Concept: Chemical properties
- Journal of controlled release : official journal of the Controlled Release Society
- Published over 4 years ago
This review provides the first comprehensive overview of the use of both nanoparticles and nanofibers for topical drug delivery. Researchers have explored the use of nanotechnology, specifically nanoparticles and nanofibers, as drug delivery systems for topical and transdermal applications. This approach employs increased drug concentration in the carrier, in order to increase drug flux into and through the skin. Both nanoparticles and nanofibers can be used to deliver hydrophobic and hydrophilic drugs and are capable of controlled release for a prolonged period of time. The examples presented provide significant evidence that this area of research has - and will continue to have - a profound impact on both clinical outcomes and the development of new products.
Smells are known to be composed of thousands of chemicals with various concentrations, and thus, the extraction of specific information from such a complex system is still challenging. Herein, we report for the first time that the nanomechanical sensing combined with machine learning realizes the specific information extraction, e.g. alcohol content quantification as a proof-of-concept, from the smells of liquors. A newly developed nanomechanical sensor platform, a Membrane-type Surface stress Sensor (MSS), was utilized. Each MSS channel was coated with functional nanoparticles, covering diverse analytes. The smells of 35 liquid samples including water, teas, liquors, and water/EtOH mixtures were measured using the functionalized MSS array. We selected characteristic features from the measured responses and kernel ridge regression was used to predict the alcohol content of the samples, resulting in successful alcohol content quantification. Moreover, the present approach provided a guideline to improve the quantification accuracy; hydrophobic coating materials worked more effectively than hydrophilic ones. On the basis of the guideline, we experimentally demonstrated that additional materials, such as hydrophobic polymers, led to much better prediction accuracy. The applicability of this data-driven nanomechanical sensing is not limited to the alcohol content quantification but to various fields including food, security, environment, and medicine.
Lipid membranes serve as effective barriers allowing cells to maintain internal composition differing from that of extracellular medium. Membrane permeation, both natural and artificial, can take place via appearance of transversal pores. The rearrangements of lipids leading to pore formation in the intact membrane are not yet understood in details. We applied continuum elasticity theory to obtain continuous trajectory of pore formation and closure, and analyzed molecular dynamics trajectories of pre-formed pore reseal. We hypothesized that a transversal pore is preceded by a hydrophobic defect: intermediate structure spanning through the membrane, the side walls of which are partially aligned by lipid tails. This prediction was confirmed by our molecular dynamics simulations. Conversion of the hydrophobic defect into the hydrophilic pore required surmounting some energy barrier. A metastable state was found for the hydrophilic pore at the radius of a few nanometers. The dependence of the energy on radius was approximately quadratic for hydrophobic defect and small hydrophilic pore, while for large radii it depended on the radius linearly. The pore energy related to its perimeter, line tension, thus depends of the pore radius. Calculated values of the line tension for large pores were in quantitative agreement with available experimental data.
- Proceedings of the National Academy of Sciences of the United States of America
- Published about 5 years ago
The majority of bacteria in the natural environment live within the confines of a biofilm. The Gram-positive bacterium Bacillus subtilis forms biofilms that exhibit a characteristic wrinkled morphology and a highly hydrophobic surface. A critical component in generating these properties is the protein BslA, which forms a coat across the surface of the sessile community. We recently reported the structure of BslA, and noted the presence of a large surface-exposed hydrophobic patch. Such surface patches are also observed in the class of surface-active proteins known as hydrophobins, and are thought to mediate their interfacial activity. However, although functionally related to the hydrophobins, BslA shares no sequence nor structural similarity, and here we show that the mechanism of action is also distinct. Specifically, our results suggest that the amino acids making up the large, surface-exposed hydrophobic cap in the crystal structure are shielded in aqueous solution by adopting a random coil conformation, enabling the protein to be soluble and monomeric. At an interface, these cap residues refold, inserting the hydrophobic side chains into the air or oil phase and forming a three-stranded β-sheet. This form then self-assembles into a well-ordered 2D rectangular lattice that stabilizes the interface. By replacing a hydrophobic leucine in the center of the cap with a positively charged lysine, we changed the energetics of adsorption and disrupted the formation of the 2D lattice. This limited structural metamorphosis represents a previously unidentified environmentally responsive mechanism for interfacial stabilization by proteins.
Hydrophobic materials that are robust to harsh environments are needed in a broad range of applications. Although durable materials such as metals and ceramics, which are generally hydrophilic, can be rendered hydrophobic by polymeric modifiers, these deteriorate in harsh environments. Here we show that a class of ceramics comprising the entire lanthanide oxide series, ranging from ceria to lutecia, is intrinsically hydrophobic. We attribute their hydrophobicity to their unique electronic structure, which inhibits hydrogen bonding with interfacial water molecules. We also show with surface-energy measurements that polar interactions are minimized at these surfaces and with Fourier transform infrared/grazing-angle attenuated total reflection that interfacial water molecules are oriented in the hydrophobic hydration structure. Moreover, we demonstrate that these ceramic materials promote dropwise condensation, repel impinging water droplets, and sustain hydrophobicity even after exposure to harsh environments. Rare-earth oxide ceramics should find widespread applicability as robust hydrophobic surfaces.
Molecular knots remain difficult to produce using the current synthetic methods of chemistry because of their topological complexity. We report here the near-quantitative self-assembly of a trefoil knot from a naphthalenediimide-based aqueous disulfide dynamic combinatorial library. The formation of the knot appears to be driven by the hydrophobic effect and leads to a structure in which the aromatic components are buried while the hydrophilic carboxylate groups remain exposed to the solvent. Moreover, the building block chirality constrains the topological conformation of the knot and results in its stereoselective synthesis. This work demonstrates that the hydrophobic effect provides a powerful strategy to direct the synthesis of entwined architectures.
The synthesis of a series of co-oligomer amphiphiles by RAFT and their self-assembly behaviour in water is described. These novel amphiphiles, comprised of styrene, butyl acrylate and alkyl hydrophobes together with ionizable acrylic acid and nonionic hydroxyethylacrylate hydrophilic moieties and with total degrees of polymerization from 5 to 17, are representatives of a new class of small-molecule surfactants formed from the immense potential library of polymerisable monomers. Examples of micellar solutions and discrete cubic, hexagonal, lamellar and inverted hexagonal lyotropic phases, as well as vesicle dispersions and coexisting lamellar phases formed over a wide composition rage, are reported and their structure characterized by small-angle scattering. In most cases, the low degree of polymerization, particularly of the hydrophobic block, leads to rapidly-equilibrating self-assembly structures. The variation of self-assembly structure with co-oligomer composition, concentration and solution conditions is interpreted by analogy with the surfactant packing parameter used for conventional small-molecule amphiphiles.
Rheological properties of welan gum and xanthan gum solutions have been characterized systematically at various concentrations, temperatures and salinities. It is found that the viscoelasticity of welan gum is higher than that of xanthan gum at the same condition though the molecular weight of welan gum is lower. In view of this, welan gum will make a good performance in enhanced oil recovery, especially in high temperature and high salinity reservoirs. Network structure can be formed in solutions of welan gum and xanthan gum for the dynamic modulus has exponential relationship with the concentration. Moreover, the molecular aggregates of welan gum adopt a different arrangement with that of xanthan gum, adjacent double helices of welan gum arrange in parallel as the zipper model. The structure formed by zipper model is still stable in high temperature and high salinity.
Comb-shaped copolymers comprised of hydrophobic and hydrophilic blocks are self-assembled in aqueous solution, which results that they are suitable for delivery of hydrophobic drug molecules. Chitosan (CS) is an important biomaterial used widely in medical applications. Herein, a comb-shaped cationic copolymer composed of long biocompatible CS main chains and short PNIPAAm side chains was prepared via atom transfer radical polymerization (ATRP) by attaching an ATRP initiating group to N-phthaloyl chitosan. By subsequent removal of the protective groups on N-phthaloyl chitosan-graft-poly(N-isopropylacrylamide) (PHCS-g-PNIPAAm) copolymer with N(2)H(4)·H(2)O lead to the polymer pendant amino groups, this study attempted to synthesize a pH/temperature multi-responsive material. This chitosan-graft-poly(N-isopropylacrylamide) (CS-g-PNIPAAm) copolymer is self-assembled in aqueous solution into stimuli-responsive core-shell micelles with hydrodynamic diameters of about 170 nm. Structural organization and solution behavior were then investigated utilizing (1)H NMR spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering (DLS).
Probe electrospray ionization (PESI) is a recently developed method that uses a sharp solid needle as electrospray emitter and the sample is loaded to the needle tip by repetitive movement of the needle probe. This method has been previously used for the analysis of sample with high salt concentration and real-world samples without sample pretreatment. Although PESI is also applicable to aqueous solution, the ion signal stability and reproducibility were not satisfactory due to the spontaneous occurrence of corona discharge taking place on the metallic needle tip.