Antibacterial Activity of Various Morphologies of Films Based on Guanidine Derivatives of Pillar[5]arene: Influence of the Nature of One Substitute on Self-assembly.

The progress of the pillar[5]arene chemistry allowed us to set out a new concept on application of the supramolecular assemblies to create antimicrobial films with variable surface morphologies and biological activities. Antibacterial films were derived from the substituted pillar[5]arenes containing nine pharmacophoric guanidine fragments and one thioalkyl substituent. Changing the only thioalkyl fragment in the macrocycle structure made it possible to control the biological activity of the resulting antibacterial coating. Pretreatment of the surface with aqueous solution of the amphiphilic pillar[5]arenes reduced the biofilm thickness by 56 ± 10% of Gram-positive Staphylococcus aureus in the case of the pillar[5]arene containing a thiooctyl fragment and by 52 ± 7% for the biofilm of Gram-negative Klebsiella pneumoniae in the case of pillar[5]arene containing a thiooctadecyl fragment. Meanwhile, the cytotoxicity of the synthesized macrocycles was examined at a concentration of 50 µg/mL, which was significantly lower than that of bis-guanidine-based antimicrobial preparations.

Linear and ring polypeptides complexed with oppositely charged surfactants: the cohesion of the complexes as revealed in atomistic simulations.

The use of linear supercharged unfolded polypeptides (SUPs) and oppositely charged surfactants in aqueous solution has demonstrated impressive adhesive properties. These substances possess biocompatibility, biodegradability and other necessary properties for practical application as a biomedical glue in wound repair. The success of these substances, coupled with limited knowledge about such systems, provides hope for enhancing the performance of the final product. One potential approach involves altering the topology of the polypeptide chain. In this article, we conduct a comparative analysis to examine the behavior of the ring and linear chains of a polypeptide in aqueous solution. This analysis utilizes full-atomic computer modeling to monitor the properties of the chains. We investigate the temperature dependence of the shape and size of individual polypeptides in the solution, as well as the formation of complexes via mixing the polypeptide chains with oppositely charged sodium dodecylbenzene sulfonate (SDBS) surfactant molecules in a stoichiometric ratio. Additionally, we explore the cohesive properties of the resulting complex through power experiments involving the extraction of single polypeptide chains out of the SUP-SDBS complexes.

Spontaneous Synchronization of Two Bistable Pyridine-Furan Nanosprings Connected by an Oligomeric Bridge.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose long-term conformational dynamics are similar to the dynamics of bistable mechanical systems such as Euler arches and Duffing oscillators. Collective synchrony in bistable dynamics of molecular-sized systems has attracted immense attention as a potential pathway to amplify the output signals of molecular nanodevices. Recently, pyridine-furan oligomers of helical shape that are a few nanometers in size and exhibit bistable dynamics similar to a Duffing oscillator have been identified through molecular dynamics simulations. In this article, we present the case of dynamical synchronization of these bistable systems. We show that two pyridine-furan springs connected by a rigid oligomeric bridge spontaneously synchronize vibrations and stochastic resonance enhances the synchronization effect.

Spontaneous Vibrations and Stochastic Resonance of Short Oligomeric Springs.

There is growing interest in molecular structures that exhibit dynamics similar to bistable mechanical systems. These structures have the potential to be used as two-state operating units for various functional purposes. Particularly intriguing are the bistable systems that display spontaneous vibrations and stochastic resonance. Previously, via molecular dynamics simulations, it was discovered that short pyridine-furan springs in water, when subjected to stretching with power loads, exhibit the bistable dynamics of a Duffing oscillator. In this study, we extend these simulations to include short pyridine-pyrrole and pyridine-furan springs in a hydrophobic solvent. Our findings demonstrate that these systems also display the bistable dynamics, accompanied by spontaneous vibrations and stochastic resonance activated by thermal noise.

Anisotropic Microgels by Supramolecular Assembly and Precipitation Polymerization of Pyrazole-Modified Monomers.

Soft colloidal macromolecular structures with programmable chemical functionalities, size, and shape are important building blocks for the fabrication of catalyst systems and adaptive biomaterials for tissue engineering. However, the development of the easy upscalable and template-free synthesis methods to obtain such colloids lack in understanding of molecular interactions that occur in the formation mechanisms of polymer colloids. Herein, a computer simulation-driven experimental synthesis approach based on the supramolecular self-assembly followed by polymerization of tailored pyrazole-modified monomers is developed. Simulations for a series of pyrazole-modified monomers with different numbers of pyrazole groups, different length and polarity of spacers between pyrazole groups and the polymerizable group are first performed. Based on simulations, monomers able to undergo π-π stacking and guide the formation of supramolecular bonds between polymer segments are synthesized and these are used in precipitation polymerization to synthesize anisotropic microgels. This study demonstrates that microgel morphologies can be tuned from spherical, raspberry-like to dumbbell-like by the increase of the pyrazole-modified monomer loading, which is concentrated at periphery of growing microgels. Combining experimental and simulation results, this work provides a quantitative and predictive approach for guiding microgel design that can be further extended to a diversity of colloidal systems and soft materials with superior properties.

Ionic Combisomes: A New Class of Biomimetic Vesicles to Fuse with Life.

The construction of biomembranes that faithfully capture the properties and dynamic functions of cell membranes remains a challenge in the development of synthetic cells and their application. Here a new concept for synthetic cell membranes based on the self-assembly of amphiphilic comb polymers into vesicles, termed ionic combisomes (i-combisomes) is introduced. These combs consist of a polyzwitterionic backbone to which hydrophobic tails are linked by electrostatic interactions. Using a range of microscopies and molecular simulations, the self-assembly of a library of combs in water is screened. It is discovered that the hydrophobic tails form the membrane's core and force the backbone into a rod conformation with nematic-like ordering confined to the interface with water. This particular organization resulted in membranes that combine the stability of classic polymersomes with the biomimetic thickness, flexibility, and lateral mobility of liposomes. Such unparalleled matching of biophysical properties and the ability to locally reconfigure the molecular topology of its constituents enable the harboring of functional components of natural membranes and fusion with living bacteria to "hijack" their periphery. This provides an almost inexhaustible palette to design the chemical and biological makeup of the i-combisomes membrane resulting in a powerful platform for fundamental studies and technological applications.

Short Pyridine-Furan Springs Exhibit Bistable Dynamics of Duffing Oscillators.

The intensive development of nanodevices acting as two-state systems has motivated the search for nanoscale molecular structures whose dynamics are similar to those of bistable mechanical systems, such as Euler arches and Duffing oscillators. Of particular interest are the molecular structures capable of spontaneous vibrations and stochastic resonance. Recently, oligomeric molecules that were a few nanometers in size and exhibited the bistable dynamics of an Euler arch were identified through molecular dynamics simulations of short fragments of thermo-responsive polymers subject to force loading. In this article, we present molecular dynamics simulations of short pyridine-furan springs a few nanometers in size and demonstrate the bistable dynamics of a Duffing oscillator with thermally-activated spontaneous vibrations and stochastic resonance.

Ultra-strong bio-glue from genetically engineered polypeptides.

The development of biomedical glues is an important, yet challenging task as seemingly mutually exclusive properties need to be combined in one material, i.e. strong adhesion and adaption to remodeling processes in healing tissue. Here, we report a biocompatible and biodegradable protein-based adhesive with high adhesion strengths. The maximum strength reaches 16.5 ± 2.2 MPa on hard substrates, which is comparable to that of commercial cyanoacrylate superglue and higher than other protein-based adhesives by at least one order of magnitude. Moreover, the strong adhesion on soft tissues qualifies the adhesive as biomedical glue outperforming some commercial products. Robust mechanical properties are realized without covalent bond formation during the adhesion process. A complex consisting of cationic supercharged polypeptides and anionic aromatic surfactants with lysine to surfactant molar ratio of 1:0.9 is driven by multiple supramolecular interactions enabling such strong adhesion. We demonstrate the glue's robust performance in vitro and in vivo for cosmetic and hemostasis applications and accelerated wound healing by comparison to surgical wound closures.

An Artificial Phase-Transitional Underwater Bioglue with Robust and Switchable Adhesion Performance.

Complex coacervation enables important wet adhesion processes in natural and artificial systems. However, existed synthetic coacervate adhesives show limited wet adhesion properties, non-thermoresponsiveness, and inferior biodegradability, greatly hampering their translations. Herein, by harnessing supramolecular assembly and rational protein design, we present a temperature-sensitive wet bioadhesive fabricated through recombinant protein and surfactant. Mechanical performance of the bioglue system is actively tunable with thermal triggers. In cold condition, adhesion strength of the bioadhesive was only about 50 kPa. By increasing temperature, the strength presented up to 600 kPa, which is remarkably stronger than other biological counterparts. This is probably due to the thermally triggered phase transition of the engineered protein and the formation of coacervate, thus leading to the enhanced wet adhesion bonding.

Selenium-Modified Microgels as Bio-Inspired Oxidation Catalysts.

Active colloidal catalysts inspired by glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. A diselenide crosslinker (Se X-linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with the conventional crosslinker N,N'-methylenebis(acrylamide) (BIS). Diselenide bonds within the microgels were cleaved through oxidation by H2 O2 and converted to seleninic acid whilst maintaining the intact microgel microstructure. Through this approach catalytically active microgels with variable amounts of seleninic acid were synthesized. Remarkably, the microgels exhibited higher catalytic activity and selectivity at low reaction temperatures than the molecular Se catalyst in a model oxidation reaction of acrolein to acrylic acid and methyl acrylate.