105466

RESUMEN

While the formation of an inorganic-rich solid electrolyte interphase (SEI) plays a crucial role, the persistent challenge lies in the formation of an organic-rich SEI due to the high solvent ratio in low-concentration electrolytes (LCEs), which hinders the achievement of high-performance lithium metal batteries. Herein, by incorporating di-fluoroethylene carbonate (DFEC) as a non-solvating cosolvent, a solvation structure dominated by anions is introduced in the innovative LCE, leading to the creation of a durable and stable inorganic-rich SEI. Leveraging this electrolyte design, the Li||NCM83 cell demonstrates exceptional cycling stability, maintaining 82.85% of its capacity over 500 cycles at 1 C. Additionally, Li||NCM83 cell with a low N/P ratio (≈2.57) and reduced electrolyte volume (30 µL) retain 87.58% of its capacity after 150 cycles at 0.5 C. Direct molecular information is utilized to reveal a strong correlation between solvation structures and reduction sequences, proving the anion-dominate solvation structure can impedes the preferential reduction of solvents and constructs an inorganic-rich SEI. These findings shed light on the pivotal role of solvation structures in dictating SEI composition and battery performance, offering valuable insights for the design of advanced electrolytes for next-generation lithium metal batteries.

11.
Small ; : e2402690, 2024 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-39165055

RESUMEN

Nucleation and growth of calcium carbonate on surfaces is of broad importance in nature and technology, being essential to the calcification of organisms, while negatively impacting energy conversion through crystallization fouling, also called scale formation. Previous work studied how confinements, surface energies, and functionalizations affect nucleation and polymorph formation, with surface-water interactions and ion mobility playing important roles. However, the influence of surface nanostructures with nanocurvature-through pit and bump morphologies-on scale formation is unknown, limiting the development of scalephobic surfaces. Here, it is shown that nanoengineered surfaces enhance the nucleation rate by orders of magnitude, despite expected inhibition through effects like induced lattice strain through surface nanocurvature. Interfacial and holographic microscopy is used to quantify crystallite growth and find that nanoengineered interfaces experience slower individual growth rates while collectively the surface has 18% more deposited mass. Reconstructions through nanoscale cross-section imaging of surfaces coupled with classical nucleation theory-utilizing local nanocurvature effects-show the collective enhancement of nano-pits.

12.
Small ; : e2405568, 2024 Sep 23.
Artículo en Inglés | MEDLINE | ID: mdl-39308439

RESUMEN

Rechargeable magnesium batteries (RMBs) face with the challenge of interphase passivation between electrolytes and Mg anodes. Compared with ether electrolytes, carbonate solvents possess the superior electrochemical stability at cathode side, but their incompatibility with Mg metal, high viscosity, and desolvation energy barrier restrict their practical utilization in RMBs. Herein, the "unwanted-impurity" water with high concentration is revisited and employed as multifunctional additive in carbonate electrolyte to improve the reversibility of RMBs. Water additive enables the localized deep eutectic effect, reduces the viscosity of carbonate electrolyte, and improves the Mg ion conductivity. The water molecules also participate the solvation sheath of Mg ions, resulting in the reduction of Mg deposition overpotential and inhibition of parasitic reaction. Furthermore, the co-intercalated water molecules in V2O5 cathode layers enable the stabilization of intercalation structure and supply of additional magnesiophilic sites. Cooperated with the binder-decorated Mg powder anode, the propylene carbonate electrolyte with water additive endows Mg||Mg symmetric cells and Mg||V2O5 full cells with satisfactory cycling performance and high-voltage stability. This work revisits the impact of impurity water and provides a practical strategy for the utilization of conventional low-cost carbonate electrolyte family, broadening the design and formulation of electrolytes for chlorine-free and high-voltage RMBs.

13.
Small ; 20(24): e2311891, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38178190

RESUMEN

The active lithium loss of lithium-ion batteries can be well addressed by adding a cathode lithium compensation agent. Due to the poor conductivity and electrochemical activity, lithium carbonate (Li2CO3) is not considered as a candidate. Herein, an effective cathode lithium compensation agent, the recrystallized Li2CO3 combined with large specific surface area disordered porous carbon (R-LCO@SPC) is prepared. The screened SPC makes it easier for nano-sized Li2CO3 to adsorb and decompose on carbon substrate, meantime, exposing plenty of catalytic active sites of C═O, which can significantly improve the electrochemical activity and conductivity of Li2CO3, thus greatly reducing the decomposition potential of Li2CO3 (4.0 V) and releasing high irreversible capacity (580 mAh g-1) compared to the unmodified Li2CO3 (nearly no capacity above 4.6 V). Meantime, the Li2CO3 can disappear completely without any by-product after the initial cycle accompanied by partially dissolved in electrolyte, optimizing the composition of SEI. The resultant lithium compensation agent applied to LMFP//graphite full cell exhibits a 19.1% increase in energy density, enhancing the rate and cycling performance, demonstrating great practical applications potential in high energy density lithium-ion batteries.

14.
Small ; : e2404865, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38984733

RESUMEN

Aqueous zinc metal batteries are regarded as a promising energy storage solution for a green and sustainable society in the future. However, the practical application of metallic zinc anode is plagued by the thermodynamic instability issue of water molecules in conventional electrolytes, which leads to severe dendrite growth and side reactions. In this work, an ultra-thin and high areal capacity metallic zinc anode is achieved by utilizing crystalline water with a stable stoichiometric ratio. Unlike conventional electrolytes, the designed electrolyte can effectively suppress the reactivity of water molecules and diminish the detrimental corrosion on the metallic zinc anode, while preserving the inherent advantages of water molecules, including great kinetic performance in electrolytes and H+ capacity contribution in cathodes. Based on the comprehensive performance of the designed electrolyte, the 10 µm Zn||10 µm Zn symmetric cell stably ran for 1000 h at the current density of 1 mA cm-2, and the areal capacity of 1 mAh cm-2, whose depth-of-discharge is over 17.1%. The electrochemical performance of the 10 µm Zn||9.3 mg cm-2 polyaniline (PANI) full-cell demonstrates the feasibility of the designed electrolyte. This work provides a crucial understanding of balancing activity of water molecules in aqueous zinc metal batteries.

15.
Small ; 20(42): e2402213, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38881352

RESUMEN

The intrinsic reactivity of lithium (Li) toward ambient air, combined with insufficient cycling stability in conventional electrolytes, hinders the practical adoption of Li metal anodes in rechargeable batteries. Here, a bilayer interphase for Li metal is introduced to address both its susceptibility to corrosion in ambient air and its deterioration during cycling in carbonate electrolytes. Initially, the Li metal anode is coated with a conformal bottom layer of polysiloxane bearing methacrylate, followed by further grafting with poly(vinyl ethylene carbonate) (PVEC) to enhance anti-corrosion capability and electrochemical stability. In contrast to single-layer applications of polysiloxane or PVEC, the bilayer design offers a highly uniform coating that effectively resists humid air and prevents dendritic Li growth. Consequently, it demonstrates stable plating/stripping behavior with only a marginal increase in overpotential over 200 cycles in carbonate electrolytes, even after exposure to ambient air with 46% relative humidity. The design concept paves the way for scalable production of high-voltage, long-cycling Li metal batteries.

16.
Small ; 20(14): e2308678, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-37990362

RESUMEN

Lithium (Li) metal is regarded as a potential candidate for the next generation of lithium secondary batteries, but it has poor cycling stability with the broadly used carbonate-based electrolytes due to the uncontrollable dendritic growth and low Coulombic efficiency (CE). LiNO3 is an effective additive and its limited solubility (<800 ppm) in carbonate-based electrolytes is still a challenge, as reported. Herein, using BF3 (Lewis acid) is proposed to enhance the solubility of LiNO3 in carbonate-based electrolytes. The dissolved NO3 - can be involved in the first solvation shell of Li+, reducing the coordination number of PF6 - and EC (ethylene carbonate). In addition, the NO3 - is proved to be preferentially reduced on Li metal by differential electrochemical mass spectrometry so that the decomposition of PF6 - and EC is suppressed. Therefore, a SEI layer containing Li3N can be obtained, which exhibits high lithium-ion conductivity, achieving even and dense Li deposits. Consequently, the CE of Li||Cu cell with BF3/LiNO3 can be increased to 98.07%. Moreover, the capacity retention of Li||LiFePO4 with a low N/P ratio (3:1) is as high as 90% after 300 cycles (≈1500 h). This work paved a new way for incorporating LiNO3 into carbonate-based electrolytes and high-performance lithium metal batteries.

17.
Small ; 20(35): e2401559, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38659393

RESUMEN

A facile gaseous CO2 mediated solid-to-solid transformation principle is adopted to insert additional CO3 2- anions into the thin single-crystal nanosheets of Bi2O2CO3, which is built of periodic arrays of intrinsic CO3 2- anions and (Bi2O2)2+ layers. The additional CO3 2- anions create abundant defects. The Bi2O2CO3 nanosheets with rich interlayer CO3 2- exhibit superior electronic properties and charge transfer kinetics than the pristine single-crystal 2D Bi2O2CO3 and display enhanced catalytic activity in photocatalytic CO2 reduction reaction and the photocatalytic oxidative degradation of organic pollutants. This work thus illustrates interlayer engineering as a flexible means to build layered 2D materials with excellent properties.

18.
Chembiochem ; 25(5): e202300828, 2024 03 01.
Artículo en Inglés | MEDLINE | ID: mdl-38236789

RESUMEN

An efficient and easy-to-use approach is presented for obtaining biocompatible polysaccharide-based nanoparticles (NP) that can act as tumor-specific drug delivery agents. Two antibodies are directly immobilized onto reactive xylan phenyl carbonate (XPC) NP; namely Cetuximab (CTX) that binds to human epidermal growth factor receptor (EGFR) and Atezolizumab (ATZ) that binds to programmed death-ligand 1 (PD-L1). High coupling efficiency (up to 100 %) are achieved without any pre-activation and no aggregation occurs during antibody immobilization. By quartz crystal microbalance experiments with dissipation monitoring (QCM-D), flow cytometry assays, and confocal laser scanning microscopy imaging it is demonstrated that the functionalized XPC-NP specifically bind to cells carrying the corresponding antigens. Moreover, the NP retain the antibody specific bioactivities (growth inhibition for CTX and induction of T-cell cytotoxicity for ATZ).


Asunto(s)
Polisacáridos , Xilanos , Humanos , Especificidad de Anticuerpos , Bioensayo , Carbonatos , Cetuximab/farmacología
19.
Appl Environ Microbiol ; 90(6): e0009324, 2024 06 18.
Artículo en Inglés | MEDLINE | ID: mdl-38819147

RESUMEN

The oxygenation of Earth's atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earth's atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earth's atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earth's surface chemistry through time.


Asunto(s)
Atmósfera , Isótopos de Carbono , Planeta Tierra , Atmósfera/química , Isótopos de Carbono/análisis , Isótopos de Carbono/metabolismo , Oxígeno/metabolismo , Metano/metabolismo , Bacterias/metabolismo , Bacterias/genética , Bacterias/clasificación , Cianobacterias/metabolismo , Cianobacterias/genética
20.
Microb Pathog ; 196: 106926, 2024 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-39270755

RESUMEN

Candida albicans (C. albicans) biofilm infections are quite difficult to manage due to their resistance against conventional antifungal drugs. To address this issue, there is a desperate need for new therapeutic drugs. In the present study, a green and efficient protocol has been developed for the synthesis of 2-amino-4H-pyran-3-carbonitrile scaffolds 4a-i, 6a-j, and 8a-g by Knoevenagel-Michael-cyclocondensation reaction between aldehydes, malononitrile, and diverse enolizable C-H activated acidic compounds using guanidinium carbonate as a catalyst either under grinding conditions or by stirring at room temperature. This protocol is operationally simple, rapid, inexpensive, has easy workup and column-free purification. A further investigation of the synthesized compounds was conducted to examine their antifungal potential and their ability to inhibit the growth and development of biofilm-forming yeasts like fungus C. albicans. According to our findings, 4b, 4d, 4e, 6e, 6f, 6g, 6i, 8c, 8d, and 8g were found to be active and potential inhibitors for biofilm infection causing C. albicans. The inhibition of biofilm by active compounds were observed using field emission scanning electron microscopy (FESEM). Biofilm inhibiting compounds were also tested for in vitro toxicity by using 3T3-L1 cell line, and 4b, 6e, 6f, 6g, 6i, 8c, and 8d were found to be biocompatible. Furthermore, the in silico ADME descriptors revealed drug-like properties with no violation of Lipinski's rule of five. Hence, the result suggested that synthesized derivatives could serve as a useful aid in the development of novel antifungal compounds for the treatment of fungal infections and virulence in C. albicans.


Asunto(s)
Antifúngicos , Biopelículas , Candida albicans , Pruebas de Sensibilidad Microbiana , Candida albicans/efectos de los fármacos , Biopelículas/efectos de los fármacos , Antifúngicos/farmacología , Antifúngicos/síntesis química , Animales , Ratones , Piranos/farmacología , Piranos/síntesis química , Piranos/química , Nitrilos/farmacología , Nitrilos/síntesis química , Tecnología Química Verde , Supervivencia Celular/efectos de los fármacos
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA