REVIEW | doi:10.20944/preprints202202.0096.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: Grain boundaries; solute decoration; correlative microscopy; cohesive strength
Online: 7 February 2022 (16:05:39 CET)
Solute decoration at grain boundaries (GB) leads to a number of phenomenon such as changes in interface structure, mobility, cohesion etc. Recent experimental investigations on interfacial segregation in steels are based on microstructural characterisation using two correlative methodologies, namely, Transmission Electron Microscopy-Atom Probe Tomography (APT) and Electron Backscatter Diffraction-APT. Considering the growing interest in this avenue, the present review is aimed at addressing the common adsorption isotherms used for quantifying interfacial segregation and providing an overview of the present state of experimental research in the area of GB segregation in steels. The areas where an understanding of GB segregation may be utilised have also been highlighted with a focus on the experimental challenges associated with understanding GB segregation in steels.
ARTICLE | doi:10.20944/preprints201705.0211.v1
Subject: Environmental And Earth Sciences, Environmental Science Keywords: solute transport, dispersion, hagen-poiseuille flow, non-fickian
Online: 30 May 2017 (07:53:21 CEST)
We present an exact expression for the upscaled dynamic dispersion coefficient (D) for one-dimensional transport by Hagen-Poiseuille flow which is the basis for modeling transport in porous media idealized as capillary tubes. The theoretical model is validated by comparing the breakthrough curves (BTCs) from a 1D advection-dispersion model with dynamic D to that from direct numerical solutions utilizing a 2D advection-diffusion model. Both Taylor dispersion theory and our new theory are good predictors of D at lower Peclet Number (Pe) regime, but gradually fail to capture most parts of BTCs as Pe increases. However, our model generally predicts the mixing and spreading of solutes better than Taylor’s theory since it covers all transport regimes from molecular diffusion, through anomalous transport, and to Taylor dispersion. The model accurately predicts D based on the early part of BTCs even at relatively high Pe regime (~62) where the Taylor’s theory fails. Furthermore, the model allows for calculation of the time scale that separates Fickian from non-Fickian transport. Therefore, our model can readily be used to calculate dispersion through short tubes of arbitrary radii such as the pore throats in a pore network model.
REVIEW | doi:10.20944/preprints202211.0062.v1
Subject: Chemistry And Materials Science, Medicinal Chemistry Keywords: membrane transporter; SLC; solute carrier; drug design; pharmacokinetics; prodrug; nanoparticle; bile acids
Online: 3 November 2022 (01:09:54 CET)
Transmembrane transport of small organic and inorganic molecules is one of the cornerstones of cellular metabolism. Among transmembrane transporters, solute carrier (SLC) proteins form the largest, albeit very diverse, superfamily with over 400 members. It has been early on recognized that xenobiotics can directly interact with SLCs and that this interaction can fundamentally determine their efficacy, including bioavailability and intertissue distribution. Apart from the well-established prodrug strategy, the chemical ligation of transporter substrates to nanoparticles of various chemical composition has recently been used as a means to enhance their targeting or absorption. In this review, we summarize efforts in drug design exploiting interactions with specific SLC transporters to optimize their therapeutic effects. Furthermore, we describe current and future challenges as well as new directions for the advanced development of therapeutics that target SLC transporters.
COMMUNICATION | doi:10.20944/preprints201908.0192.v1
Subject: Chemistry And Materials Science, Applied Chemistry Keywords: caffeine; colloidal coffee; optical absorption; pH sensor; solute-solvent interactions; UV absorber
Online: 19 August 2019 (04:14:30 CEST)
Coffee and caffeine have been used as solar absorbers and also to increase the thermal stability and efficiency of perovskite solar cells. In this work, we report the sensing of extremely alkaline pH by colloidal coffee solution aided by generation of an optical absorption band in the near-UV region. This generation of absorption band could be explained by the orientation induced dipole-dipole interactions arising from differing caffeine-solvent interactions with varying pH. Such a generation leads to the lowering of direct as well as indirect bandgaps from 4 eV-->2.8 eV& 3.4 eV-->2.5 eV, respectively. We also estimate the changes in optical energy storage efficiency, inferring it to be highest for pH 11 having the highest intensity of the generated absorption band (λ_abs≈360 nm). With these observations and further deductions, the work reported in this paper would be of immense interest to the researchers working in the field of development of chemical pH sensors and also in the development of novel UV absorbers.
ARTICLE | doi:10.20944/preprints201901.0033.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: W-O alloy, interstitial solid solution, screw dislocations, solute diffusion, stress coupling
Online: 4 January 2019 (08:42:36 CET)
Plastic flow in body-centered cubic (bcc) alloys is governed by the thermally-activated screw dislocation motion. In bcc interstitial solid solutions, solute diffusion can occur at very fast rates owing to low migration energies and solute concentrations. Under mechanical loading, solutes may move on the same or similar time scale as dislocations glide, even at low temperatures, potentially resulting in very rich co-evolution processes that may have important effects in the overall material response. It is therefore important to accurately quantify the coupling between interstitial impurities and dislocations, so that larger-scale models can correctly account for their (co)evolution. In this paper, we use electronic structure calculations to obtain the energetics of oxygen diffusion under stress and its interaction energy with screw dislocation cores in bcc tungsten. We find that oxygen atoms preferentially migrate from tetrahedral to tetrahedral sites with an energy of 0.2 eV. This energy couples only weakly to hydrostatic and deviatoric deformations, with activation volumes of less than $0.02$ and $0.2b^3$, respectively. The strongest effect is found for the inelastic interaction between O atoms and screw dislocation cores, which leads to attractive energies on the order of 1.5 eV and a structural transformation of the screw dislocation core from an `easy' to a `hard' core configuration
REVIEW | doi:10.20944/preprints202111.0482.v1
Subject: Environmental And Earth Sciences, Environmental Science Keywords: Solute Transport; Bio-geo-chemical reactions; Dispersion; Mixing; Heterogeneity; Effective transport; Microbial communities, Biofilms
Online: 25 November 2021 (15:53:41 CET)
Reactive transport (RT) couples bio-geo-chemical reactions and transport. RT is important to understand numerous scientific questions and solve some engineering problems. RT is highly multidisciplinary, which hinders the development of a body of knowledge shared by RT modelers and developers. The goal of this paper is to review the basic conceptual issues shared by all RT problems, so as to facilitate advance along the current frontier: biochemical reactions. To this end, we review the basic equations to point that chemical systems are controlled by the set of equilibrium reactions, which are easy to model, but whose rate is controlled by mixing. Since mixing is not properly represented by the standard advection-dispersion equation (ADE), we conclude that this equation is poor for RT. This leads us to review alternative transport formulations, and the methods to solve RT problems using both the ADE and alternative equations. Since equilibrium is easy, difficulties arise for kinetic reactions, which is especially true for biochemistry, where numerous frontiers are open (how to represent microbial communities, impact of genomics, effect of biofilms on flow and transport, etc.). We conclude with the basic 10 issues that we consider fundamental for any conceptually sound RT effort.
ARTICLE | doi:10.20944/preprints202001.0269.v1
Subject: Chemistry And Materials Science, Metals, Alloys And Metallurgy Keywords: Niobium-titanium microalloyed steel; Electrical resistivity; Atom probe tomography; Solute niobium; Scanning transmission electron microscopy
Online: 23 January 2020 (16:15:44 CET)
Microalloying of low carbon steel with niobium (Nb) and titanium (Ti) is standardly applied in high-strength low-alloy (HSLA) steels enabling austenite conditioning during thermo-mechanical controlled processing (TMCP), which results in pronounced grain refinement in the finished steel. The metallurgical effects of microalloying elements are related solute drag and precipitate particle pinning, both acting on the austenite grain boundary thereby delaying or suppressing recrystallization of the deformed grain. In that respect it is important to better understand the precipitation kinetics as well as the precipitation sequence in a typical Nb-Ti-microalloyed steel. Various characterization methods have been utilized in this study for tracing microalloy precipitation after simulating different austenite TMCP conditions in a Gleeble apparatus. Atom probe tomography (APT), scanning transmission electron microscopy in a focused ion beam equipped scanning electron microscope (STEM-on-FIB) and electrical resistivity measurements provide complementary information on the precipitation status and are correlated with each other. It will be demonstrated that accurate electrical resistivity measurements can monitor the general consumption of solute microalloys (Nb) during hot working which was complemented by APT measurements of the steel matrix. On the other hand, STEM revealed that a large part of Nb-containing particles during hot working are co-precipitated with titanium during cooling from the austenitizing temperature. Precipitates that form during cooling or isothermal holding can be distinguished from strain-induced precipitates by corroborating STEM measurements with APT results. APT specifically allows obtaining detailed information about the chemical composition of precipitates as well as the distribution of elements inside the particle. Electrical resistivity measurement, on the contrary, provides macroscopic information on the progress of precipitation and can be calibrated by APT. The current paper highlights the complementarity of these methods and shows first results within the framework of a larger study on strain-induced precipitation.
ARTICLE | doi:10.20944/preprints202306.1933.v1
Subject: Biology And Life Sciences, Ecology, Evolution, Behavior And Systematics Keywords: Andes mountains; drought tolerance; elevation; solute leakage; tropical forest; understory plants; turgor loss point; cuticular conductance
Online: 27 June 2023 (15:02:29 CEST)
Little is known about how differences in water availability within the “super humid” tropics can influence the distribution of understory plant species and the composition of understory plant communities. We investigated variation in the physiological drought tolerances of understory plants and plant communities across a large elevation and precipitation gradient. We established 58 understory plots along a gradient of 400 – 3600 m asl elevation and 1000 – 6000 mm yr-1 rainfall in and around Manu National Park in southeastern Peru. Within the plots, we sampled all understory woody plants and measured three metrics of physiological leaf drought tolerance - turgor loss point (TLP), cuticular conductance (Gmin), and solute leakage (SL) - and assessed how the community-level means of these traits related to mean annual precipitation (MAP) and elevation (in the study gradient temperature decreases linearly and vapor pressure deficit increases monotonically with elevation). We did not find any correlations between the three metrics of leaf drought tolerance, suggesting that they represent independent strategies for coping with low water availability. Despite being widely used metrics of leaf drought tolerance, neither TLP nor Gmin showed any significant relationships with elevation or MAP. In contrast, SL, which has only recently been developed for use in ecological field studies, increased significantly at higher precipitations and at lower elevations (i.e., plants in colder and drier habitats have lower SL, indicating greater drought tolerances). Our results illustrate that differences in water availability may play a strong role in structuring plant communities even in in the wet tropics and highlight the potential for SL assays to be an efficient and effective tool for measuring drought tolerances in the field.