How Water's Properties Are Encoded in Its Molecular Structure and Energies.

How are water's material properties encoded within the structure of the water molecule? This is pertinent to understanding Earth's living systems, its materials, its geochemistry and geophysics, and a broad spectrum of its industrial chemistry. Water has distinctive liquid and solid properties: It is highly cohesive. It has volumetric anomalies-water's solid (ice) floats on its liquid; pressure can melt the solid rather than freezing the liquid; heating can shrink the liquid. It has more solid phases than other materials. Its supercooled liquid has divergent thermodynamic response functions. Its glassy state is neither fragile nor strong. Its component ions-hydroxide and protons-diffuse much faster than other ions. Aqueous solvation of ions or oils entails large entropies and heat capacities. We review how these properties are encoded within water's molecular structure and energies, as understood from theories, simulations, and experiments. Like simpler liquids, water molecules are nearly spherical and interact with each other through van der Waals forces. Unlike simpler liquids, water's orientation-dependent hydrogen bonding leads to open tetrahedral cage-like structuring that contributes to its remarkable volumetric and thermal properties

Stainless Steel Foil-Based Label-Free Modular Thin-Film Electrochemical Detector for Solvent Identification

Most organic solvents are colorless liquids, usually stored in sealed containers. In many cases, their identification depends on the appropriate description on the container to prevent mishandling or mixing with other materials. Although modern laboratories rely heavily on identification technologies, such as digitized inventories and spectroscopic methods (e.g., NMR or FTIR), there may be situations where these cannot be used due to technical failure, lack of equipment, or time. An example of a portable and cost-effective solution to this problem is an electrochemical sensor. However, these are often limited to electrochemical impedance spectroscopy (EIS) or voltammetry methods. To address this problem, we present a novel modular electrochemical sensor for solvent identification that can be used with either an EIS-enabled potentiostat/galvanostat or a simple multimeter. A novel method of fabricating and using a sensor consisting of a thin-film coating of an organic substance on a stainless-steel electrode substrate is presented. The differences in the solubility of the thin film in different solvents are used to distinguish between common organic solvents such as water, ethanol, and tetrahydrofuran

Modulating role of co-solutes in complexation between bovine serum albumin and sodium polystyrene sulfonate

The action of three types of co-solutes: (i) salts (NaCl, NaBr, NaI), (ii) polymer (polyethylene glycolPEG-400, PEG-3000, PEG-20000), and (iii) sugars (sucrose, sucralose) on the complexation between bovine serum albumin (BSA) and sodium polystyrene sulfonate (NaPSS) was studied. Three critical pH parameters were extracted from the pH dependence of the solution’s turbidity: pH$_c$ corresponding to the formation of the soluble complexes, pH$_Φ$ corresponding to the formation of the insoluble complexes, and pH$_{opt}$ corresponding to the charge neutralization of the complexes. In the presence of salts, the formation of soluble and insoluble complexes as well as the charge neutralization of complexes was hindered, which is a consequence of the electrostatic screening of attractive interactions between BSA and NaPSS. Distinct anion-specific trends were observed in which the stabilizing effect of the salt increased in the order: NaCl < NaBr < NaI. The presence of PEG, regardless of its molecular weight, showed no measurable effect on the formation of soluble complexes. PEG-400 and PEG-3000 showed no effect on the formation of insoluble complexes, but PEG-20000 in high concentrations promoted their formation due to the molecular crowding effect. The presence of sugar molecules had little effect on BSA-NaPSS complexation. Sucralose showed a minor stabilizing effect with respect to the onset of complex formation, which was due to its propensity to the protein surface. This was confirmed by the fluorescence quenching assay (Stern-Volmer relationship) and all-atom MD simulations. This study highlights that when evaluating the modulatory effect of co-solutes on protein-polyelectrolyte interactions, (co-solute)-protein interactions and their subsequent impact on protein aggregation must also be considered

Zaupanje med politiko, stroko in javnostjo

Besedilo predstavlja sociotehnološke vidike izvedbe zanesljivih, transparentnih in družbeno sprejetih e-volitev. Ključni elementi so: dvotočkovni sistem preverjanja istovetnosti in varen prenos podatkov, možnost ponovne oddaje glasu po sistemu Zadnji glas velja, anonimnost glasu, odprtokodna metoda razvoja ter jasen in pregleden uporabniški vmesnik in podporni sistem, ki temelji na dvosmerni komunikaciji. Le z vključitvijo politike, stroke in javnosti v načrtovanje in izvedbo e-volitev dosežemo pozitivno implementacijo le-teh v praksi.The text considers the socio-technological aspects of reliable, transparent and socially acceptable e-voting. The key elements are: a two-point system of identity verification and a safe data transfer, the possibility of casting a vote according to the Last Vote Counts system, voter anonymity, an open source development method and a clear and transparent user interface and support system based on two-way communication. Only by including politicians, experts and the public in the development and realisation of e-voting can we achieve its positive implementation

Biomolecular complexation on the “wrong side”

In the protein purification, drug delivery, food industry, and biotechnological applications involving protein−polyelectrolyte complexation, proper selection of co-solutes and solution conditions plays a crucial role. The onset of (bio)macromolecular complexation occurs even on the so-called “wrong side” of the protein isoionic point where both the protein and the polyelectrolyte are net like-charged. To gain mechanistic insights into the modulatory role of salts (NaCl, NaBr, and NaI) and sugars (sucrose and sucralose) in protein−polyelectrolyte complexation under such conditions, interaction between bovine serum albumin (BSA) and sodium polystyrene sulfonate (NaPSS) at pH = 8.0 was studied by a combination of isothermal titration calorimetry, fluorescence spectroscopy, circular dichroism, and thermodynamic modeling. The BSA−NaPSS complexation proceeds by two binding processes (first, formation of intrapolymer complexes and then formation of interpolymer complexes), both driven by favorable electrostatic interactions between the negatively charged sulfonic groups (−SO$_3^−$) of NaPSS and positively charged patches on the BSA surface. Two such positive patches were identified, each responsible for one of the two binding processes. The presence of salts screened both short-range attractive and long-range repulsive electrostatic interactions between both macromolecules, resulting in a nonmonotonic dependence of the binding affinity on the total ionic strength for both binding processes. In addition, distinct anion-specific effects were observed (NaCl < NaBr < NaI). The effect of sugars was less pronounced: sucrose had no effect on the complexation, but its chlorinated analogue, sucralose, promoted it slightly due to the screening of long-range repulsive electrostatic interactions between BSA and NaPSS. Although short-range non-electrostatic interactions are frequently mentioned in the literature in relation to BSA or NaPSS, we found that the main driving force of complexation on the “wrong side” are electrostatic interactions

Towards an accurate method for column void volume determination using liquid chromatography-mass spectrometry

Prediction of analyte retention times requires prior knowledge of the column void volume, the measurement of which is still highly contested within the literature and therefore experimental based prediction is often used. In this study, we investigated deuterated acetonitrile as an isotopically labelled mobile phase component to observe its elution behaviour in a binary mixture with water at 25 different mobile phase compositions (from 5 to 95 vol. % of acetonitrile), on two stationary phases (C8 and C18), and at two temperatures (30 and 40 ◦C) using LC-MS. The same experimental design was additionally used for three commonly used neutral void volume markers: uracil, phloroglucinol and N,N-dimethylformamide. Temperature was observed to influence the elution of acetonitrile in an inversely proportional manner with higher temperatures coinciding with lower elution times. By utilizing a three-way ANOVA, the composition of the mobile phase has been shown to have a significant effect on deuterated acetonitrile and other investigated void volume markers, demonstrating the fact that both void volume markers and acetonitrile itself exhibit retention-like behaviour. Excess adsorption isotherms for acetonitrile were calculated using deuterated acetonitrile elution data. The comparison of void volumes, obtained with conventional neutral void volume markers, revealed the former to be 24–36% lower than the void volume obtained using deuterated acetonitrile, as an isotopically labelled mobile phase component. For awater:acetonitrile mobile phase, the minor disturbance method using deuterated acetonitrile to obtain an integral average void volume (2.08 and 2.05 mL for C18 at 30 and 40 ◦C, respectively and 2.16 and 2.13 mL for C8 at 30 and 40 ◦C, respectively) was found to be the most appropriate method for determining the elusive column void volume

Electrochromic device demonstrator from household materials

Electrochromism encompasses reversible changes of material’s optical properties (color, opacity) under the influence of an external electric current or applied voltage. The effect has been known for decades, but its importance continues to grow due to the rapid development of smart systems and the accompanying demand to build devices that consume less power. Most commercial electrochromic devices (ECDs) require sophisticated chemicals and advanced material preparation techniques. Also, the demonstration of electrochromism in chemistry classes mainly uses expensive WO$_3$ films, intrinsically conductive polymers, and/or optically transparent electrodes (OTEs). The aim of this article is to present a simple and fast educational method to build ECDs from household materials without the need for OTEs: unsharpened kitchen knives are used as electrodes, curcumin from turmeric is used as the electrochromic dye, and baking soda is used as the electrolyte. The laboratory experiments presented will help students gain a deeper understanding of the fundamentals of electrochemistry (electrolysis, pH change) and electrochromism (in our case, color changes due to pH-induced keto-enol tautomerism of curcumin)

Use of different metal oxide coatings in stainless steel based ECDs for smart textiles

Electrochromism is the ability of a material to selectively change its coloration under the influence of an external electric current/potential and maintain it even after the power source has been disconnected. Devices that use such a mechanism are known as electrochromic devices (ECDs). Over the years, significant effort has been invested into the development of flexible ECDs. Such electrochromic tapes or fibers can be used as smart textiles. Recently, we utilized a novel geometrical approach in assembling electrochromic tapes which does not require the use of optically transparent electrodes. The so-called inverted sandwich ECD configuration can employ various colorchanging mechanisms, e.g., intercalation, redox reactions of electrolytes or reactions on electrode surfaces. One of the most frequently used electrochromic metal oxides is WO$_3$. However, other metal oxides with different coloration responses also exist. In this paper, we explore the use of V$_2$O$_5$ and TiO$_2$ in metal-tape-based ECDs in the inverted sandwich configuration and compare their performance with WO$_3$-based devices. Morphological features of metal oxide thin layers were investigated with scanning electron microscopy (SEM), and the performance of the tapes was investigated electrochemically and spectroscopically. We demonstrate that well-established preparation techniques (e.g., sol–gel synthesis) along with coating approaches (e.g., dipping) are adequate to prepare optically nontransparent fiber electrodes. Depending on the metal oxide, flexible electrochromic fiber devices exhibiting different coloration patterns can be assembled. Devices with TiO$_2$ showed little coloration response, while much better performance was achieved in the case of V$_2$O$_5$ and WO$_3$ ECDs

Influence of low molecular weight salts on the viscosity of aqueous-buffer bovine serum albumin solutions

Pharmaceutical design of protein formulations aims at maximum efficiency (protein concentration) and minimum viscosity. Therefore, it is important to know the nature of protein-protein interactions and their influence on viscosity. In this work, we investigated the dependence of the viscosity of BSA in an aqueous 20 mM acetate buffer at pH = 4.3 on protein concentration and on temperature (5–45 °C). The viscosity of the solution increased with protein concentration and was 230% higher than the viscosity of the protein-free formulation at 160 mg/mL. The viscosity decreased by almost 60% in the temperature range from 5 to 45 °C. The agreement of the modified Arrhenius theory with experiment was quantitative, whereas a hard-sphere model provided only a qualitative description of the experimental results. We also investigated the viscosity of a 100 mg/mL BSA solution as a function of the concentration of added low molecular weight salts (LiCl, NaCl, KCl, RbCl, CsCl, NaBr, NaI) in the range of salt concentrations up to 1.75 mol/L. In addition, the particle size and zeta potential of BSA-salt mixtures were determined for solutions containing 0.5 mol/L salt. The trends with respect to the different anions followed a direct Hofmeister series (Cl$^–$ > Br$^–$ > I$^–$), whereas for cations in the case of viscosity the indirect Hofmeister series was observed (Li$^+$ > Na$^+$ > K$^+$ > Rb$^+$ > Cs$^+$), but the values of particle sizes and zeta potential did not show cation-specific effects. Since the protein is positively charged at pH = 4.3, anions are more attracted to the protein surface and shield its charge, while the interaction with cations is less pronounced. We hypothesize that salt surface charge shielding reduces protein colloidal stability and promotes protein aggregate formation