The specific ion effect (SIE), the control of polymer solubility in aqueous solutions by the added ions, has been a phenomenon known for more than a century. The seemingly simple nature of the ion-polymer-water interactions can lead to complex behaviors, which have also been exploited in many applications in biochemistry, electrochemistry, and energy harvesting. Here, we show an emerging diversification of actuation behaviors in "salty" hydrogel and hydrogel-paper actuators.
View Article and Find Full Text PDFDynamical fluctuations of the elastic strain in strongly correlated systems are known to affect the onset of metal-to-insulator or superconducting transitions. Here we report their effect on the properties of a family of bandwidth-controlled alkali-intercalated fullerene superconductors. We introduce elastic strain through static local structural disorder in a systematic and controllable way in the fcc-structured K Cs C (with potassium content, 0.
View Article and Find Full Text PDFThe multisystemic effects of COVID-19 may continue for a longer time period following the acute phase, depending on the severity of the disease. However, long-term systemic transcriptomic changes associated with COVID-19 disease and the impact of disease severity are not fully understood. We aimed to investigate the impact of COVID-19 and its severity on transcriptomic alterations in peripheral blood mononuclear cells (PBMCs) following 1 year of the disease.
View Article and Find Full Text PDFHydrophobic surfaces in contact with aqueous media are omnipresent in nature. A plethora of key biological and physiological processes occur at the interface of immiscible fluids. Besides its fundamental importance, probing such interfaces is rather challenging, especially when one medium is bathed in the other.
View Article and Find Full Text PDFIons influence the solution properties of macromolecules. Although much is known about anions, cationic effects are considered mostly in terms of weak interactions or exclusion from neutral interfaces. Herein, we have systematically studied the effect of quaternary tetraalkylammonium cations (NH, NMe, NEt, NPr, NBu) on the phase transition of poly(-isopropylacrylamide) (PNIPAM) in aqueous solution.
View Article and Find Full Text PDFThe effects of CaCl and MgCl on the cloud point temperature of two different elastin-like polypeptides (ELPs) were studied using a combination of cloud point measurements, molecular dynamics simulations, and infrared spectroscopy. Changes in the cloud point for the ELPs in aqueous divalent metal cation solutions were primarily governed by two competing interactions: the cation-amide oxygen electrostatic interaction and the hydration of the cation. In particular, Ca cations can more readily shed their hydration shells and directly contact two amide oxygens by the formation of ion bridges.
View Article and Find Full Text PDFWhen a nanoparticle (NP) is introduced into a biological environment, its identity and interactions are immediately attributed to the dense layer of proteins that quickly covers the particle. The formation of this layer, dubbed the protein corona, is in general a combination of proteins interacting with the surface of the NP and a contest between other proteins for binding sites either at the surface of the NP or upon the dense layer. Despite the importance for surface engineering and drug development, the molecular mechanisms and structure behind interfacial biomolecule action have largely remained elusive.
View Article and Find Full Text PDFMeasuring the high-affinity binding of proteins to liposome membranes remains a challenge. Here, we show an ultrasensitive and direct detection of protein binding to liposome membranes using high throughput second harmonic scattering (SHS). Perfringolysin O (PFO), a pore-forming toxin, with a highly membrane selective insertion into cholesterol-rich membranes is used.
View Article and Find Full Text PDFThe lyotropic liquid crystalline (LLC) mesophase forms upon evaporation of water from aqueous solutions of LiX salts (X is Cl, Br, NO, or SCN) and a surfactant [CH(OCHCH)OH, abbreviated as CE]. The LiX/CE/HO aqueous solutions have been monitored (during evaporation of their excess water to obtain stable LLC mesophases) by gravimetric, spectroscopic, and conductivity measurements to elucidate the role of water in these mesophases. The water/salt molar ratio in stable mesophases changes from 1.
View Article and Find Full Text PDFMorphological and gel-to-liquid phase transitions of lipid membranes are generally considered to primarily depend on the structural motifs in the hydrophobic core of the bilayer. Structural changes in the aqueous headgroup phase are typically not considered, primarily because they are difficult to quantify. Here, we investigate structural changes of the hydration shells around large unilamellar vesicles (LUVs) in aqueous solution, using differential scanning calorimetry (DSC), and temperature-dependent ζ-potential and high-throughput angle-resolved second harmonic scattering measurements (AR-SHS).
View Article and Find Full Text PDFWeakly hydrated anions help to solubilize hydrophobic macromolecules in aqueous solutions, but small molecules comprising the same chemical constituents precipitate out when exposed to these ions. Here, this apparent contradiction is resolved by systematically investigating the interactions of NaSCN with polyethylene oxide oligomers and polymers of varying molecular weight. A combination of spectroscopic and computational results reveals that SCN accumulates near the surface of polymers, but is excluded from monomers.
View Article and Find Full Text PDFVibrational Stark shifts were explored in aqueous solutions of organic molecules with carbonyl- and nitrile-containing constituents. In many cases, the vibrational resonances from these moieties shifted toward lower frequency as salt was introduced into solution. This is in contrast to the blue-shift that would be expected based upon Onsager's reaction field theory.
View Article and Find Full Text PDFHyaluronan (HA) is an anionic, highly hydrated bio-polyelectrolyte found in the extracellular environment, like the synovial fluid between joints. We explore the extended hydration shell structure of HA in water using femtosecond elastic second-harmonic scattering (fs-ESHS). HA enhances orientational water-water correlations.
View Article and Find Full Text PDFBackground: Oesophageal colonic interposition in oesophageal atresia (OA) patients is almost exclusively done as a staged operation with an initial oesophagostomy and gastrostomy followed by the definitive surgery months later. This study presents a series of patients in whom a cervical oesophagostomy was not performed before the substitution surgery.
Patients And Methods: Records of EA patients were evaluated for those who underwent colon interposition without cervical oesophagostomy.
Ion identity and concentration influence the solubility of macromolecules. To date, substantial effort has been focused on obtaining a molecular level understanding of specific effects for anions. By contrast, the role of cations has received significantly less attention and the underlying mechanisms by which cations interact with macromolecules remain more elusive.
View Article and Find Full Text PDFAngle-resolved X-ray photoelectron spectroscopy and contact-angle measurements guided by a signal attenuation model are utilized to extract molar composition and anion enrichment in the vacuum interface of a binary ionic liquid mixture, having a common quaternary ammonium cation and two different anions. By using the intensity ratio of the F1s peaks belonging to the two different anions recorded at the full electron take-off angle range, from 0° to 80°, we have determined that only a fractionally covered and anion enriched surface layer can predict the AR-XPS data, which is also consistent with surface tension measurements. Moreover, the more bulky and non-spherical anion enrichment is evident even at the conventional and the so assumed bulk sensitive take-off angle of 0°.
View Article and Find Full Text PDFNew Microbes New Infect
September 2020
Dornase alfa, the recombinant form of the human DNase I enzyme, breaks down neutrophil extracellular traps (NET) that include a vast amount of DNA fragments, histones, microbicidal proteins and oxidant enzymes released from necrotic neutrophils in the highly viscous mucus of cystic fibrosis patients. Dornase alfa has been used for decades in patients with cystic fibrosis to reduce the viscoelasticity of respiratory tract secretions, to decrease the severity of respiratory tract infections, and to improve lung function. Previous studies have linked abnormal NET formations to lung diseases, especially to acute respiratory distress syndrome (ARDS).
View Article and Find Full Text PDFThis article has been withdrawn at the request of the author(s). The Publisher apologizes for any inconvenience this may cause. The full Elsevier Policy on Article Withdrawal can be found at https://www.
View Article and Find Full Text PDFHydrophobic oil droplets, particles, and air bubbles can be dispersed in water as kinetically stabilized dispersions. It has been established since the 19th century that such objects harbor a negative electrostatic potential roughly twice larger than the thermal energy. The source of this charge continues to be one of the core observations in relation to hydrophobicity, and its molecular explanation is still debated.
View Article and Find Full Text PDFIons interact with water via short-ranged ion-dipole interactions. Recently, an additional unexpected long-ranged interaction was found: The total electric field of ions influences water-water correlations over tens of hydration shells, leading to the Jones Ray effect, a 0.3% surface tension depression.
View Article and Find Full Text PDFCell membranes are composed of a hydrated lipid bilayer that is molecularly complex and diverse, and the link between molecular hydration structure and membrane macroscopic properties is not well understood, due to a lack of technology that can probe and relate molecular level hydration information to micro- and macroscopic properties. Here, we demonstrate a direct link between lipid hydration structure and macroscopic dynamic curvature fluctuations. Using high-throughput wide-field second harmonic (SH) microscopy, we observe the formation of transient domains of ordered water at the interface of freestanding lipid membranes.
View Article and Find Full Text PDFCsO adopts two distinct crystal structures at ambient pressure. At temperatures below ∼200 K, its ground state structure is tetragonal, incorporating two symmetry-distinct dioxygen anions, diamagnetic peroxide, O, and paramagnetic superoxide, O, units in a 1:2 ratio, consistent with the presence of charge and orbital order. At high temperatures, its ground state structure is cubic, comprising symmetry-equivalent dioxygen units with an average oxidation state of -/, consistent with the adoption of a charge-disordered state.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
December 2019
CsO is a mixed-valence molecular oxide with a cubic structure, comprising valency-delocalized O units and with properties highly sensitive to cooling protocols. Here we use neutron powder diffraction to authenticate that, while upon deep quenching the cubic phase is kinetically arrested down to cryogenic temperatures, ultraslow cooling results in an incomplete structural transition to a contracted tetragonal phase. Two dioxygen anions in a 1:2 ratio are identified, providing evidence that the transition is accompanied by charge and orbital order and stabilizes a Robin-Day Class II mixed-valence state, comprising O and O anions.
View Article and Find Full Text PDFAqueous two-phase system (ATPS) formation is the macroscopic completion of liquid-liquid phase separation (LLPS), a process by which aqueous solutions demix into 2 distinct phases. We report the temperature-dependent kinetics of ATPS formation for solutions containing a monoclonal antibody and polyethylene glycol. Measurements are made by capturing dark-field images of protein-rich droplet suspensions as a function of time along a linear temperature gradient.
View Article and Find Full Text PDF