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"Viscometry"
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Impact of Ergothioneine, Hercynine, and Histidine on Oxidative Degradation of Hyaluronan and Wound Healing
2020
A high-molecular weight hyaluronan is oxidatively degraded by Cu(II) ions and ascorbate—the so called Weissberger biogenic oxidative system—which is one of the most potent generators of reactive oxygen species, namely •OH radicals. Ergothioneine, hercynine, or histidine were loaded into chitosan/hyaluronan composite membranes to examine their effect on skin wound healing in ischemic rabbits. We also explored the ability of ergothioneine, hercynine, or histidine to inhibit hyaluronan degradation. Rotational viscometry showed that ergothioneine decreased the degree of hyaluronan radical degradation in a dose-dependent manner. While histidine was shown to be potent in scavenging •OH radicals, however, hercynine was ineffective. In vivo results showed that the addition of each investigated agent to chitosan/hyaluronan membranes contributed to a more potent treatment of ischemic skin wounds in rabbits compared to untreated animals and animals treated only with chitosan/hyaluronan membranes.
Journal Article
Antioxidant vs. Prooxidant Properties of the Flavonoid, Kaempferol, in the Presence of Cu(II) Ions: A ROS-Scavenging Activity, Fenton Reaction and DNA Damage Study
by
Alhazza, Ibrahim
,
Simunkova, Miriama
,
Alwasel, Saleh H.
in
Antioxidants
,
Binding sites
,
Deoxyribonucleic acid
2021
Kaempferol is a flavonoid that occurs in tea and in many vegetables and fruits, including broccoli, cabbage, beans, grapes, apples, and strawberries. The efficacy of Kaempferol has been demonstrated in the treatment of breast, esophageal, cervical, ovarian, and liver cancers and leukemia, which very likely arises from its prooxidant properties and the activation of pro-apoptotic pathways. Indeed, this matter has already been the focus of a number of published studies and reviews. The aim of the present study was to elucidate the antioxidant vs. prooxidant properties of flavonoids in the presence of the redox-active metal, copper (II) ion, by means of the Fenton reaction. The specific motivation of this work is that, since an increased level of Cu(II) ions is known to be associated with many disease states such as neurological conditions (Alzheimer’s disease) and cancer, any interaction between these ions and flavonoids might affect the outcome of therapeutic uses of the latter. The structure of the Cu-kaempferol complex in DMSO was investigated by means of low temperature EPR spectroscopy, which confirmed the existence of at least two distinct coordination environments around the copper (II) ion. UV vis-spectra of kaempferol and its Cu(II) complex in DMSO revealed an interaction between the 5-OH (A ring) group and the 4-CO (C ring) group of kaempferol with Cu(II) ions. An ABTS assay confirmed that kaempferol acted as an effective radical scavenger, and that this effect was further enhanced in the form of the Cu(II)-kaempferol complex. Quantitative EPR spin trapping experiments, using DMPO as the spin trap, confirmed suppression of the formation of a mixture of hydroxyl, superoxide, and methyl radicals, in a Fenton reaction system, upon coordination of kaempferol to the redox-active Cu(II) ions, by 80% with respect to the free Cu(II) ions. A viscometric study revealed a better DNA-intercalating ability of the Cu-kaempferol complex than for free kaempferol, essential for conferring anticancer activity of these substances. The results of the viscometric measurements were compared with those from a DNA damage study of Cu-kaempferol complexes in a Fenton reaction system, using gel electrophoresis. At low concentrations of kaempferol (Cu–kaempferol ratios of 1:1 and 1:2), a very weak protective effect on DNA was noted, whereas when kaempferol was present in excess, a significant DNA-protective effect was found. This can be explained if the weakly intercalated kaempferol molecules present at the surface of DNA provide protection against attack by ROS that originate from the Fenton reaction involving intercalated Cu(II)-kaempferol complexes. Following the application of ROS scavengers, L-histidine, DMSO, and SOD, gel electrophoresis confirmed the formation of singlet oxygen, hydroxyl radicals, and superoxide radical anions, respectively. We propose that the prooxidant properties of Cu-kaempferol complexes may provide anticancer activity of these substances. When present in excess, kaempferol displays antioxidant properties under Cu-Fenton conditions. This suggests that kaempferol might prove a suitable candidate for the prevention or treatment of oxidative stress related medical conditions that involve a disturbed metabolism of redox metals such as copper, for example, Menkes disease, and neurological disorders, including Alzheimer’s disease. For the potential use of kaempferol in clinical practice, it will be necessary to optimize the dose size and critical age of the patient so that this flavonoid may be beneficial as a preventive drug against cancer and neurological disorders.
Journal Article
Capillary Viscometry for Routine Measurements of Newtonian Liquids
by
Fareleira, João M. N. A.
,
Sequeira, Maria C. M.
,
Caetano, Fernando J. P.
in
Atmospheric pressure
,
Blood vessels
,
Calibration
2024
Viscosity is a thermophysical property of paramount importance, being essential for many scientific and industrial applications. The most common instruments for its measurement are glass capillary viscometers. Therefore, the use of capillary viscometers is widespread both in industry and in research. The range of viscosities of interest range from lower than that of water to several orders of magnitude higher values, the measurement of which requires different capillary viscometers. Most of the practical applications concern routine instruments, mainly for quality control. One main issue for the utilization of capillary viscometers relates to the need for their calibration, assuring its traceability to the water primary viscosity standard, to certify its worldwide validity. The present paper focuses on capillary instruments dedicated to perform viscosity measurements on Newtonian organic liquids at atmospheric pressure, as it is assumed that is the most widespread type of application for these viscometers. Capillary viscometry has a completely well-defined working equation, namely, the Hagen–Poiseuille equation. However, the practical performance of the measuring instruments deviates from that working equation. Most of those deviations are currently considered by many users. However, some of those deviations have not reached that status yet, like those concerning the effects due to the surface tension of the sample on the measurements. All these aspects are summarized and analyzed in the present article, together with a brief general description of the most common types of capillary viscometers, namely, the Ostwald and the constant-level or Ubbelohde instruments.
Journal Article
Dynamic Viscosity of the NaF-KF-NdF3 Molten System
by
Rudenko, Alexei
,
Tkacheva, Olga
,
Kataev, Alexander
in
Datasets
,
Exponential equations
,
Fluorides
2022
The dynamic viscosity (η) of the molten system (NaF-KF)eut-NdF3 containing NdF3 in an amount from 0 to 15 mol.% was studied by rotational viscometry using a high-temperature rheometer, FRS 1600. Viscosity measurements were carried out in the temperature range from liquidus to 1153 K. The measurement procedure was tested on the (LiF-NaF-KF)eut melt. The choice of the parameter shear rate was carried out according to the viscosity and flow curves. Viscosity does not depend on shear rate, and therefore the investigated melts behave like Newtonian fluids, in the range of 9–19 s−1. The experimentally obtained viscosity values for (NaF-KF)eut-NdF3 melts in a wide temperature range are described by an exponential equation. In the coordinates ln(η) = f(1/T), they are straight lines; however, their temperature coefficients are noticeably different, which indicates significant impacts of composition and temperature.
Journal Article
Reproducible mini-slump test procedure for measuring the yield stress of cementitious pastes
by
Tan, Zhijun
,
Provis, John L.
,
Bernal, Susan A.
in
Building construction
,
Building Materials
,
Cements
2017
The mini-slump test is a fast, inexpensive and widely adopted method for evaluating the workability of fresh cementitious pastes. However, this method lacks a standardised procedure for its experimental implementation, which is crucial to guarantee reproducibility and reliability of the test results. This study investigates and proposes a guideline procedure for mini-slump testing, focusing on the influence of key experimental (mixing and testing) parameters on the statistical performance of the results. The importance of preparation of always testing at the same time after mixing, testing each batch once rather than conducting multiple tests on a single batch of material, is highlighted. A set of alkali-activated fly ash-slag pastes, spanning from 1 to 75 Pa yield stresses, were used to validate the test method, by comparison of calculated yield stresses with the results obtained using a conventional vane viscometer. The proposed experimental procedure for mini-slump testing produces highly reproducible results, and the yield stress calculated from mini-slump values correlate very well with those measured by viscometer, in the case of fresh paste of pure shear flow. Mini-slump testing is a reliable method that can be utilised for the assessment of workability of cements.
Journal Article
Spreading of a viscous drop after impact onto a spherical target
by
Abbot, Mete
,
Lannert, Max
,
Bakshi, Shamit
in
Asymptotic methods
,
Axisymmetric flow
,
Boundary layers
2024
Drop collision with a solid particle is a ubiquitous phenomenon in a wide range of applications, including rain, spray coating, cooling or cleaning, particle encapsulation, inkjet printing, and additive manufacturing. Understanding the dynamics of drop collision is essential for optimizing these processes. In this study, we present a comprehensive experimental and analytical investigation of non-axisymmetric as well as axisymmetric drop impact on a solid particle. We use a high-speed video system to visualize the drop profile during the impact, and measure the drop height and spreading diameter for different liquid viscosities, ratios of the target to drop diameters, offsets, and various other impact parameters. We then develop a theoretical model for drop spreading on a solid spherical particle that relies on the formulation of a remote asymptotic solution for the inviscid flows, generated by non-axisymmetric drop impact. Next, the viscous effects in a thin viscous boundary layer are considered, which allows the formulation of an expression for the residual lamella thickness and maximum spreading. The theoretically predicted evolution of the lamella thickness, the residual film thickness, and the maximum spreading angle agree well with the experimental data presented in this work and the literature. Finally, we present a novel approach for in situ measurement of liquid viscosity, drop impact viscometry, at high shear rates via a single drop impact experiment, with potential application in industries where non-Newtonian drops play a major role, such as pesticide spraying, paint droplet spreading, blood drop impact and fuel injectors.
Journal Article
Experimental Constraints on the Rheology of Lavas From 2021 Cumbre Vieja Eruption (La Palma, Spain)
2023
The 2021 Tajogaite eruption of Cumbre Vieja (La Palma, Spain) was typified by the emission of low viscosity lavas that flowed at high velocities and inundated a large area. We experimentally investigated the rheological evolution of melt feeding the eruption through concentric cylinder viscometry to understand the exceptional flowing ability of these lavas and constrain its emplacement dynamics. We conducted a set of cooling deformation experiments at different cooling rates (from 0.1 to 10 °C/min), and isothermal deformation experiments at subliquidus dwell temperatures between 1225 and 1175°C. All experiments were conducted at a shear rate of 10 s−1. Results show that disequilibrium crystallization and its timescale fundamentally control the rheological evolution of the melt, resulting in different rheological response to deformation of the crystal‐bearing magmatic suspension. Integrating rheological data with field observations allows us to shed light on the mechanisms that govern the high flowability of these lavas. Plain Language Summary Understanding and modeling the mechanisms controlling the inundation ability of lava flows is pivotal for hazard assessment and mitigation of related risk. Lavas flowing across the Earth's surface experience different cooling conditions. These conditions are related to the thermal gradients generated at various levels within the flow's thickness. Especially for extremely fluid magmas such as those erupted at Cumbre Vieja, the different cooling paths (and different disequilibrium conditions) that lava flows experience strongly influence the crystallization processes. Both cooling and crystallization produce an increase of lava viscosity, hindering lava flowability. If crystallization occurs over timescales shorter than those of cooling, the presence of crystals may give rise to more complex flow behavior and emplacement style, including flow rupture and separation. Such conditions may favor the development of flow decoupling and lava tunnel formation. In this study we experimentally investigate the viscosity evolution of the Tajogaite lavas and the transition from pure viscous flow to more complex responses to deformation. Then, we use our data set in concert with field observation to constrain the dynamics governing the emplacement style of these lavas. Key Points High‐T deformation experiments characterize the rheology of Cumbre Vieja lavas under both disequilibrium and equilibrium conditions Two different rheological responses are observed in relation to the increased disequilibrium conditions at which the melt is subjected Integration of experimental and field data permits to understand the mechanisms that enhance the flowing ability of these lavas
Journal Article
Red blood cell aggregates and their effect on non-Newtonian blood viscosity at low hematocrit in a two-fluid low shear rate microfluidic system
by
Fenech, Marianne
,
Mehri, Rym
,
Mavriplis, Catherine
in
Agglomeration
,
Aggregates
,
Biology and Life Sciences
2018
Red blood cells (RBCs) are the most abundant cells in human blood. Remarkably RBCs deform and bridge together to form aggregates under very low shear rates. The theory and mechanics behind aggregation are, however, not yet completely understood. The main objective of this work is to quantify and characterize RBC aggregates in order to enhance the current understanding of the non-Newtonian behaviour of blood in microcirculation. Suspensions of human blood were flowed and observed in vitro in poly-di-methyl-siloxane (PDMS) microchannels to characterize RBC aggregates. These microchannels were fabricated using standard photolithography methods. Experiments were performed using a micro particle image velocimetry (μPIV) system for shear rate measurements, coupled with a high-speed camera for flow visualization. RBC aggregate sizes were quantified in controlled and measurable shear rate environments for 5, 10 and 15% hematocrit. Aggregate sizes were determined using image processing techniques, while apparent viscosity was measured using optical viscometry. For the samples suspended at 5% H, aggregate size was not strongly correlated with shear rate. For the 10% H suspensions, in contrast, lowering the shear rate below 10 s-1 resulted in a significant increase of RBC aggregate sizes. The viscosity was found to increase with decreasing shear rate and increasing hematocrit, exemplifying the established non-Newtonian shear-thinning behaviour of blood. Increase in aggregation size did not translate into a linear increase of the blood viscosity. Temperature was shown to affect blood viscosity as expected, however, no correlation for aggregate size with temperature was observed. Non-Newtonian parameters associated with power law and Carreau models were determined by fitting the experimental data and can be used towards the simple modeling of blood's non-Newtonian behaviour in microcirculation. This work establishes a relationship between RBC aggregate sizes and corresponding shear rates and one between RBC aggregate sizes and apparent blood viscosity at body and room temperatures, in a microfluidic environment for low hematocrit. Effects of hematocrit, shear rate, viscosity and temperature on RBC aggregate sizes have been quantified.
Journal Article
Assessing rheometry for measuring the viscosity-average degree of polymerisation of cellulose in paper degradation studies
by
Hoefnagels, Johan P. M
,
Maraghechi, Siavash
,
Bosco, Emanuela
in
Cellulose
,
Degradation
,
Degree of polymerization
2023
In paper degradation studies, the viscosity-average degree of polymerisation (DPv) is often used as a key indicator of the extent of degradation of cellulosic paper. DPv can be deduced from the viscosity of dilute paper solutions, as typically measured through glass capillary viscometry. The current study proposes an efficient, alternative method to evaluate DPv of cellulosic paper, which is based on rotational rheometry. The proposed methodology relies on the application of a shear flow in a thin film of cellulose solution to measure its dynamic viscosity, from which DPv can be subsequently derived in a straightforward fashion. Rheometry allows to measure the viscosity for a range of shear rates, which results in multiple DPv evaluations per sample, and thus in statistically representative data from an individual test. Further, rheometry typically requires considerably less paper mass per test than glass capillary viscometry, which makes the method attractive for paper degradation studies with limited sample availability. Also, rheometry measurements are less work-intensive than glass capillary viscometry measurements. The rheometry method has been applied to 4 hygrothermally aged cellulose paper samples and the unaged counterpart. The measurement results regarding the age-dependency of DPv and the number of cellulose chain scissions are compared to those obtained by glass capillary viscometry, showing a very good agreement. At a longer ageing time, both experimental methods reveal a non-linear decrease in time of DPv, and a non-linear increase in time of the number of cellulose chain scissions, which indicate that the cellulose ageing process is realistically captured. The agreement in measurement results further demonstrates that rheometry is an easy-to-use, accurate and efficient alternative for DPv measurements by glass capillary viscometry.
Journal Article
Utilization of CO2 in supercritical conditions for the synthesis of cyclic poly (N-isopropylacrylamide) via emulsion and homogeneous reactions
2022
In this study, cyclic poly (N-isopropylacrylamide) (cPNIPAAM) was synthesized in supercritical carbon dioxide (SC-CO
2
) using emulsion and homogeneous reactions for the first time. This was accomplished by applying free radical polymerization and nitroxide compounds to produce low molecular weight precursors in the SC-CO
2
solvent. The cyclization reaction occurred in a homogeneous phase in the SC-CO
2
solvent, with dimethylformamide (DMF) serving as a co-solvent for dissolving the linear precursor. This reaction was also conducted in emulsion of SC-CO
2
in water. The effects of pressure and time on the morphology, molecular weight, and yield of a difunctionalized chain were investigated, where a higher pressure led to a higher yield. The maximum yield was 64% at 23 MPa, and the chain molecular weight (M
w
) was 4368 (gr/mol). Additionally, a lower pressure reduced the solubility of materials (particularly terminator) in SC-CO
2
and resulted in a chain with a higher molecular weight 9326 (gr/mol), leading to a lower conversion. Furthermore, the effect of cyclization reaction types on the properties of cyclic polymers was investigated. In cyclic reactions, the addition of DMF as a co-solvent resulted in the formation of a polymer with a high viscosity average molecular weight (M
v
) and a high degree of cyclization (100%), whereas the CO
2
/water emulsion resulted in the formation of a polymer with a lower M
v
and increased porosity. Polymers were characterized by
1
HNMR, FTIR, DSC, TLC, GPC, and viscometry tests. The results were presented and thoroughly discussed.
Journal Article