Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 741
Filtrar
2.
Appl Radiat Isot ; 207: 111245, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38430827

RESUMO

Radioactive scandium-46 microspheres have applications in mapping flow in a chemical reactor through a technique known as radioactive particle tracking (RPT). In the present study a novel microfluidic method has been developed for synthesis of controlled size scandium oxide microspheres. An inline/in-situ mixing of the scandium precursor and gelling agents was implemented which makes the microfluidic platform amenable for truly continuous operation. Microspheres of size varying from 937 to 666 µm were produced by varying O/A ratio from 10 to 30. Perfectly spherical and monodispersed (PDI <10 %) microspheres were obtained at O/A 15 and beyond. The morphology, elemental composition, and structure of the microspheres were analysed by SEM, EDS and XRD, respectively. Subsequently the microspheres were irradiated with thermal neutrons in a nuclear reactor to obtain radioactive Sc-46 oxide microspheres. The activity produced on each Sc-46 microspheres with different sizes was in the range 19.5-34.0 MBq.

3.
Indian J Hematol Blood Transfus ; 40(1): 139-145, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38312185

RESUMO

Iron deficiency anemia (IDA) forms a major share of global burden of anemia. Frequent blood donation is a common iatrogenic cause of iron insufficiency in healthy adults. Serum iron and hemoglobin levels are normal despite low serum ferritin levels, referred to as latent iron deficiency (LID). Aim of the present study was to evaluate the role of novel RBC parameters-percentage of hypochromic RBCs (%HPO), percentage of microcytic RBCs (%MIC), and haemoglobin content of reticulocytes (MCHr) of Abbott Alinity autoanalyzer as indicators of latent iron deficiency in blood donors. 260 consenting and eligible blood donors were included in the study. Complete blood counts including new RBC parameters on Abbott Alinity autoanalyzer and serum iron profile were measured for all donors. Donors were categorized into LID and No LID based on Ferritin and Transferrin saturation (TSAT). Serum transferrin receptors (sTfR) were studied in a subset of samples [LID (n = 46), No LID (n = 18) and IDA (n = 27)]. Statistical analyses was done on IBM SPSS version 22. Among 260 donors, 56 (21.5%) were found to have LID. The difference in mean values for % HPO, % MIC, and MCHr were not found to be statistically significant in LID and No LID groups. sTfR results between LID, No LID and IDA sub-groups revealed significant difference. This study does not support the role of % HPO, % MIC and MCHr measured on Abott Alinity analyzer, as potential screening parameters for LID amongst blood donors. STfr was more informative in this regard. Further research on much larger sample size is required to confirm these findings. Supplementary Information: The online version contains supplementary material available at 10.1007/s12288-023-01683-w.

4.
Phys Rev Lett ; 132(5): 058202, 2024 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-38364148

RESUMO

A crossover from a non-Gaussian to Gaussian subdiffusion has been observed ubiquitously in various polymeric and molecular glassformers. We have developed a framework that generalizes the fractional Brownian motion model to incorporate non-Gaussian features by introducing a jump kernel. We illustrate that the non-Gaussian fractional Brownian motion model accurately characterizes the subdiffusion crossover. From the solutions of the non-Gaussian fractional Brownian motion model, we gain insights into the nature of van Hove self-correlation in non-Gaussian subdiffusive regime, which is found to exhibit exponential tails, providing first such experimental evidence in molecular glassformers. The validity of the model is supported by comparison with incoherent quasielastic neutron scattering data obtained from several molecular and polymeric glassformers.

5.
J Phys Chem Lett ; 14(43): 9766-9773, 2023 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-37882461

RESUMO

The relationship between Stokes-Einstein breakdown (SEB) and dynamical heterogeneity (DH) is of paramount importance in the physical chemistry of complex fluids. In this work, we employ neutron scattering to probe the DH and SEB in a series of deep eutectic solvents (DESs) composed of acetamide and lithium salts. Quasielastic neutron scattering experiments reveal SEB in the jump diffusion of acetamide, represented by a fractional Stokes-Einstein relationship. Among these DESs, lithium perchlorate exhibits the most pronounced SEB while lithium bromide displays the weakest. Concurrently, elastic incoherent neutron scans identify that bromide DES is the most heterogeneous and perchlorate is the least. For the first time, our study unveils a counterintuitive incommensurate relationship between DH and SEB. Further, it reveals the intricate contrasting nature of the SEB-DH relationship when investigated in proximity to the glass-transition temperature and further away from it.

6.
Pediatr Dermatol ; 40(4): 627-632, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37269189

RESUMO

BACKGROUND: Moisturizers are first-line therapy for treatment of atopic dermatitis (AD). Although there are multiple types of moisturizers available, head-to-head trials between different moisturizers are limited. OBJECTIVE: To evaluate if a paraffin-based moisturizer is as effective as ceramide-based moisturizer in children with AD. MATERIALS AND METHODS: In this double-blind, randomized comparative trial of pediatric patients with mild to moderate AD, subjects applied either a paraffin-based or ceramide-based moisturizer twice daily. Clinical disease activity using SCOring Atopic Dermatitis (SCORAD), quality of life using Children/Infants Dermatology Life Quality Index (CDLQI/IDLQI), and transepidermal water loss (TEWL) were measured at baseline and at follow-up at 1, 3, and 6 months. RESULTS: Fifty-three patients were recruited (27 ceramide group and 26 paraffin group) with a mean age of 8.2 years and mean disease duration of 60 months. The mean change in SCORAD at 3 months in the ceramide-based and paraffin-based moisturizer groups was 22.1 and 21.4, respectively (p = .37). The change in CDLQI/IDLQI, TEWL over forearm and back, amount and days of topical corticosteroid required, median time to remission and disease-free days at 3 months were similar in both groups. As the 95% confidence interval (CI) of mean change in SCORAD at 3 months in both groups (0.78, 95% CI: -7.21 to 7.52) was not within the predefined margin of equivalence (-4 to +4), the conclusion of equivalence could not be proven. CONCLUSION: Both the paraffin-based and ceramide-based moisturizers were comparable in improving the disease activity in children with mild to moderate AD.


Assuntos
Dermatite Atópica , Lactente , Criança , Humanos , Dermatite Atópica/tratamento farmacológico , Emolientes/uso terapêutico , Parafina/uso terapêutico , Ceramidas , Qualidade de Vida , Resultado do Tratamento , Método Duplo-Cego , Índice de Gravidade de Doença
7.
Appl Radiat Isot ; 192: 110570, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36462300

RESUMO

The anaerobic digesters find usage in treating the huge amount of waste such as trash, garbage, human waste and animal waste. The sustained performance of an anaerobic digester depends on the flow pattern and mixing behaviour in the digester. A cylindrical digester tank with vertical baffles can provide flow behaviour approaching that of a plug flow reactor. However, the presence of dead zones and recirculating regions cause non-ideal flow in the digester. In this work, the mixing behaviour in two scaled-down models of baffled digester tanks is characterized by measurement of residence time distribution (RTD) using a radioactive tracer. While the first design has three vertical baffles, the second design include horizontal static flaps on the baffles. The flow behaviour in the digester is also simulated using computational fluid dynamics (CFD) and RTD is obtained computationally. The comparison of RTD curves obtained from CFD simulations with those obtained from radiotracer experiments show good agreement between them. There appear to be only minor difference in the flow behaviour and the RTD curves in the two digester designs. Using the RTD curve data, two commonly used RTD models, tank-in-series and dispersion models, have been fitted and both models are able to predict the RTD in the digester qualitatively.


Assuntos
Reatores Biológicos , Hidrodinâmica , Humanos , Simulação por Computador , Anaerobiose
8.
Front Microbiol ; 14: 1265265, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38370576

RESUMO

Introduction: The yield of chickpea is severely hampered by infection wilt caused by several races of Fusarium oxysporum f. sp. ciceris (Foc). Methods: To understand the underlying molecular mechanisms of resistance against Foc4 Fusarium wilt, RNA sequencing-based shoot transcriptome data of two contrasting chickpea genotypes, namely KWR 108 (resistant) and GL 13001 (susceptible), were generated and analyzed. Results and Discussion: The shoot transcriptome data showed 1,103 and 1,221 significant DEGs in chickpea genotypes KWR 108 and GL 13001, respectively. Among these, 495 and 608 genes were significantly down and up-regulated in genotypes KWR 108, and 427 and 794 genes were significantly down and up-regulated in genotype GL 13001. The gene ontology (GO) analysis of significant DEGs was performed and the GO of the top 50 DEGs in two contrasting chickpea genotypes showed the highest cellular components as membrane and nucleus, and molecular functions including nucleotide binding, metal ion binding, transferase, kinase, and oxidoreductase activity involved in biological processes such as phosphorylation, oxidation-reduction, cell redox homeostasis process, and DNA repair. Compared to the susceptible genotype which showed significant up-regulation of genes involved in processes like DNA repair, the significantly up-regulated DEGs of the resistant genotypes were involved in processes like energy metabolism and environmental adaptation, particularly host-pathogen interaction. This indicates an efficient utilization of environmental adaptation pathways, energy homeostasis, and stable DNA molecules as the strategy to cope with Fusarium wilt infection in chickpea. The findings of the study will be useful in targeting the genes in designing gene-based markers for association mapping with the traits of interest in chickpea under Fusarium wilt which could be efficiently utilized in marker-assisted breeding of chickpea, particularly against Foc4 Fusarium wilt.

9.
Soft Matter ; 19(1): 57-68, 2022 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-36458871

RESUMO

The anionic dimyristoyl phosphatidylglycerol (DMPG) membrane in solvents with a low ionic strength is known to exhibit an unusually wide melting regime between the gel and fluid phase characterized by various anomalous macroscopic characteristics, such as low turbidity and high electrical conductivity and viscosity. A recent neutron spin echo study [Kelley, E. G. et al., Struct. Dyn., 7 (2020) 054704] revealed that during the extended melting phase transition the DMPG membrane becomes softer and exhibits faster collective bending fluctuation compared to the higher temperature fluid phase. In contrast, in the present work, using incoherent quasielastic neutron scattering through the anomalous phase transition regime we find that single-particle lateral and internal lipid motions in the DMPG membrane show regular temperature dependence, with no enhanced dynamics evident in the anomalous melting regime. Further, we find that incorporation of NaCl in DMPG suppresses the anomalous extended melting regime, concurrently enhancing the single-particle lipid dynamics, both the lateral diffusivity and (to a lesser extent) the internal lipid motion. This seems rather counterintuitive and in variance with the dynamic suppression effect exerted by a salt on a zwitterionic membrane. However, since incorporation of a salt in anionic DMPG leads to enhanced cooperativity, the disrupted cooperativity in the salt-free DMPG is associated with the baseline lipid dynamics that is suppressed to begin with, whereas addition of salt partially restores the cooperativity, thus enhancing lipid dynamics compared to the salt-free baseline DMPG membrane state. These results provide new insights into the ion-membrane interaction and divulge a correlation between microscopic dynamics and the structure of the lipid bilayer.


Assuntos
Fosfatidilgliceróis , Cloreto de Sódio , Temperatura , Fosfatidilgliceróis/química , Bicamadas Lipídicas/química
10.
Front Microbiol ; 13: 924407, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36187978

RESUMO

Excessive dependence on chemical fertilizers and ignorance to organic and microbial inputs under intensive cropping systems are the basic components of contemporary agriculture, which evolves several sustainability issues, such as degraded soil health and sub-optimal crop productivity. This scenario urges for integrated nutrient management approaches, such as microbes-mediated integrated plant nutrition for curtailing the high doses as chemical fertilizers. Rationally, experiment has been conducted in pigeonpea at ICAR-IARI, New Delhi, with the aim of identifying the appropriate nutrient management technique involving microbial and organic nutrient sources for improved rhizo-modulation, crop productivity, and soil bio-fertility. The randomized block-designed experiment consisted nine treatments viz. Control, Recommended dose of fertilizers (RDF), RDF+ Microbial inoculants (MI), Vermicompost (VC), Farm Yard Manure (FYM), Leaf Compost (LC), VC + MI, FYM + MI, and LC + MI. Rhizobium spp., Pseudomonas spp., Bacillus spp., and Frateuria aurantia were used as seed-inoculating microbes. The results indicated the significant response of integration following the trend VC + MI > FYM + MI > LC + MI > RDF + MI for various plant shoot-root growth attributes and soil microbial and enzymatic properties. FYM + MI significantly improved the water-stable aggregates (22%), mean weight diameter (1.13 mm), and geometric mean diameter (0.93 mm), soil organic carbon (SOC), SOC stock, and SOC sequestration. The chemical properties viz. available N, P, and K were significantly improved with VC + MI. The study summarizes that FYM + MI could result in better soil physico-chemical and biological properties and shoot-root development; however; VC + MI could improve available nutrients in the soil and may enhance the growth of pigeonpea more effectively. The outcomes of the study are postulated as a viable and alternative solution for excessive chemical fertilizer-based nutrient management and would also promote the microbial consortia and organic manures-based agro-industries. This would add to the goal of sustainable agricultural development by producing quality crop produce, maintaining agro-biodiversity and making the soils fertile and healthy that would be a "gift to the society."

11.
J Phys Chem B ; 126(44): 9026-9037, 2022 11 10.
Artigo em Inglês | MEDLINE | ID: mdl-36315464

RESUMO

Aqueous mixtures of deep eutectic solvents (DESs) have gained traction recently as an effective template to tailor their physicochemical properties. But detailed microscopic insights into the effects of water on the molecular relaxation phenomenon in DESs are not entirely understood. DESs are strong network-forming liquids due to the extensive hydrogen bonding and complex formation between their species, and therefore, water can behave as a controlled disruptor altering the microscopic structure and dynamics in DESs. In this study, the role of water in the diffusion mechanism of acetamide in the aqueous mixtures of DESs synthesized using acetamide and lithium perchlorate is investigated using molecular dynamics (MD) simulation and quasielastic neutron scattering (QENS). The acetamide dynamics comprises localized diffusion within transient cages and a jump diffusion process across cages. The jump diffusion process is observed to be strongly enhanced by about a factor of 10 as the water content in the system is increased. Meanwhile, the geometry of the localized dynamics is unaltered by addition of water, but the localized diffusion becomes significantly faster and more heterogeneous with increasing water concentration. The accelerating effects of water on localized diffusion are also substantiated by QENS experiments. The water concentration in the DES is observed to control the solvation structure of lithium ions, with the ions becoming significantly hydrated at 20 wt % water. The formation of interwater and water-acetamide hydrogen bonds is observed. The increase in water concentration is found to increase the number of H-bonds; however, their lifetimes are found to decrease substantially. Similarly, the lifetimes of acetamide-lithium complexes are also found to be diminished by increasing water concentration. A power-law scaling relationship between lifetimes and diffusion constants is established, elucidating the extent of coupling between diffusive processes and hydrogen bonding and microscopic complexation. This study demonstrates the ability to use water as an agent to probe the role of structural relaxation and complex lifetimes of diffusive processes at different time and length scales.


Assuntos
Solventes Eutéticos Profundos , Lítio , Água/química , Íons/química , Acetamidas , Solventes/química
12.
Prog Lipid Res ; 87: 101179, 2022 07.
Artigo em Inglês | MEDLINE | ID: mdl-35780913

RESUMO

The plasma membrane is one of the principal structural components of the cell and, therefore, one of the key components of the cellular life. Because the membrane's dynamics links the membrane's structure and function, the complexity and the broad range of the membrane's motions are essential for the enormously diverse functionality of the cell membrane. Even for the main membrane component, the lipid bilayer, considered alone, the range and complexity of the lipid motions are remarkable. Spanning the time scale from sub-picosecond to minutes and hours, the lipid motion in a bilayer is challenging to study even when a broad array of dynamic measurement techniques is employed. Neutron scattering plays a special role among such dynamic measurement techniques, particularly, because it involves the energy transfers commensurate with the typical intra- and inter- molecular dynamics and the momentum transfers commensurate with intra- and inter-molecular distances. Thus, using neutron scattering-based techniques, the spatial and temporal information on the lipid motion can be obtained and analysed simultaneously. Protium vs. deuterium sensitivity and non-destructive character of the neutron probe add to the remarkable prowess of neutron scattering for elucidating the lipid dynamics. Herein we present an overview of the neutron scattering-based studies of lipid dynamics in model membranes, with a discussion of the direct relevance and implications to the real-life cell membranes. The latter are much more complex systems than simple model membranes, consisting of heterogeneous non-stationary domains composed of lipids, proteins, and other small molecules, such as carbohydrates. Yet many fundamental aspects of the membrane behavior and membrane interactions with other molecules can be understood from neutron scattering measurements of the model membranes. For example, such studies can provide a great deal of information on the interactions of antimicrobial compounds with the lipid matrix of a pathogen membrane, or the interactions of drug molecules with the plasma membrane. Finally, we briefly discuss the recently emerging field of neutron scattering membrane studies with a reach far beyond the model membrane systems.


Assuntos
Bicamadas Lipídicas , Difração de Nêutrons , Bicamadas Lipídicas/química , Simulação de Dinâmica Molecular , Difração de Nêutrons/métodos , Nêutrons , Análise Espectral
13.
Sci Rep ; 12(1): 3161, 2022 02 24.
Artigo em Inglês | MEDLINE | ID: mdl-35210519

RESUMO

Maize is an important industrial crop where yield and quality enhancement both assume greater importance. Clean production technologies like conservation agriculture and integrated nutrient management hold the key to enhance productivity and quality besides improving soil health and environment. Hence, maize productivity and quality were assessed under a maize-wheat cropping system (MWCS) using four crop-establishment and tillage management practices [FBCT-FBCT (Flat bed-conventional tillage both in maize and wheat); RBCT-RBZT (Raised bed-CT in maize and raised bed-zero tillage in wheat); FBZT-FBZT (FBZT both in maize and wheat); PRBZT-PRBZT (Permanent raised bed-ZT both in maize and wheat], and five P-fertilization practices [P100 (100% soil applied-P); P50 + 2FSP (50% soil applied-P + 2 foliar-sprays of P through 2% DAP both in maize and wheat); P50 + PSB + AM-fungi; P50 + PSB + AMF + 2FSP; and P0 (100% NK with no-P)] in split-plot design replicated-thrice. Double zero-tilled PRBZT-PRBZT system significantly enhanced the maize grain, starch, protein and oil yield by 13.1-19% over conventional FBCT-FBCT. P50 + PSB + AMF + 2FSP, integrating soil applied-P, microbial-inoculants and foliar-P, had significantly higher grain, starch, protein and oil yield by 12.5-17.2% over P100 besides saving 34.7% fertilizer-P both in maize and on cropping-system basis. P50 + PSB + AMF + 2FSP again had significantly higher starch, lysine and tryptophan content by 4.6-10.4% over P100 due to sustained and synchronized P-bioavailability. Higher amylose content (24.1%) was observed in grains under P50 + PSB + AMF + 2FSP, a beneficial trait due to its lower glycemic-index highly required for diabetic patients, where current COVID-19 pandemic further necessitated the use of such dietary ingredients. Double zero-tilled PRBZT-PRBZT reported greater MUFA (oleic acid, 37.1%), MUFA: PUFA ratio and P/S index with 6.9% higher P/S index in corn-oil (an oil quality parameter highly required for heart-health) over RBCT-RBCT. MUFA, MUFA: PUFA ratio and P/S index were also higher under P50 + PSB + AMF + 2FSP; avowing the obvious role of foliar-P and microbial-inoculants in influencing maize fatty acid composition. Overall, double zero-tilled PRBZT-PRBZT with crop residue retention at 6 t/ha per year along with P50 + PSB + AMF + 2FSP while saving 34.7% fertilizer-P in MWCS, may prove beneficial in enhancing maize productivity and quality so as to reinforce the food and nutritional security besides boosting food, corn-oil and starch industry in south-Asia and collateral arid agro-ecologies across the globe.

14.
QJM ; 115(1): 7-11, 2022 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-32810234

RESUMO

BACKGROUND: Transient hyperglycaemia in the context of illness with or without known diabetes has been termed as 'stress hyperglycaemia'. Stress hyperglycaemia can result in poor functional outcomes in patients with acute ischaemic stroke (AIS) who underwent mechanical thrombectomy. We investigated the association between stress hyperglycaemia and clinical outcomes in AIS patients undergoing intravenous thrombolysis (IVT). METHODS: We examined 666 consecutive patients with AIS who underwent IVT from 2006 to 2018. All patients had a glycated haemoglobin level (HbA1c) and fasting venous blood glucose measured within 24 h of admission. Stress hyperglycaemia ratio (SHR) was defined as the ratio of the fasting glucose to the HbA1c. Univariate and multivariate analyses were employed to identify predictors of poor functional outcomes (modified Rankin Scale 3-6 at 3 months) after IVT. RESULTS: Three-hundred and sixty-one patients (54.2%) had good functional outcomes. These patients tended to be younger (60.7 ± 12.7 vs. 70 ± 14.4 years, P < 0.001), male (70.7% vs. 51.5%, P < 0.001), had lower prevalence of atrial fibrillation (13.0% vs. 20.7%, P = 0.008) and lower SHR (0.88 ± 0.20 vs. 0.99 ± 26, P < 0.001). Patients with high SHR (≥0.97) were slightly older than those with low SHR (<0.97) and were more likely to have diabetes mellitus. On multivariate analysis, higher SHR was independently associated with poor functional outcomes (adjusted odds ratio 3.85, 95% confidence interval 1.59-9.09, P = 0.003). CONCLUSION: SHR appears to be an important predictor of functional outcomes in patients with AIS undergoing IVT. This may have important implications on the role of glycaemic control in the acute management of ischaemic stroke.


Assuntos
Isquemia Encefálica , Hiperglicemia , AVC Isquêmico , Acidente Vascular Cerebral , Isquemia Encefálica/complicações , Isquemia Encefálica/tratamento farmacológico , Fibrinolíticos/uso terapêutico , Humanos , Hiperglicemia/tratamento farmacológico , Masculino , Acidente Vascular Cerebral/tratamento farmacológico , Terapia Trombolítica , Resultado do Tratamento
15.
Clin Exp Dermatol ; 47(1): 125-128, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34236705

RESUMO

Tattoos with blue/black ink show good lightening of pigment after treatment with 1064 nm Q-switched (QS) neodymium-doped yttrium-aluminium-garnet (Nd:YAG) laser. In this randomized trial, we compared the efficacy of a novel three pass, one session procedure (R15 method) with a conventional method for treating blue/black tattoos in darker skin types. Tattoos were treated with 1064 nm QS Nd:YAG Laser with a spot size of 4 mm, fluence of 5 J/cm2 and frequency of 5 Hz. The tattoo pigment lightening was comparable with both methods. Thread-like tattoos had significantly better pigment lightening with fewer side effects than the broad band-like tattoos. We would like to recommend the R15 method of the QS Nd:YAG laser for thread-like tattoos, which can save patients' time, cut short the frequency of their hospital visits and, more importantly, decrease the cost involved in it.


Assuntos
Lasers de Estado Sólido/uso terapêutico , Pigmentação da Pele , Pele/efeitos da radiação , Tatuagem , Vesícula/etiologia , Cicatriz/etiologia , Humanos , Lasers de Estado Sólido/efeitos adversos , Lesões por Radiação/etiologia
16.
Phys Chem Chem Phys ; 23(40): 22854-22873, 2021 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34505589

RESUMO

Deep eutectic solvents (DESs) have become ubiquitous in a variety of industrial and pharmaceutical applications since their discovery. However, the fundamental understanding of their physicochemical properties and their emergence from the microscopic features is still being explored fervently. Particularly, the knowledge of transport mechanisms in DESs is essential to tune their properties, which shall aid in expanding the territory of their applications. This perspective presents the current state of understanding of the bulk/macroscopic transport properties and microscopic relaxation processes in DESs. The dependence of these properties on the components and composition of the DES is explored, highlighting the role of hydrogen bonding (H-bonding) interactions. Modulation of these interactions by water and other additives, and their subsequent effect on the transport mechanisms, is also discussed. Various models (e.g. hole theory, free volume theory, etc.) have been proposed to explain the macroscopic transport phenomena from a microscopic origin. But the formation of H-bond networks and clusters in the DES reveals the insufficiency of these models, and establishes an antecedent for dynamic heterogeneity. Even significantly above the glass transition, the microscopic relaxation processes in DESs are rife with temporal and spatial heterogeneity, which causes a substantial decoupling between the viscosity and microscopic diffusion processes. However, we propose that a thorough understanding of the structural relaxation associated to the H-bond dynamics in DESs will provide the necessary framework to interpret the emergence of bulk transport properties from their microscopic counterparts.

17.
J Chem Phys ; 155(2): 024505, 2021 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-34266283

RESUMO

Deep eutectic solvents (DESs) have become a prevalent and promising medium in various industrial applications. The addition of water to DESs has attracted a lot of attention as a scheme to modulate their functionalities and improve their physicochemical properties. In this work, we study the effects of water on an acetamide based DES by probing its microscopic structure and dynamics using classical molecular dynamics simulation. It is observed that, at low water content, acetamide still remains the dominant solvate in the first solvation shell of lithium ions, however, beyond 10 wt. %, it is replaced by water. The increase in the water content in the solvent accelerates the H-bond dynamics by drastically decreasing the lifetimes of acetamide-lithium H-bond complexes. Additionally, water-lithium H-bond complexes are also found to form, with systematically longer lifetimes in comparison to acetamide-lithium complexes. Consequently, the diffusivity and ionic conductivity of all the species in the DES are found to increase substantially. Non-Gaussianity parameters for translational motions of acetamide and water in the DES show a conspicuous decrease with addition of water in the system. The signature of jump-like reorientation of acetamide is observed in the DES by quantifying the deviation from rotational Brownian motion. However, a notable decrease in the deviation is observed with an increase in the water content in the DES. This study demonstrates the intricate connection between H-bond dynamics and various microscopic dynamical parameters in the DES, by investigating the modulation of the former with addition of water.

19.
Rep Prog Phys ; 84(6)2021 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-33740783

RESUMO

Fluids exhibit remarkable variation in their structural and dynamic properties when they are confined at the nanoscopic scale. Various factors, including geometric restriction, the size and shape of the guest molecules, the topology of the host, and guest-host interactions, are responsible for the alterations in these properties. Due to their porous structures, aluminosilicates provide a suitable host system for studying the diffusion of sorbates in confinement. Zeolites and clays are two classes of the aluminosilicate family, comprising very ordered porous or layered structures. Zeolitic materials are important due to their high catalytic activity and molecular sieving properties. Guest molecules adsorbed by zeolites display many interesting features including unidimensional diffusion, non-isotropic rotation, preferred orientation and levitation effects, depending on the guest and host characteristics. These are useful for the separation of hydrocarbons which commonly exist as mixtures in nature. Similarly, clay materials have found application in catalysis, desalination, enhanced oil recovery, and isolation barriers used in radioactive waste disposal. It has been shown that the bonding interactions, level of hydration, interlayer spacing, and number of charge-balancing cations are the important factors that determine the nature of diffusion of water molecules in clays. Here, we present a review of the current status of the diffusion mechanisms of various adsorbed species in different microporous zeolites and clays, as investigated using quasielastic neutron scattering and classical molecular dynamics simulation techniques. It is impossible to write an exhaustive review of the subject matter, as it has been explored over several decades and involves many research topics. However, an effort is made to cover the relevant issues specific to the dynamics of different molecules in microporous zeolites and clay materials and to highlight a variety of interesting features that are important for both practical applications and fundamental aspects.

20.
J Colloid Interface Sci ; 590: 94-102, 2021 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-33524724

RESUMO

Bicontinuous microemulsions (BµEs) are a promising biomembrane mimetic system for investigating the behavior of antimicrobial peptides (AMPs) and their delivery to open wounds to combat antibiotic-resistant microorganisms. The properties of the BµE host are in turn affected by the guest AMP and can deviate from those of the unperturbed BµEs, especially at higher AMP concentrations. Here we report the effect of an archetypal AMP, melittin, over a wide range of concentrations, on the nanoscopic dynamics of BµEs formed by water/sodium dodecyl sulfate (SDS)/1-pentanol/dodecane, investigated using quasi-elastic neutron scattering (QENS). Two distinct motions are observed, namely, (i) the lateral motion of the surfactant on the surface of the oil channels and (ii) the internal motion of the surfactants. It is found that melittin restricts both the lateral and the internal motion, thereby acting as a stiffening agent. The lateral motion is more strongly affected, at low concentration of melittin. The lateral diffusion coefficient decreased sharply, approaching a constant value at higher melittin concentration. These results are in sharp contrast with the recent dynamic light scattering and neutron spin echo results which showed that at the length and time scales longer than those probed in the current work, melittin enhanced the long-range collective and local undulation motions of BµEs. Considered together, our results indicate that incorporation of melittin modulates the dynamics differently depending on the spatial and temporal regimes, in which the dynamics are being probed. The addition of melittin at low concentrations increased the magnitude of the zeta potential, but further increase of the melittin concentration decreased it. This suggests that addition of melittin at low concentrations led to increase in the surfactant concentration, but did not affect the negative charge per surfactant molecule, while further addition of melittin led to ion pairing of melittin with the oppositely charged surfactant. This study therefore demonstrates how the addition of melittin hinders the lateral motion of surfactants as a result of the strong association between melittin and SDS, suggesting that the release of AMPs from BµE-based delivery vehicles may be hindered.


Assuntos
Meliteno , Tensoativos , Emulsões , Dodecilsulfato de Sódio , Água
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA