Voltage and concentration gradients across membraneless interface generated next to hydrogels: relation to glycocalyx.

Next to many hydrophilic surfaces, including those of biological cells and tissues, a layer of water that effectively excludes solutes and particles can be generated. This interfacial water is the subject of research aiming for practical applications such as removal of salts, pathogens or manipulation of biomolecules. However, the exact mechanism of its creation is still elusive because its persistence and extension contradict hydrogen-bond dynamics and electric double layer predictions. The experimentally recorded negative voltage of this interfacial water remains to be properly explained. Even less is known about the nature of such water layers in biological systems. We present experimental evidence for ion and particle exclusion as a result of separation of ionic charges with distinct diffusion rates across a liquid junction at the gel/water interface and the subsequent repulsion of ions of a given sign by a like-charged gel surface. Gels represent features of biological interfaces (in terms of functional groups and porosity) and are subject to biologically relevant chemical triggers. Our results show that gels with -OSO3- and -COO- groups can effectively generate ion- and particle-depleted regions of water reaching over 100 µm and having negative voltage up to -30 mV. Exclusion distance and electric potential depend on the liquid junction potential at the gel/water interface and on the concentration gradient at the depleted region/bulk interface, respectively. The voltage and extension of these ion- and particle-depleted water layers can be effectively modified by CO2 (respiratory gas) or KH2PO4 (cell metabolite). Possible implications pertain to biologically unstirred water layers and a cell's bioenergetics.

Beyond esterase-like activity of serum albumin. Histidine-(nitro)phenol radical formation in conversion cascade of p-nitrophenyl acetate and the role of infrared light.

Serum albumin, recognized mainly for its capacity to act as a carrier protein for many compounds, can also actively transform some organic molecules. As a starting point in this study, we consider esterase-like activity of bovine serum albumin (BSA) toward p-nitrophenyl acetate (p-NPA). Our results reveal that the reaction goes beyond ester hydrolysis step. In fact, the transformation product, p-nitrophenol (p-NP), becomes a substrate for further reaction with BSA in which its nitro group in subtracted and released in the form of HNO2 . Spectral data indicate that this cascade of events proceeds through formation of phenoxyl radical via proton-coupled electron transport (PCET) between OH group of p-NP and imidazole ring of histidine from the protein. Furthermore, the effect of application of electromagnetic radiation in the infrared range suggests that this remote physical trigger can support interactions based on PCET mechanism by acting on polarization and mutual alignment of water dipoles serving as effective water wires.

Spontaneous emulsification in ionic liquid/water systems and its use for templating of solids.

We report on the spontaneous formation of nano-sized ionic liquid/water (IL/W) emulsions in a simple system solely composed of an IL and aqueous solution of an inorganic salt. The IL ions play a dual role, that of both a surfactant and the dispersed phase. No extra surfactant is needed to promote emulsification. Droplets generation at the IL/W interface is captured by nanoparticulate and porous films that imprint the morphology of this unstable interface. The emulsion droplets are employed to create core-shell microcrystals with potential functionality.

Dependence of cell's membrane potential on extracellular voltage observed in Chara globularis.

The membrane potential (Vm) of a cell results from the selective movement of ions across the cell membrane. Recent studies have revealed the presence of a gradient of voltage within a few nanometers adjacent to erythrocytes. Very notably this voltage is modified in response to changes in cell's membrane potential thus effectively extending the potential beyond the membrane and into the solution. In this study, using the microelectrode technique, we provide experimental evidence for the existence of a gradient of negative extracellular voltage (Vz) in a wide zone close to the cell wall of algal cells, extending over several micrometers. Modulating the ionic concentration of the extracellular solution with CO2 alters the extracellular voltage and causes an immediate change in Vm. Elevated extracellular CO2 levels depolarize the cell and hyperpolarize the zone of extracellular voltage (ZEV) by the same magnitude. This observation strongly suggests a coupling effect between Vz and Vm. An increase in the level of intracellular CO2 (dark respiration) leads to hyperpolarization of the cell without any immediate effect on the extracellular voltage. Therefore, the metabolic activity of a cell can proceed without inducing changes in Vz. Conversely, Vz can be modified by external stimulation without metabolic input from the cell. The evolution of the ZEV, particularly around spines and wounded cells, where ion exchange is enhanced, suggests that the formation of the ZEV may be attributed to the exchange of ions across the cell wall and cell membrane. By comparing the changes in Vm in response to external stimuli, as measured by electrodes and observed using a potential-sensitive dye, we provide experimental evidence demonstrating the significance of extracellular voltage in determining the cell's membrane potential. This may have implications for our understanding of cell membrane potential generation beyond the activities of ion channels.

Antiviral, Antibacterial, Antifungal, and Antiparasitic Properties of Propolis: A Review.

Propolis is a complex phytocompound made from resinous and balsamic material harvested by bees from flowers, branches, pollen, and tree exudates. Humans have used propolis therapeutically for centuries. The aim of this article is to provide comprehensive review of the antiviral, antibacterial, antifungal, and antiparasitic properties of propolis. The mechanisms of action of propolis are discussed. There are two distinct impacts with regards to antimicrobial and anti-parasitic properties of propolis, on the pathogens and on the host. With regards to the pathogens, propolis acts by disrupting the ability of the pathogens to invade the host cells by forming a physical barrier and inhibiting enzymes and proteins needed for invasion into the host cells. Propolis also inhibits the replication process of the pathogens. Moreover, propolis inhibits the metabolic processes of the pathogens by disrupting cellular organelles and components responsible for energy production. With regard to the host, propolis functions as an immunomodulator. It upregulates the innate immunity and modulates the inflammatory signaling pathways. Propolis also helps maintain the host's cellular antioxidant status. More importantly, a small number of human clinical trials have demonstrated the efficacy and the safety of propolis as an adjuvant therapy for pathogenic infections.

Propolis-induced exclusion of colloids: Possible new mechanism of biological action.

Propolis is a natural product originating from life activity of honeybees. It exhibits wide range of biological properties applicable in medicine, the food industry, and cosmetics. Chemically, propolis is a complex and variable mixture with more than 300 identified biologically active components. Propolis's many health-promoting effects are attributed to different biochemical mechanisms, mediated by often-concerted actions of some of its many constituents. Propolis is considered safe and biocompatible. Yet due to its intrinsic complexity, standardization of propolis preparations for medical use as well as prediction of e.g. pathogen-specific interactions becomes a non-trivial task. In this work we demonstrate a new physical mechanism of propolis action, largely independent of specific nuances of propolis chemistry, which may underlie some of its biological actions. We show that propolis-bearing surfaces generate an extensive exclusion zone (EZ) water layer. EZ is an interfacial region of water capable of excluding solutes ranging from ions to microorganisms. Propolis-generated EZ may constitute an effective barrier, physically disabling the approach of various pathogens to the propolis-functionalized surfaces. We suggest possible implications of this new mechanism for propolis-based prevention of respiratory infections.

Cells in New Light: Ion Concentration, Voltage, and Pressure Gradients across a Hydrogel Membrane.

The ionic compositions of the intra- and extracellular environments are distinct from one another, with K+ being the main cation in the cytosol and Na+ being the most abundant cation outside of the cell. Specific ions can permeate into and out of the cell at different rates, bringing about uneven distribution of charges and development of negative electric potential inside the cell. Each healthy cell must maintain a specific ion concentration gradient and voltage. To account for these functions, various ionic pumps and channels located within the cell membrane have been invoked. In this work, we use a porous alginate hydrogel as a model gelatinous network representing the plant cell wall or cytoskeleton of the animal cell. We show that the gel barrier is able to maintain a stable separation of ionic solutions of different ionic strengths and chemical compositions without any pumping activity. For the Na+/K+ concentration gradient sustained across the barrier, a negative electric potential develops within the K+-rich side. The situation is reminiscent of that in the cell. Furthermore, also the advective flow of water molecules across the gel barrier is restricted, despite the gel's large pores and the osmotic or hydrostatic pressure gradients across it. This feature has important implications for osmoregulation. We propose a mechanism in which charge separation and electric fields developing across the permselective (gel) membrane prevent ion and bulk fluid flows ordinarily driven by chemical and pressure gradients.

Moving Water Droplets: The Role of Atmospheric CO2 and Incident Radiant Energy in Charge Separation at the Air-Water Interface.

One of the characteristics of aqueous interfaces is their negative charge, whose origin is still a subject of scientific debate. In this work, we provide spectroscopic evidence that bicarbonate anions, from dissolution of atmospheric CO2, can be a source of negative charge at the air-water and/or solid-water interface. Also, interfacial charge separation, with a negatively charged droplet rim and positive charges gathering more toward the interior, makes water droplets receptive systems. We found that these droplets move in a controlled fashion because of electrostatic forces acting between droplets and a solid support possessing a static electric charge. A trigger used to induce droplets' motion is IR emitted by different common objects. We interpret IR action as resulting from its ability to enhance the negative charge of the interfacial water. Droplets that leave negatively charged residues adsorbed to the solid, therefore acquiring a net positive charge, can defy the force of gravity and jump off the charged surface instead of falling, as observed in our experiments. Insights obtained from infrared emission of water agree with the possibility of excess protons residing in droplets after their contact with the solid. Our results show that (i) aqueous interfaces in contact with CO2 gas from the atmosphere (or possibly from cellular respiration inside of the organisms) acquire a negative surface charge, and (ii) infrared energy, abundant externally from the sun and internally from metabolic heat, can impact this process.