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1.
Ind Eng Chem Res ; 62(49): 21152-21163, 2023 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-38107750

RESUMO

Despite offering low-carbon and reliable energy, the utilization of nuclear energy is declining globally due to high upfront capital costs and longer returns on investments. Nuclear cogeneration of valuable chemicals from waste biomass-derived feedstocks could have beneficial impacts while harnessing the underutilized resource of ionizing energy. Here, we demonstrate selective methanol or acetaldehyde production from ethylene glycol, a feedstock derived from glycerol, a byproduct of biodiesel, using irradiations from a nuclear fission reactor. The influence of radiation quality, dose rate, and the absorbed dose of irradiations on radiochemical yields (G-value) has been studied. Under low-dose-rate, γ-only radiolysis during reactor shutdown rate (<0.018 kGy min-1), acetaldehyde is produced at a maximum G-value of 8.28 ± 1.05 µmol J-1 and a mass productivity of 0.73 ± 0.06% from the 20 kGy irradiation of neat ethylene glycol. When exposed to a high-dose-rate (6.5 kGy min-1), 100 kGy mixed-field of neutron + γ-ray radiations, the radiolytic selectivity is adjusted from acetaldehyde to generate methanol at a G-value of 2.91 ± 0.78 µmol J-1 and a mass productivity of 0.93 ± 0.23%. Notably, utilizing 422 theoretical systems could contribute to 4.96% of worldwide acetaldehyde production using a spent fuel pool γ-ray scheme. This research reports G-values and production capacities for acetaldehyde for high-dose scenarios and shows the potential selectivity of a nuclear cogeneration process to synthesize chemicals based on their irradiation conditions from the same reagent.

2.
Clin Nutr ESPEN ; 49: 40-52, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35623844

RESUMO

BACKGROUND & AIMS: Elevated circulating uric acid concentrations have been linked to various cardio-metabolic diseases. Bolus consumption of a nucleotide-rich dietary protein source increases postprandial serum uric acid concentrations. We assessed the impact of twice-daily nucleotide-rich mixed-meal consumption for one week on postabsorptive serum uric acid concentrations, insulin sensitivity (IS), glycaemic control and the plasma lipidome. METHODS: Twenty healthy adults participated in a randomised, controlled, parallel-group trial in which they consumed a 7 d fully-controlled eucaloric diet where lunch and dinner contained either nucleotide-depleted (LOW) or high-nucleotide (HIGH) mycoprotein. Postabsorptive blood samples were obtained pre, throughout and post-intervention, and oral glucose tolerance tests were performed pre- and post-intervention. Daily waking urine samples and 24 h continuous blood glucose measurements were collected throughout. RESULTS: Postabsorptive serum uric acid concentrations remained unchanged in LOW but increased throughout the intervention week in HIGH (from 295 ± 17 to 472 ± 29 µmol L-1 by day 6; P < 0.05). Urinary uric acid did not change throughout the intervention in either group. The intervention did not affect indices of IS, 24 h glycaemic control, nor had a meaningful impact on the plasma lipidome. CONCLUSIONS: One week of twice-daily consumption of nucleotide-rich mixed-meals increases postabsorptive serum uric acid concentrations above clinically acceptable thresholds but these changes are not associated with deleterious effects on IS, daily glycaemic control or plasma lipid composition. CLINICAL TRIAL REGISTRY: NCT02984358 (https://clinicaltrials.gov/ct2/show/NCT02984358).


Assuntos
Resistência à Insulina , Ácido Úrico , Adulto , Glicemia/metabolismo , Dieta , Humanos , Nucleotídeos , Período Pós-Prandial
3.
Commun Chem ; 4(1): 132, 2021 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-36697630

RESUMO

Non-intermittent, low-carbon energy from nuclear or biofuels is integral to many strategies to achieve Carbon Budget Reduction targets. However, nuclear plants have high, upfront costs and biodiesel manufacture produces waste glycerol with few secondary uses. Combining these technologies, to precipitate valuable feedstocks from waste glycerol using ionizing radiation, could diversify nuclear energy use whilst valorizing biodiesel waste. Here, we demonstrate solketal (2,2-dimethyl-1,3-dioxolane-4-yl) and acetol (1-hydroxypropan-2-one) production is enhanced in selected aqueous glycerol-acetone mixtures with γ radiation with yields of 1.5 ± 0.2 µmol J-1 and 1.8 ± 0.2 µmol J-1, respectively. This is consistent with the generation of either the stabilized, protonated glycerol cation (CH2OH-CHOH-CH2OH2+ ) from the direct action of glycerol, or the hydronium species, H3O+, via water radiolysis, and their role in the subsequent acid-catalyzed mechanisms for acetol and solketal production. Scaled to a hypothetically compatible range of nuclear facilities in Europe (i.e., contemporary Pressurised Water Reactor designs or spent nuclear fuel stores), we estimate annual solketal production at approximately (1.0 ± 0.1) × 104 t year-1. Given a forecast increase of 5% to 20% v/v% in the renewable proportion of commercial petroleum blends by 2030, nuclear-driven, biomass-derived solketal could contribute towards net-zero emissions targets, combining low-carbon co-generation and co-production.

4.
Nutrients ; 12(4)2020 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-32316391

RESUMO

Circulating uric acid concentrations have been linked to various metabolic diseases. Consumption of large boluses of nucleotides increases serum uric acid concentrations. We investigated the effect of a nucleotide-rich mixed meal on postprandial circulating uric acid, glucose, and insulin responses. Ten healthy adults participated in a randomised, controlled, double-blind, crossover trial in which they consumed a mixed-meal containing either nucleotide-depleted mycoprotein (L-NU) or high-nucleotide mycoprotein (H-NU) on two separate visits. Blood samples were collected in the postabsorptive state and throughout a 24 h postprandial period, and were used to determine circulating uric acid, glucose, and insulin concentrations. Mixed meal ingestion had divergent effects on serum uric acid concentrations across conditions (time x condition interaction; P < 0.001), with L-NU decreasing transiently (from 45 to 240 min postprandially) by ~7% (from 279 ± 16 to 257 ± 14 µmol·L-1) and H-NU resulting in a ~12% increase (from 284 ± 13 to 319 ± 12 µmol·L-1 after 210 min), remaining elevated for 12 h and returning to baseline concentrations after 24 h. There were no differences between conditions in blood glucose or serum insulin responses, nor in indices of insulin sensitivity. The ingestion of a nucleotide-rich mixed-meal increases serum uric acid concentrations for ~12 h, but does not influence postprandial blood glucose or serum insulin concentrations.


Assuntos
Glicemia/metabolismo , Dieta , Proteínas Alimentares/administração & dosagem , Suplementos Nutricionais , Ingestão de Alimentos/fisiologia , Voluntários Saudáveis , Insulina/sangue , Nucleotídeos/administração & dosagem , Nucleotídeos/farmacologia , Período Pós-Prandial , Ácido Úrico/sangue , Adulto , Estudos Cross-Over , Proteínas Alimentares/química , Proteínas Alimentares/farmacologia , Método Duplo-Cego , Feminino , Humanos , Masculino , Fatores de Tempo , Adulto Jovem
5.
J Phys Chem B ; 115(26): 8481-92, 2011 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-21604799

RESUMO

Densities and molar excess volumes of the solutions of pyridine or nicotine in liquid polyethylene glycol, PEG200 and PEG400, have been determined at several temperatures. The experimental molar excess volumes are negative, thus indicating strong attractive interactions between the components, as could be expected considering their highly polar nature and good hydrogen bond abilities. For the pyridine systems, this negativity is slightly increased as the temperature rises, while the opposite tendency is observed for the nicotine mixtures. When pyridine and nicotine solutions are compared, the former-particularly those with PEG400-exhibit substantially more negative molar excess volumes than the latter. The effect of the polymer chain length on the results for the nicotine solutions is almost negligible. However, this is not the case when pyridine is one of the components: a longer chain induced considerably higher compression on mixing. The Fourier-transform infrared analysis allowed interpretation of the negative experimental molar excess volumes in terms of specific inter- and intramolecular interactions.


Assuntos
Nicotina/química , Polietilenoglicóis/química , Piridinas/química , Soluções/química , Humanos , Bicamadas Lipídicas/química , Estrutura Molecular , Peso Molecular , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
6.
Acc Chem Res ; 40(11): 1114-21, 2007 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-17622178

RESUMO

The fascinating, complex behavior of ionic liquids is analyzed using a molecular perspective that emphasizes the doubly dual nature of ionic liquids underlying the existence of cations and anions forming high- and low-charge-density regions. Our work bridges the liquid, gas, and solid phases spanning 5 years of research on themes as diverse as the vaporization, liquid-liquid demixing, solidification, and thermophysical behavior of ionic liquids and their mixtures and solutions.


Assuntos
Líquidos Iônicos/química , Modelos Químicos , Termodinâmica , Transição de Fase
7.
J Am Chem Soc ; 127(18): 6542-3, 2005 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-15869269

RESUMO

Lower critical solution temperatures (LCST)-type of phase diagrams, including the presence of closed loops, have been encountered for the first time in binary and quasi-binary liquid solutions of ionic liquids. Furthermore, the results constitute the first experimental support for the existence of a theoretically postulated, but never encountered, special kind of type VII phase diagram. Two distinct mechanisms are involved in the appearance of demixing upon temperature increase. These findings underlie the presence of specific, oriented interactions between the ionic liquid, 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide, [Cnmim][NTf2], and trichloromethane, as well as aggregation phenomena.

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