Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 19.148
Filtrar
1.
Artif Cells Nanomed Biotechnol ; 52(1): 291-299, 2024 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-38733371

RESUMEN

Haemorrhagic shock is a leading cause of death worldwide. Blood transfusions can be used to treat patients suffering severe blood loss but donated red blood cells (RBCs) have several limitations that limit their availability and use. To solve the problems associated with donated RBCs, several acellular haemoglobin-based oxygen carriers (HBOCs) have been developed to restore the most important function of blood: oxygen transport. One promising HBOC is the naturally extracellular haemoglobin (i.e. erythrocruorin) of Lumbricus terrestris (LtEc). The goal of this study was to maximise the portability of LtEc by lyophilising it and then testing its stability at elevated temperatures. To prevent oxidation, several cryoprotectants were screened to determine the optimum formulation for lyophilisation that could minimise oxidation of the haem iron and maximise recovery. Furthermore, samples were also deoxygenated prior to storage to decrease auto-oxidation, while resuspension in a solution containing ascorbic acid was shown to partially reduce LtEc that had oxidised during storage (e.g. from 42% Fe3+ to 11% Fe3+). Analysis of the oxygen equilibria and size of the resuspended LtEc showed that the lyophilisation, storage, and resuspension processes did not affect the oxygen transport properties or the structure of the LtEc, even after 6 months of storage at 40 °C. Altogether, these efforts have yielded a shelf-stable LtEc powder that can be stored for long periods at high temperatures, but future animal studies will be necessary to prove that the resuspended product is a safe and effective oxygen transporter in vivo.


Asunto(s)
Liofilización , Hemoglobinas , Oligoquetos , Animales , Oligoquetos/metabolismo , Hemoglobinas/química , Hemoglobinas/metabolismo , Oxígeno/metabolismo , Oxígeno/química , Oxidación-Reducción , Sustitutos Sanguíneos/química
2.
Water Sci Technol ; 89(9): 2273-2289, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38747949

RESUMEN

Water quality predicted accuracy is beneficial to river ecological management and water pollution prevention. Owing to water quality data has the characteristics of nonlinearity and instability, it is difficult to predict the change of water quality. This paper proposes a hybrid water quality prediction model based on variational mode decomposition optimized by the sparrow search algorithm (SSA-VMD) and bidirectional gated recursive unit (BiGRU). First, the sparrow search algorithm selects fuzzy entropy (FE) as the fitness function to optimize the two parameters of VMD, which improves the adaptability of VMD. Second, SSA-VMD is used to decompose the original data into several components with different center frequencies. Finally, BiGRU is employed to predict each component separately, which significantly improves predicted accuracy. The proposed model is validated using data about dissolved oxygen (DO) and the potential of hydrogen (pH) from the Xiaojinshan Monitoring Station in Qiandao Lake, Hangzhou, China. The experimental results show that the proposed model has superior prediction accuracy and stability when compared with other models, such as EMD-based models and other CEEMDAN-based models. The prediction accuracy of DO can reach 97.8% and pH is 96.1%. Therefore, the proposed model can provide technical support for river water quality protection and pollution prevention.


Asunto(s)
Modelos Teóricos , Calidad del Agua , Algoritmos , Oxígeno/química , Oxígeno/análisis , Monitoreo del Ambiente/métodos , Concentración de Iones de Hidrógeno , China
3.
Chem Pharm Bull (Tokyo) ; 72(5): 432-453, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38692858

RESUMEN

We have developed efficient synthetic reactions using enamines and enamides carrying oxygen atom substituent on nitrogen, such as N-alkoxyenamines, N,α-dialkoxyenamines, N-alkoxyanamides, and N-(benzoyloxy)enamides. The umpolung reaction by polarity inversion at the ß-position of N-alkoxyenamines afforded α-alkyl-, α-aryl-, α-alkenyl-, and α-heteroarylketones by using aluminum reagent as nucleophiles. Furthermore, one-pot umpolung α-phenylation of ketones has been also developed. We applied this method to umpolung reaction of N,α-dialkoxyenamine, generated from N-alkoxyamide to afford α-arylamides. The vicinal functionalization of N-alkoxyenamines has been achieved with the formation of two new carbon-carbon bonds by using an organo-aluminum reagent and subsequent allyl magnesium bromide or tributyltin cyanide. A sequential retro-ene arylation has been developed for the conversion of N-alkoxyenamides to the corresponding tert-alkylamines. The [3,3]-sigmatropic rearrangement of N-(benzoyloxy)enamides followed by arylation afforded cyclic ß-aryl-ß-amino alcohols bearing a tetrasubstituted carbon center. The resulting products were converted into the corresponding sterically congested cyclic ß-amino alcohols, as well as the dissociative anesthetic agent Tiletamine.


Asunto(s)
Amidas , Aminas , Amidas/química , Amidas/síntesis química , Aminas/química , Aminas/síntesis química , Estructura Molecular , Nitrógeno/química , Oxígeno/química
4.
Luminescence ; 39(5): e4762, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38698695

RESUMEN

Broadband near-infrared (NIR) spectroscopy has gained significant attention due to its versatile application in various fields. In the realm of NIR phosphors, Fe3+ ion is an excellent activator known for its nontoxic and harmless nature. In this study, we prepared an Fe3+-activated SrGa12O19 (SGO) NIR phosphor and analyzed its phase and luminescence properties. Upon excitation at 326 nm, the SGO:Fe3+ phosphor exhibited a broadband emission in the range 700-1000 nm, peaking at 816 nm. The optical band gap of SGO:Fe3+ was evaluated. To enhance the long-lasting phosphorescence, an oxygen vacancy-rich SGO:Fe3+ (VO-SGO:Fe3+) sample was prepared for activation. Interestingly, the increase in the oxygen-vacancy concentration indeed contributed to the activation of persistent luminescence of Fe3+ ions. The VO-SGO:Fe3+ sample has a long duration and high charge storage capacity, allowing it to perform efficiently in various applications. This work provides the foundation for further design of Cr3+-free PersL phosphors with efficient NIR PersL.


Asunto(s)
Luminiscencia , Sustancias Luminiscentes , Oxígeno , Oxígeno/química , Sustancias Luminiscentes/química , Estroncio/química , Mediciones Luminiscentes , Compuestos Férricos/química , Galio/química , Hierro/química , Espectroscopía Infrarroja Corta
5.
Bioresour Technol ; 401: 130760, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38692376

RESUMEN

This study aims to apply the Absorbing oxygen carriers (AOCs) to induce the migration and transformation of phosphorus compounds during the microwave thermal conversion of sludge so the hard-to-extract organic phosphorus (OP) can be converted to easy-to-extract inorganic phosphorus (IP) and be enriched onto the sludge char. The AOCs were recycled by screen separation from the IP-rich sludge char, with the latter being a renewable phosphorus source from sludge. The AOCs in this novel process enhanced the conversion efficiency of OP into non-apatite inorganic phosphorus (NAlP), which was further converted to apatite inorganic phosphorus (AP). Most phosphorus in the sludge char is presented in the form of orthophosphate.


Asunto(s)
Microondas , Oxígeno , Fósforo , Aguas del Alcantarillado , Aguas del Alcantarillado/química , Oxígeno/química , Temperatura
6.
J Colloid Interface Sci ; 668: 618-633, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38696990

RESUMEN

Tumor metastasis and recurrence are closely related to immune escape and hypoxia. Chemodynamic therapy (CDT), photodynamic therapy (PDT), and photothermal therapy (PTT) can induce immunogenic cell death (ICD), and their combination with immune checkpoint agents is a promising therapeutic strategy. Iron based nanomaterials have received more and more attention, but their low Fenton reaction efficiency has hindered their clinical application. In this study, Fe3O4-carbon dots complex (Fe3O4-CDs) was synthesized, which was modified with ferrocenedicarboxylic acid by amide bond, and crosslinked into Fe3O4-CDs@Fc nano complex. The CDs catalyzed the Fenton reaction activity of Fe3O4 by helping to improve the electron transfer efficiency, extended the reaction pH condition to 7.4. The Fe3O4-CDs@Fc exhibit exceptional optical activity, achieving a thermal conversion efficiency of 56.43 % under 808 nm light and a photosensitive single-line state oxygen quantum yield of 33 % under 660 nm light. Fe3O4-CDs@Fc improved intracellular oxygen level and inhibited hypoxia-inducing factor (HIF-1α) by in-situ oxygen production based on Fenton reaction. The multimodal combination of Fe3O4-CDs@Fc (CDT/PDT/PTT) strongly induced immune cell death (ICD). The expression of immune-related protein and HIF-1α was investigated by immunofluorescence method. In vivo, Fe3O4-CDs@Fc combined with immune checkpoint blocker (antibody PD-L1, αPD-L1) effectively ablated primary tumors and inhibited distal tumor growth. Fe3O4-CDs@Fc is a promising immune-antitumor drug.


Asunto(s)
Carbono , Oxígeno , Puntos Cuánticos , Ratones , Animales , Puntos Cuánticos/química , Carbono/química , Humanos , Catálisis , Oxígeno/química , Inmunoterapia , Tamaño de la Partícula , Antineoplásicos/farmacología , Antineoplásicos/química , Fotoquimioterapia , Ratones Endogámicos BALB C , Línea Celular Tumoral , Hierro/química , Peróxido de Hidrógeno/química , Peróxido de Hidrógeno/farmacología , Propiedades de Superficie , Supervivencia Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Ensayos de Selección de Medicamentos Antitumorales , Femenino
7.
J Colloid Interface Sci ; 668: 88-97, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38669999

RESUMEN

Nanotheranostic platforms, which can respond to tumor microenvironments (TME, such as low pH and hypoxia), are immensely appealing for photodynamic therapy (PDT). However, hypoxia in solid tumors harms the treatment outcome of PDT which depends on oxygen molecules to generate cytotoxic singlet oxygen (1O2). Herein, we report the design of TME-responsive smart nanotheranostic platform (DOX/ZnO2@Zr-Ce6/Pt/PEG) which can generate endogenously hydrogen peroxide (H2O2) and oxygen (O2) to alleviate hypoxia for improving photodynamic-chemo combination therapy of tumors. DOX/ZnO2@Zr-Ce6/Pt/PEG nanocomposite was prepared by the synthesis of ZnO2 nanoparticles, in-situ assembly of Zr-Ce6 as typical metal-organic framework (MOF) on ZnO2 surface, in-situ reduction of Pt nanozymes, amphiphilic lipids surface coating and then doxorubicin (DOX) loading. DOX/ZnO2@Zr-Ce6/Pt/PEG nanocomposite exhibits average sizes of ∼78 nm and possesses a good loading capacity (48.8 %) for DOX. When DOX/ZnO2@Zr-Ce6/Pt/PEG dispersions are intratumorally injected into mice, the weak acidic TEM induces the decomposition of ZnO2 core to generate endogenously H2O2, then Pt nanozymes catalyze H2O2 to produce O2 for alleviating tumor hypoxia. Upon laser (630 nm) irradiation, the Zr-Ce6 component in DOX/ZnO2@Zr-Ce6/Pt/PEG can produce cytotoxic 1O2, and 1O2 generation rate can be enhanced by 2.94 times due to the cascaded generation of endogenous H2O2/O2. Furthermore, the generated O2 can suppress the expression of hypoxia-inducible factor α, and further enable tumor cells to become more sensitive to chemotherapy, thereby leading to an increased effectiveness of chemotherapy treatment. The photodynamic-chemo combination therapy from DOX/ZnO2@Zr-Ce6/Pt/PEG nanoplatform exhibits remarkable tumor growth inhibition compared to chemotherapy or PDT. Thus, the present study is a good demonstration of a TME-responsive nanoplatform in a multimodal approach for cancer therapy.


Asunto(s)
Doxorrubicina , Peróxido de Hidrógeno , Oxígeno , Fotoquimioterapia , Nanomedicina Teranóstica , Peróxido de Hidrógeno/química , Peróxido de Hidrógeno/metabolismo , Animales , Ratones , Doxorrubicina/farmacología , Doxorrubicina/química , Doxorrubicina/administración & dosificación , Oxígeno/química , Oxígeno/metabolismo , Humanos , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Tamaño de la Partícula , Propiedades de Superficie , Ensayos de Selección de Medicamentos Antitumorales , Supervivencia Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Línea Celular Tumoral , Peróxidos/química , Peróxidos/farmacología , Nanopartículas/química , Ratones Endogámicos BALB C , Zinc/química , Zinc/farmacología , Microambiente Tumoral/efectos de los fármacos , Antibióticos Antineoplásicos/farmacología , Antibióticos Antineoplásicos/química , Antibióticos Antineoplásicos/administración & dosificación
8.
J Photochem Photobiol B ; 255: 112924, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38688041

RESUMEN

Whether rapid oxygen isotopic exchange between bicarbonate and water occurs in photosynthesis is the key to determine the source of oxygen by classic 18O-labeled photosynthetic oxygen evolution experiments. Here we show that both Microcystis aeruginosa and Chlamydomonas reinhardtii utilize a significant proportion (>16%) of added bicarbonate as a carbon source for photosynthesis. However, oxygen isotopic signal in added bicarbonate cannot be traced in the oxygen in organic matter synthesized by these photosynthetic organisms. This contradicts the current photosynthesis theory, which states that photosynthetic oxygen evolution comes only from water, and oxygen in photosynthetic organic matter comes only from carbon dioxide. We conclude that the photosynthetic organisms undergo rapid exchange of oxygen isotope between bicarbonate and water during photosynthesis. At the same time, this study also provides isotopic evidence for a new mechanism that half of the oxygen in photosynthetic oxygen evolution comes from bicarbonate photolysis and half comes from water photolysis, which provides a new explanation for the bicarbonate effect, and suggests that the Kok-Joliot cycle of photosynthetic oxygen evolution, must be modified to include a molecule of bicarbonate in addition to one molecule of water which in turn must be incorporated into the cycle instead of two water molecules. Furthermore, this study provides a theoretical basis for constructing a newer artificial photosynthetic reactor coupling light reactions with the dark reactions.


Asunto(s)
Bicarbonatos , Chlamydomonas reinhardtii , Isótopos de Oxígeno , Fotosíntesis , Agua , Bicarbonatos/química , Bicarbonatos/metabolismo , Agua/química , Agua/metabolismo , Isótopos de Oxígeno/química , Chlamydomonas reinhardtii/metabolismo , Microcystis/metabolismo , Oxígeno/metabolismo , Oxígeno/química , Dióxido de Carbono/metabolismo , Dióxido de Carbono/química
9.
Chemosphere ; 357: 142040, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38615949

RESUMEN

1,2,3-Trichloropropane (TCP) is an emerging groundwater pollutant, but there is a lack of reported studies on the abiotic natural attenuation of TCP by iron minerals. Furthermore, perturbation by O2 is common in the shallow subsurface by both natural and artificial processes. In this study, natural magnetite was selected as the reactive iron mineral to investigate its role in the degradation of TCP under O2 perturbation. The results indicated that the mineral structural Fe(II) on magnetite reacted with dissolved oxygen to generate O2-· and HO·. Both O2-· and HO· contributed to TCP degradation, with O2-· playing a more important role. After 56 days of reaction, 66.7% of TCP was completely dechlorinated. This study revealed that higher magnetite concentrations, smaller magnetite particle sizes, and lower initial TCP concentrations favored TCP degradation. The presence of <10 mg/L natural organic matter (NOM) did not affect TCP degradation. These findings significantly advance our understanding of the abiotic natural attenuation mechanisms facilitated by iron minerals under O2 perturbation, providing crucial insights for the study of natural attenuation.


Asunto(s)
Óxido Ferrosoférrico , Oxígeno , Propano , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/química , Oxígeno/química , Óxido Ferrosoférrico/química , Propano/química , Propano/análogos & derivados , Agua Subterránea/química , Hierro/química , Biodegradación Ambiental
10.
Bioprocess Biosyst Eng ; 47(5): 633-649, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38557906

RESUMEN

Fluid hydrodynamic stress has a deterministic effect on the morphology of filamentous fungi. Although the coaxial mixer has been recognized as a suitable gas dispersion system for minimizing inhomogeneities within a bioreactor, its performance for achieving enhanced oxygen transfer while operating at a reduced shear environment has not been investigated yet, specifically upon scale-up. Therefore, the influence of the impeller type, aeration rate, and central impeller retrofitting on the efficacy of an abiotic coaxial system containing a shear-thinning fluid was examined. The aim was to assess the hydrodynamic parameters, including stress, mass transfer, bubble size, and gas hold-up, upon conducting a scale-up study. The investigation was conducted through dynamic gassing-in, tomography, and computational fluid dynamics combined with population balance methods. It was observed that the coaxial bioreactor performance was strongly influenced by the agitator type. In addition, coaxial bioreactors are scalable in terms of shear environment and oxygen transfer rate.


Asunto(s)
Reactores Biológicos , Hidrodinámica , Fermentación , Oxígeno/metabolismo , Oxígeno/química , Estrés Mecánico
11.
Nat Commun ; 15(1): 3439, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38653759

RESUMEN

Oxygen in marine sediments regulates many key biogeochemical processes, playing a crucial role in shaping Earth's climate and benthic ecosystems. In this context, branched glycerol dialkyl glycerol tetraethers (brGDGTs), essential biomarkers in paleoenvironmental research, exhibit an as-yet-unresolved association with sediment oxygen conditions. Here, we investigated brGDGTs in sediments from three deep-sea regions (4045 to 10,100 m water depth) dominated by three respective trench systems and integrated the results with in situ oxygen microprofile data. Our results demonstrate robust correlations between diffusive oxygen uptake (DOU) obtained from microprofiles and brGDGT methylation and isomerization degrees, indicating their primary production within sediments and their strong linkage with microbial diagenetic activity. We establish a quantitative relationship between the Isomerization and Methylation index of Branched Tetraethers (IMBT) and DOU, suggesting its potential validity across deep-sea environments. Increased brGDGT methylation and isomerization likely enhance the fitness of source organisms in deep-sea habitats. Our study positions brGDGTs as a promising tool for quantifying benthic DOU in deep-sea settings, where DOU is a key metric for assessing sedimentary organic carbon degradation and microbial activity.


Asunto(s)
Bacterias , Sedimentos Geológicos , Oxígeno , Sedimentos Geológicos/microbiología , Sedimentos Geológicos/química , Oxígeno/metabolismo , Oxígeno/química , Bacterias/metabolismo , Bacterias/genética , Ecosistema , Éteres/metabolismo , Éteres/química , Lípidos/química , Metilación , Agua de Mar/microbiología , Agua de Mar/química
12.
Chemosphere ; 356: 141952, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38599329

RESUMEN

Photo-Fenton-like technology based on H2O2 is considered as an ideal strategy to generate reactive oxygen species (ROS) for antibiotic degradation, but O2 overflow in the process severely limits the utilization efficiency of H2O2. Herein, we fabricate Bi2MoO6 (BMO) photocatalyst modified with Frustrated Lewis pairs (FLPs) as a Fenton catalyst model for enhancing reuse of spilled O2. The FLPs created by the introduction of cerium and oxygen vacancy were found to contribute to regulate the electronic structure of BMO and further improve the acidic and basic properties of photocatalyst surface. More importantly, the frustrated acid and base sites can enhance the H2O2 and O2 interfacial adsorption process and provide an Ce4+-Ov-O2- active site on the surface of Ce-BMO nanosheets, which can promote O2/•O2-/1O2/H2O2 redox cycles to achieve high H2O2 utilization efficiency. Specifically, in the experiment using tetracycline as a photocatalytic degradation object, the degradation activity of Ce-BMO was 2.15 times higher than that of BMO pure phase. Quenching experiments and EPR assays also confirmed that 1O2 and •O2- were the dominant oxidative species. This study systematically reveals the design of Fenton photocatalytic active sites at the atomic scale and provides new insights into constructing FLPs photocatalysts with high H2O2 utilization efficiency.


Asunto(s)
Bismuto , Cerio , Peróxido de Hidrógeno , Fotólisis , Peróxido de Hidrógeno/química , Bismuto/química , Cerio/química , Catálisis , Molibdeno/química , Hierro/química , Especies Reactivas de Oxígeno/química , Oxidación-Reducción , Oxígeno/química
13.
Chemosphere ; 356: 141929, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38604520

RESUMEN

The cleaning and utilization of industry wastewater are still a big challenge. In this work, we mainly investigate the effect of electron transfer among multi-interfaces on water electrolysis reaction. Typically, the CoS2, Co3S4/CoS2 (designated as CS4-2) and Co3S4/Co9S8/CoS2 (designated as CS4-8-2) samples are prepared on a large scale by one-step molten salt method. It is found that because of the different work functions (designated as WF; WF(Co3S4) = 4.48eV, WF(CoS2) = 4.41eV, WF(Co9S8) = 4.18 eV), the effective heterojunctions at the multi-interfaces of CS4-8-2 sample, which obviously improve interface charge transfer. Thus, the CS4-8-2 sample shows an excellent oxygen evolution reaction (OER) activity (134 mV/10 mA cm-2, 40 mV dec-1). The larger double-layer capacitance (Cdl = 17.1 mF cm-2) of the CS4-8-2 sample indicates more electrochemical active sites, compared to the CoS2 and CS4-2 samples. Density functional theory (DFT) calculation proves that due to interface polarization under electric field, the multi-interfaces effectively promote electron transfer and regulate electron structure, thus promoting the adsorption of OH- and dissociation of H2O. Moreover, an innovative norfloxacin (NFX) electrolytic cell (EC) is developed through introducing NFX into the electrolyte, in which efficient NFX degradation and hydrogen production are synergistically achieved. To reach 50 mA cm-2, the required cell voltage of NFX-EC has decreased by 35.2%, compared to conventional KOH-EC. After 2h running at 1 V, 25.5% NFX was degraded in the NFX EC. This innovative NFX-EC is highly energy-efficient, which is promising for the synergistic cleaning and utilization of industry wastewater.


Asunto(s)
Electrólisis , Hidrógeno , Aguas Residuales , Agua , Hidrógeno/química , Aguas Residuales/química , Agua/química , Transporte de Electrón , Contaminantes Químicos del Agua/química , Eliminación de Residuos Líquidos/métodos , Oxígeno/química , Electrones
14.
Int J Biol Macromol ; 267(Pt 2): 131481, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38599431

RESUMEN

We developed an effective and eco-friendly strategy using chitosan gel-molten salt to achieve high loading (2.23 At. %) of single Fe-NX as assistive active sites. These sites were combined with small NiCo alloy NPs distributed on porous carbon aerogels to boost the ORR performance. The FeSAs-NiCo alloy@N-C sphere exhibits exceptional mass activity and specific activity of 3.705 A.mg-1 and 8.79 mA.cm-2(ECSA), respectively, at 0.85 V versus RHE. It has a superior onset potential of 1.08 V versus RHE, surpassing that of its nanoparticle Fe counterpart and NiCo alloy@N-C sphere. The significant improvement in ORR performance of the FeSAs-NiCo alloy@N-C sphere could be attributed to the positive effects of increased lattice strain due to the single atoms of Fe-NX hybridized with small NiCo alloy NPs. The chitosan gel-assisted molten salt strategy and assistive active sites of Fe-NX hybridized with NiCo alloy NPs regulate the electronic properties of the FeSAs-NiCo alloy@N-C sphere, both geometrically via lattice strain mismatch and electronically through shifting of the d-band center. This could influence the binding energies for oxygen and/or oxygen reduction intermediate adsorption/desorption. The additional improvement in the ORR performance of the FeSAs-NiCo alloy@N-C sphere also benefits from having a lower electrochemical activation energy.


Asunto(s)
Aleaciones , Quitosano , Geles , Oxidación-Reducción , Oxígeno , Quitosano/química , Oxígeno/química , Aleaciones/química , Geles/química , Hierro/química , Nanopartículas del Metal/química , Níquel/química , Cobalto/química , Catálisis , Sales (Química)/química
15.
J Phys Chem B ; 128(16): 3870-3884, 2024 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-38602496

RESUMEN

The O2-evolving Mn4CaO5 cluster in photosystem II is ligated by six carboxylate residues. One of these is D170 of the D1 subunit. This carboxylate bridges between one Mn ion (Mn4) and the Ca ion. A second carboxylate ligand is D342 of the D1 subunit. This carboxylate bridges between two Mn ions (Mn1 and Mn2). D170 and D342 are located on opposite sides of the Mn4CaO5 cluster. Recently, it was shown that the D170E mutation perturbs both the intricate networks of H-bonds that surround the Mn4CaO5 cluster and the equilibrium between different conformers of the cluster in two of its lower oxidation states, S1 and S2, while still supporting O2 evolution at approximately 50% the rate of the wild type. In this study, we show that the D342E mutation produces much the same alterations to the cluster's FTIR and EPR spectra as D170E, while still supporting O2 evolution at approximately 20% the rate of the wild type. Furthermore, the double mutation, D170E + D342E, behaves similarly to the two single mutations. We conclude that D342E alters the equilibrium between different conformers of the cluster in its S1 and S2 states in the same manner as D170E and perturbs the H-bond networks in a similar fashion. This is the second identification of a Mn4CaO5 metal ligand whose mutation influences the equilibrium between the different conformers of the S1 and S2 states without eliminating O2 evolution. This finding has implications for our understanding of the mechanism of O2 formation in terms of catalytically active/inactive conformations of the Mn4CaO5 cluster in its lower oxidation states.


Asunto(s)
Ácidos Carboxílicos , Mutación , Oxígeno , Complejo de Proteína del Fotosistema II , Calcio/metabolismo , Calcio/química , Ácidos Carboxílicos/química , Ácidos Carboxílicos/metabolismo , Espectroscopía de Resonancia por Spin del Electrón , Ligandos , Manganeso/química , Manganeso/metabolismo , Modelos Moleculares , Oxígeno/química , Oxígeno/metabolismo , Complejo de Proteína del Fotosistema II/química , Complejo de Proteína del Fotosistema II/metabolismo , Complejo de Proteína del Fotosistema II/genética , Espectroscopía Infrarroja por Transformada de Fourier
16.
ACS Nano ; 18(19): 12168-12186, 2024 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-38687976

RESUMEN

Assessment of hypoxia, nutrients, metabolite gradients, and other hallmarks of the tumor microenvironment within 3D multicellular spheroid and organoid models represents a challenging analytical task. Here, we report red/near-infrared (NIR) emitting cell staining with O2-sensitive nanoparticles, which enable measurements of spheroid oxygenation on a conventional fluorescence microscope. Nanosensor probes, termed "MMIR" (multimodal infrared), incorporate an NIR O2-sensitive metalloporphyrin (PtTPTBPF) and deep red aza-BODIPY reference dyes within a biocompatible polymer shell, allowing for oxygen gradient quantification via fluorescence ratio and phosphorescence lifetime readouts. We optimized staining techniques and evaluated the nanosensor probe characteristics and cytotoxicity. Subsequently, we applied nanosensors to the live spheroid models based on HCT116, DPSCs, and SKOV3 cells, at rest, and treated with drugs affecting cell respiration. We found that the growth medium viscosity, spheroid size, and formation method influenced spheroid oxygenation. Some spheroids produced from HCT116 and dental pulp stem cells exhibited "inverted" oxygenation gradients, with higher core oxygen levels than the periphery. This contrasted with the frequently encountered "normal" gradient of hypoxia toward the core caused by diffusion. Further microscopy analysis of spheroids with an "inverted" gradient demonstrated metabolic stratification of cells within spheroids: thus, autofluorescence FLIM of NAD(P)H indicated the formation of a glycolytic core and localization of OxPhos-active cells at the periphery. Collectively, we demonstrate a strong potential of NIR-emitting ratiometric nanosensors for advanced microscopy studies targeting live and quantitative real-time monitoring of cell metabolism and hypoxia in complex 3D tissue models.


Asunto(s)
Nanopartículas , Oxígeno , Esferoides Celulares , Humanos , Esferoides Celulares/metabolismo , Esferoides Celulares/efectos de los fármacos , Oxígeno/metabolismo , Oxígeno/química , Nanopartículas/química , Microscopía Fluorescente , Rayos Infrarrojos , Metaloporfirinas/química , Metaloporfirinas/farmacología
17.
ACS Sens ; 9(4): 2101-2109, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38574240

RESUMEN

Single-atom catalysts (SACs) hold great promise in highly sensitive and selective gas sensors due to their ultrahigh atomic efficiency and excellent catalytic activity. However, due to the extremely high surface energy of SACs, it is still a huge challenge to synthesize a stable single-atom metal on sensitive materials. Here, we report an atomic layer deposition (ALD) strategy for the elaborate synthesis of single-atom Pt on oxygen vacancy-rich Fe2O3 nanosheets (Pt-Fe2O3-Vo), which displayed ultrafast and sensitive detection to H2, achieving the stability of Pt single atoms. Gas-sensing investigation showed that the Pt-Fe2O3-Vo materials enabled a significantly enhanced response of 26.5-50 ppm of H2, which was 17-fold higher than that of pure Fe2O3, as well as ultrafast response time (2 s), extremely low detection limit (86 ppb), and improved stability. The experimental and density functional theory (DFT) studies revealed that the abundant oxygen vacancy sites of Fe2O3 contributed to stabilizing the Pt atoms via electron transfer. In addition, the stabilized Pt atoms also greatly promote the electron transfer of H2 molecules to Fe2O3, thereby achieving an excellent H2 sensing performance. This work provides a potential strategy for the development of highly selective and stable chemical sensors.


Asunto(s)
Compuestos Férricos , Hidrógeno , Nanoestructuras , Oxígeno , Platino (Metal) , Platino (Metal)/química , Oxígeno/química , Hidrógeno/química , Compuestos Férricos/química , Nanoestructuras/química , Teoría Funcional de la Densidad , Catálisis , Límite de Detección
18.
Acta Biomater ; 179: 61-82, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38579919

RESUMEN

In the field of tissue engineering, local hypoxia in large-cell structures (larger than 1 mm3) poses a significant challenge. Oxygen-releasing biomaterials supply an innovative solution through oxygen ⁠ delivery in a sustained and controlled manner. Compared to traditional methods such as emulsion, sonication, and agitation, microfluidic technology offers distinct benefits for oxygen-releasing material production, including controllability, flexibility, and applicability. It holds enormous potential in the production of smart oxygen-releasing materials. This review comprehensively covers the fabrication and application of microfluidic-enabled oxygen-releasing biomaterials. To begin with, the physical mechanism of various microfluidic technologies and their differences in oxygen carrier preparation are explained. Then, the distinctions among diverse oxygen-releasing components in regards for oxygen-releasing mechanism, oxygen-carrying capacity, and duration of oxygen release are presented. Finally, the present obstacles and anticipated development trends are examined together with the application outcomes of oxygen-releasing biomaterials based on microfluidic technology in the biomedical area. STATEMENT OF SIGNIFICANCE: Oxygen is essential for sustaining life, and hypoxia (a condition of low oxygen) is a significant challenge in various diseases. Microfluidic-based oxygen-releasing biomaterials offer precise control and outstanding performance, providing unique advantages over traditional approaches for tissue engineering. However, comprehensive reviews on this topic are currently lacking. In this review, we provide a comprehensive analysis of various microfluidic technologies and their applications for developing oxygen-releasing biomaterials. We compare the characteristics of organic and inorganic oxygen-releasing biomaterials and highlight the latest advancements in microfluidic-enabled oxygen-releasing biomaterials for tissue engineering, wound healing, and drug delivery. This review may hold the potential to make a significant contribution to the field, with a profound impact on the scientific community.


Asunto(s)
Materiales Biocompatibles , Oxígeno , Ingeniería de Tejidos , Oxígeno/química , Humanos , Materiales Biocompatibles/química , Ingeniería de Tejidos/métodos , Animales , Microfluídica/métodos
19.
ACS Sens ; 9(4): 2183-2193, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38588327

RESUMEN

Sensitive and selective acetone detection is of great significance in the fields of environmental protection, industrial production, and individual health monitoring from exhaled breath. To achieve this goal, bimetallic Au@Pt core-shell nanospheres (BNSs) functionalized-electrospun ZnFe2O4 nanofibers (ZFO NFs) are prepared in this work. Compared to pure NFs-650 analogue, the ZFO NFs/BNSs-2 sensor exhibits a stronger mean response (3.32 vs 1.84), quicker response/recovery speeds (33 s/28 s vs 54 s/42 s), and lower operating temperature (188 vs 273 °C) toward 0.5 ppm acetone. Note that an experimental detection limit of 30 ppb is achieved, which ranks among the best cases reported thus far. Besides the demonstrated excellent repeatability, humidity-enhanced response, and long-term stability, the selectivity toward acetone is remarkably improved after BNSs functionalization. Through material characterizations and DFT calculations, all these improvements could be attributed to the boosted oxygen vacancies and abundant Schottky junctions between ZFO NFs and BNSs, and the synergistic catalytic effect of BNSs. This work offers an alternative strategy to realize selective subppm acetone under high-humidity conditions catering for the future requirements of noninvasive breath diabetes diagnosis in the field of individual healthcare.


Asunto(s)
Acetona , Pruebas Respiratorias , Oro , Nanofibras , Nanosferas , Platino (Metal) , Acetona/análisis , Acetona/química , Nanofibras/química , Oro/química , Pruebas Respiratorias/métodos , Nanosferas/química , Platino (Metal)/química , Humanos , Límite de Detección , Oxígeno/química , Técnicas Electroquímicas/métodos
20.
ACS Sens ; 9(4): 1938-1944, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38591496

RESUMEN

The adsorption of oxygen and its reaction with target gases are the basis of the gas detection mechanism by using metal oxides. Here, we present a theoretical analysis of the sensor response, within the ionosorption model, for an n-type polycrystalline semiconductor. Our goal of our work is to reveal the mechanisms of gas sensing from a fundamental point of view. We revisit the existing models in which the sensor response presents a power-law behavior with a reducing gas partial pressure. Then, we show, based on the Wolkenstein theory of chemisorption, that the sensor response depends not only on the reducing gas partial pressure but also on the oxygen partial pressure. We also find that the obtained sensor response does not explicitly depend on the grain size, and if it does, it is exclusively through the rate constants related to the involved reactions.


Asunto(s)
Gases , Óxidos , Oxígeno , Oxígeno/química , Óxidos/química , Gases/química , Semiconductores , Presión , Metales/química , Adsorción , Oxidación-Reducción
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA