The effect of water dynamics on conformation changes of albumin in pre-denaturation state:photon correlation spectroscopy and simulation

Water is essential for protein three-dimensional structure, conformational dynamics, and activity. Human serum albumin (HSA) is one of major blood plasma proteins, and its functioning is fundamentally determined by the dynamics of surrounding water. The goal of this study is to link the conformational dynamics of albumin to the thermal motions in water taking place in the physiological temperature range. We report the results of photon correlation spectroscopy and molecular dynamics simulations of HSA in aqueous solution. The experimental data processing produced the temperature dependence of the HSA hydrodynamic radius and its zeta potential. Molecular dynamics reproduced the results of experiments and revealed changes in the secondary structure caused by the destruction of hydrogen bonds in the macromolecule's globule

A nanocomplex of C60 fullerene with cisplatin: design, characterization and toxicity

The self-organization of C60 fullerene and cisplatin in aqueous solution was investigated using the computer simulation, dynamic light scattering and atomic force microscopy techniques. The results evidence the complexation between the two compound

Sustainable polyethylene fabrics with engineered moisture transport for passive cooling

Polyethylene (PE) has emerged recently as a promising polymer for incorporation in wearable textiles owing to its high infrared transparency and tuneable visible opacity, which allows the human body to cool via thermal radiation, potentially saving energy on building refrigeration. Here, we show that single-material PE fabrics may offer a sustainable, high-performance alternative to conventional textiles, extending beyond radiative cooling. PE fabrics exhibit ultra-light weight, low material cost and recyclability. Industrial materials sustainability (Higg) index calculations predict a low environmental footprint for PE fabrics in the production phase. We engineered PE fibres, yarns and fabrics to achieve efficient water wicking and fast-drying performance which, combined with their excellent stain resistance, offer promise in reducing energy and water consumption as well as the environmental footprint of PE textiles in their use phase. Unlike previously explored nanoporous PE materials, the high-performance PE fabrics in this study are made from fibres melt spun and woven on standard equipment used by the textile industry worldwide and do not require any chemical coatings. We further demonstrate that these PE fibres can be dry coloured during fabrication, resulting in dramatic water savings without masking the PE molecular fingerprints scanned during the automated recycling process

Sustainable polyethylene fabrics with engineered moisture transport for passive cooling

Polyethylene (PE) has emerged recently as a promising polymer for incorporation in wearable textiles owing to its high infrared transparency and tuneable visible opacity, which allows the human body to cool via thermal radiation, potentially saving energy on building refrigeration. Here, we show that single-material PE fabrics may offer a sustainable, high-performance alternative to conventional textiles, extending beyond radiative cooling. PE fabrics exhibit ultra-light weight, low material cost and recyclability. Industrial materials sustainability (Higg) index calculations predict a low environmental footprint for PE fabrics in the production phase. We engineered PE fibres, yarns and fabrics to achieve efficient water wicking and fast-drying performance which, combined with their excellent stain resistance, offer promise in reducing energy and water consumption as well as the environmental footprint of PE textiles in their use phase. Unlike previously explored nanoporous PE materials, the high-performance PE fabrics in this study are made from fibres melt spun and woven on standard equipment used by the textile industry worldwide and do not require any chemical coatings. We further demonstrate that these PE fibres can be dry coloured during fabrication, resulting in dramatic water savings without masking the PE molecular fingerprints scanned during the automated recycling process.The textile industry is one of the largest polluters. Here the authors show that polyethylene is a sustainable alternative textile with water wicking and fast-drying performance. The fabrication of polyethylene fabrics is compatible with standard equipment and could be dry-coloured, further reducing water consumption

Hierarchical Assembly of Star Polymer Polymersomes into Responsive Multicompartmental Microcapsules

We report a novel approach to realizing programmable encapsulation and following release of different compounds in a sequential way from multicompartmental microcapsules assembled from preformed polymersomes. The polymersomes, or polymeric vesicles, are formed through electrostatic interactions between a cationic miktoarm star polymer, namely poly­(ethylene oxide)₁₁₃-(quaternized poly­(2-(dimethylamino)­ethyl methacrylate)₆₀)₄, and a linear anionic polyelectrolyte, (poly­(styrenesulfonate)₂₀), and then used as the main component to fabricate microcapsules with tannic acid via hydrogen-bonded layer-by-layer assembly. The hydrogen bonding between tannic acid and polymersomes is sensitive to external pH, and the structure of the polymersomes strongly depends on the ionic strength of the surrounding media. This combination facilitates dual-responsive behavior of these multicompartmental polymersome-based microcapsules with the programmable release of two different types of encapsulated molecules (anionic and cationic molecules) from core and shell regions of the microcapsules independently. The integration of responsive nanocarriers into functional microcapsules provides a new way to fabricate multiresponsive hierarchical microstructures with programmed sequential release of different molecules

Assembly of Amphiphilic Hyperbranched Polymeric Ionic Liquids in Aqueous Media at Different pH and Ionic Strength

We demonstrated the assembly of amphiphilic hyperbranched protic ionic liquids (HBP-ILs) based on aliphatic hyperbranched polyester (HBP) in aqueous media in a wide range of pH and ionic conditions. The series of new branched polyionic liquids with different terminal groups, HBP-ILs, was synthesized by neutralization of carboxylic and sulfonic terminal acid groups of hypebranched core with <i>N</i>-methyl­imidazole (Im) and 1,2,4-1<i>H</i>-triazole (Tr). HBP-IL compounds with triazole and imidazole counterions form 12–16 nm core–corona micelles at pH 11.6. We found that the introduction of long hydrophobic terminal groups such as <i>n</i>-octadecylurethane tails to initial hydrophobic HBP core has larger effect on the size of micellar assemblies than the introduction of ionic terminals groups. Furthermore, tuning the hydrophilic/hydrophobic balance of HBP-ILs can be achieved by changing the degree of ionization of terminal groups and counterions by reducing pH from 11.6 to 5.2 or ionic strength to 0.1 M. These changes caused the formation of much larger micellar aggregates with the size of 150–200 nm due to reduced ionization of carboxylic groups. At the same time, for sulfonate-containing HBP-ILs the micelle size increased modestly (to 25–40 nm) because of the higher degree of ionization of sulfonate terminal groups. The diverse aggregation behavior of these branched polymeric ionic liquids enables control over their micellar morphologies in solution and bulk states

Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations

A library of linear and branched amphiphilic poly­(ionic liquid)­s based on hydrophobic cores and peripheral thermally sensitive shells was synthesized and studied with regard to their ability to form stimuli-responsive, organized assemblies in aqueous media. The thermally responsive derivatives of poly­(ionic liquid)­s were synthesized by neutralizing 32 terminal carboxyl groups of functionalized polyester cores by amine-terminated poly­(<i>N</i>-isopropyl­acrylamide)­s (PNIPAM) (50% and 100%). We observed that these hyperbranched poly­(ionic liquid)­s possessed a narrow low critical solution transition (LCST) window with LCST for hyperbranched compounds being consistently lower than that for linear PNIPAM containing counterparts. We found that the poly­(ionic liquid)­s form spherical micellar assemblies with diverse morphologies, such as micelles and their aggregates, depending on the terminal compositions with reduced sizes for hyperbranched poly­(ionic liquid)­s. Increasing temperature above LCST promoted formation of network-like aggregates, large vesicles, and spherical micelles. Moreover, all PNIPAM-terminated compounds exhibited distinct unimolecular prolate nanodomain morphology in contrast to common spherical domains of initial cores. We proposed a multilength scale organized morphology to describe the thermoresponsive poly­(ionic liquid)­s micellar assemblies and discussed their morphological transformations during phase transitions associated with changes in hydrophobic–hydrophilic balance of poly­(ionic liquid)­s with distinct hydrophobic cores and variable peripheral shells

Template-Guided Assembly of Silk Fibroin on Cellulose Nanofibers for Robust Nanostructures with Ultrafast Water Transport

The construction of multilength scaled hierarchical nanostructures from diverse natural components is critical in the progress toward all-natural nanocomposites with structural robustness and versatile added functionalities. Here, we report a spontaneous formation of peculiar “shish kebab” nanostructures with the periodic arrangement of silk fibroin domains along straight segments of cellulose nanofibers. We suggest that the formation of these shish kebab nanostructures is facilitated by the preferential organization of heterogeneous (β-sheets and amorphous silk) domains along the cellulose nanofiber driven by modulated axial distribution of crystalline planes, hydrogen bonding, and hydrophobic interactions as suggested by all-atom molecular dynamic simulations. Such shish kebab nanostructures enable the ultrathin membrane to possess open, transparent, mechanically robust interlocked networks with high mechanical performance with up to 30 GPa in stiffness and 260 MPa in strength. These nanoporous robust membranes allow for the extremely high water flux, up to 3.5 × 10⁴ L h^–1 m^–2 bar^–1 combined with high rejection rate for various organic molecules, capability of capturing heavy metal ions and their further reduction into metal nanoparticles for added SERS detection capability and catalytic functionalities

Template-Guided Assembly of Silk Fibroin on Cellulose Nanofibers for Robust Nanostructures with Ultrafast Water Transport

The construction of multilength scaled hierarchical nanostructures from diverse natural components is critical in the progress toward all-natural nanocomposites with structural robustness and versatile added functionalities. Here, we report a spontaneous formation of peculiar “shish kebab” nanostructures with the periodic arrangement of silk fibroin domains along straight segments of cellulose nanofibers. We suggest that the formation of these shish kebab nanostructures is facilitated by the preferential organization of heterogeneous (β-sheets and amorphous silk) domains along the cellulose nanofiber driven by modulated axial distribution of crystalline planes, hydrogen bonding, and hydrophobic interactions as suggested by all-atom molecular dynamic simulations. Such shish kebab nanostructures enable the ultrathin membrane to possess open, transparent, mechanically robust interlocked networks with high mechanical performance with up to 30 GPa in stiffness and 260 MPa in strength. These nanoporous robust membranes allow for the extremely high water flux, up to 3.5 × 10⁴ L h^–1 m^–2 bar^–1 combined with high rejection rate for various organic molecules, capability of capturing heavy metal ions and their further reduction into metal nanoparticles for added SERS detection capability and catalytic functionalities