Compact polyelectrolyte complexes: "saloplastic" candidates for biomaterials.
Ontology highlight
ABSTRACT:
SUBMITTER: Porcel CH
PROVIDER: S-EPMC2774624 | biostudies-other | 2009 Nov
REPOSITORIES: biostudies-other
Similar Datasets
Project description:Polyelectrolyte complexes (PEC) are formed by mixing the solutions of oppositely charged polyelectrolytes, which were hitherto deemed "impossible" to process, since they are infusible and brittle when dry. Here, we describe the process of fabricating free-standing micro-patterned PEC films containing array of hollow or filled microchambers by one-step casting with small applied pressure and a PDMS mould. These structures are compared with polyelectrolyte multilayers (PEM) thin films having array of hollow microchambers produced from a layer-by-layer self-assembly of the same polyelectrolytes on the same PDMS moulds. PEM microchambers "cap" and "wall" thickness depend on the number of PEM bilayers, while the "cap" and "wall" of the PEC microchambers can be tuned by varying the applied pressure and the type of patterned mould. The proposed PEC production process omits layering approaches currently employed for PEMs, reducing the production time from ~2 days down to 2 hours. The error-free structured PEC area was found to be significantly larger compared to the currently-employed microcontact printing for PEMs. The sensitivity of PEC chambers towards aqueous environments was found to be higher compared to those composed of PEM.
| S-EPMC5103270 | biostudies-literature
Project description:Oil-in-water (O/W) microemulsion droplets are convenient carriers for hydrophobic molecules in an aqueous phase and are used for a wide range of applications. We studied weakly charged O/W microemulsion droplets complexed with oppositely charged polyacrylates that form long linear arrangements of droplets. All samples showed rather low viscosities, which is in contrast to similar systems of hydrophobically interconnected droplets. Here, we applied small-angle neutron scattering, dynamic light scattering and neutron spin-echo spectroscopy to characterise the dynamic properties of polyacrylate/microemulsion complexes in order to understand the origin of the low-viscous behaviour. We found that the electrostatic interactions lead to very dynamic complexes with high exchange rates of droplets and only a fraction of the droplets is contained within the transient complexes at a given time. These results were only accessible by the combination of different methods as one method alone would have given an incomplete picture.
| S-EPMC9419170 | biostudies-literature
Project description:Complexes of sodium poly(4-styrenesulfonate) (NaPSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were formed on mixing equimolar solutions in high salt concentration. Under ultracentrifugal fields, the complex precipitates were transformed into compact polyelectrolyte complexes (CoPECs), which showed extensive porosity. The mechanical properties of CoPECS make them attractive for bioimplants and tissue engineering applications. Free NaPSS chains in the closed pores of CoPECs create excess osmotic pressure, which controls the pore size and contributes to the mechanical resistance of the material. The mechanical properties of CoPECs, modulated by the ionic strength of the doping medium, were studied by uniaxial tensile testing and the stress-strain data were fit to a three-element Maxwell model which revealed at least two regimes of stress relaxation.
| S-EPMC2994323 | biostudies-literature
Project description:Polyelectrolyte complexation is a versatile platform for the design of self-assembled materials. Here we use rational design to create ionic hydrophobically-patterned peptides that allow us to precisely explore the role of hydrophobicity on electrostatic self-assembly. Polycations and polyanions were designed and synthesized with an alternating sequence of d- and l-chiral patterns of lysine or glutamic acid with either glycine, alanine or leucine due to their increasing hydrophobicity index, respectively. Two motifs were considered for the oppositely charged patterned peptides; one with equal residues of charged and uncharged amino acids and the other with increased charge density. Mass spectroscopy, circular dichroism, H- and F-NMR spectroscopy were used to characterize the polypeptides. Polyelectrolyte complexes (PECs) formed using the sequences were characterized using turbidity measurements, optical microscopy and infrared spectroscopy. Our results show that the critical salt concentration, a key measure of PEC stability, increased with both increasing charge density as well as hydrophobicity. Furthermore, by increasing the hydrophobicity, the amount of PEC formed increased with temperature, contrary to purely ionic PECs. Lastly, we assessed the encapsulation behavior of these materials using a hydrophobic dye. Concluding that encapsulation efficiency increased with hydrophobic content of the complexes providing insight for future work on the application of these materials for drug delivery.
| S-EPMC6429441 | biostudies-literature
Project description:DNA mismatch repair (MMR) corrects errors that occur during DNA replication. In humans, mutations in the proteins MutSα and MutLα that initiate MMR cause Lynch syndrome, the most common hereditary cancer. MutSα surveilles the DNA, and upon recognition of a replication error it undergoes adenosine triphosphate-dependent conformational changes and recruits MutLα. Subsequently, proliferating cell nuclear antigen (PCNA) activates MutLα to nick the error-containing strand to allow excision and resynthesis. The structure-function properties of these obligate MutSα-MutLα complexes remain mostly unexplored in higher eukaryotes, and models are predominately based on studies of prokaryotic proteins. Here, we utilize atomic force microscopy (AFM) coupled with other methods to reveal time- and concentration-dependent stoichiometries and conformations of assembling human MutSα-MutLα-DNA complexes. We find that they assemble into multimeric complexes comprising three to eight proteins around a mismatch on DNA. On the timescale of a few minutes, these complexes rearrange, folding and compacting the DNA. These observations contrast with dominant models of MMR initiation that envision diffusive MutS-MutL complexes that move away from the mismatch. Our results suggest MutSα localizes MutLα near the mismatch and promotes DNA configurations that could enhance MMR efficiency by facilitating MutLα nicking the DNA at multiple sites around the mismatch. In addition, such complexes may also protect the mismatch region from nucleosome reassembly until repair occurs, and they could potentially remodel adjacent nucleosomes.
| S-EPMC7368325 | biostudies-literature
Project description:For the first time, temperature-dependent conductivities at constant water content for a series of solid polyelectrolyte complexes with varying mixing ratios of anionic poly(sodium 4-styrene sulfonate) and poly(diallyldimethylammonium chloride) are presented. For water absorption, the samples are first equilibrated at an ambient temperature and at fixed relative humidity (RH). During the conductivity measurements, the so achieved water content of the samples is kept constant. At all of the hydration levels, the dc conductivities of the hydrated polyelectrolyte complexes (PEC) display Arrhenius behavior with activation enthalpies that are significantly lower than those of dry complexes. The activation enthalpy decreases linearly with water content. The lower activation enthalpies in case of hydrated as compared to dried complexes are attributed to a lowering of the energy barriers for ion motion. Finally, it is shown that the temperature-dependent conductivity spectra at constant water content obey the time-temperature superposition principle. Additionally, temperature-dependent conductivities at constant water content are compared to data sets determined in a separate study with constant RH at all of the temperatures. For the latter case, the influence of the type of alkali ion is also considered. Using the broad variety of data sets, the influences of water content and temperature on the conductivity mechanism can be separated from each other.
| S-EPMC6418868 | biostudies-literature
Project description:The ionic assembly of oppositely charged polyelectrolyte-surfactant complexes (PESCs) is often done with the aim of constructing more functional colloids, for instance as advanced delivery systems. However, PESCs are often not easily loaded with a solubilisate due to intrinsic restrictions of such complexes. This question was addressed from a different starting point: by employing microemulsion droplets as heavily loaded surfactant systems and thereby avoiding potential solubilisation limitations from the beginning. We investigated mixtures of cationic oil-in-water (O/W) microemulsion droplets and oppositely charged sodium polyacrylate (NaPA) and determined structure and phase behaviour as a function of the mixing ratio for different droplet sizes and different M w (NaPA). Around an equimolar charge ratio an extended precipitate region is present, which becomes wider for larger droplets and with increasing M w of the NaPA. Static and dynamic light scattering (SLS and DLS) and small-angle neutron scattering (SANS) show the formation of one-dimensional arrangements of microemulsion droplets for polyelectrolyte excess, which become more elongated with increasing M w (NaPA) and less so with increasing NaPA excess. What is interesting is a marked sensitivity to ionic strength, where already a modest increase to ∼20 mM leads to a dissolution of the complexes. This work shows that polyelectrolyte/microemulsion complexes (PEMECs) are structurally very versatile hybrid systems, combining the high solubilisate loading of microemulsions with the larger-scale structuring induced by the polymer, thereby markedly extending the concept of conventional PESCs. This type of system has not been described before and is highly promising for future applications where high payloads are to be formulated.
| S-EPMC6334502 | biostudies-literature
Project description:Structural maintenance of chromosomes (SMC) protein complexes are key determinants of chromosome conformation. Using Hi-C and polymer modelling, we study how cohesin and condensin, two deeply conserved SMC complexes, organize chromosomes in the budding yeast Saccharomyces cerevisiae. The canonical role of cohesin is to co-align sister chromatids, while condensin generally compacts mitotic chromosomes. We find strikingly different roles for the two complexes in budding yeast mitosis. First, cohesin is responsible for compacting mitotic chromosome arms, independently of sister chromatid cohesion. Polymer simulations demonstrate that this role can be fully accounted for through cis-looping of chromatin. Second, condensin is generally dispensable for compaction along chromosome arms. Instead, it plays a targeted role compacting the rDNA proximal regions and promoting resolution of peri-centromeric regions. Our results argue that the conserved mechanism of SMC complexes is to form chromatin loops and that distinct SMC-dependent looping activities are selectively deployed to appropriately compact chromosomes.
| S-EPMC5640152 | biostudies-literature
Project description:Polyelectrolyte complexation is critical to the formation and properties of many biological and polymeric materials, and is typically initiated by aqueous mixing followed by fluid-fluid phase separation, such as coacervation. Yet little to nothing is known about how coacervates evolve into intricate solid microarchitectures. Inspired by the chemical features of the cement proteins of the sandcastle worm, here we report a versatile and strong wet-contact microporous adhesive resulting from polyelectrolyte complexation triggered by solvent exchange. After premixing a catechol-functionalized weak polyanion with a polycation in dimethyl sulphoxide (DMSO), the solution was applied underwater to various substrates whereupon electrostatic complexation, phase inversion, and rapid setting were simultaneously actuated by water-DMSO solvent exchange. Spatial and temporal coordination of complexation, inversion and setting fostered rapid (?25?s) and robust underwater contact adhesion (Wad ? 2?J?m(-2)) of complexed catecholic polyelectrolytes to all tested surfaces including plastics, glasses, metals and biological materials.
| S-EPMC4939084 | biostudies-literature
Project description:Chitosan (CS) and chondroitin sulfate (CHS) are natural polymers with demonstrated applicability in drug delivery, while nanoparticles are one of the most explored carriers for transmucosal delivery of biopharmaceuticals. In this work we have prepared CS/CHS nanoparticles and associated for the first time the therapeutic protein insulin. Fluorescein isothiocyanate bovine serum albumin (FITC-BSA) was also used to enable comparison of behaviors regarding differences in molecular weight (5.7 kDa versus 67 kDa). Nanoparticles of approximately 200 nm and positive zeta potential around +20 mV were obtained. These parameters remained stable for up to 1 month at 4 °C. Proteins were associated with efficiencies of more than 50%. The release of FITC-BSA in PBS pH 7.4 was more sustained (50% in 24 h) than that of insulin (85% in 24 h). The biocompatibility of nanoparticles was tested in Calu-3 and A549 cells by means of three different assays. The metabolic assay MTT, the determination of lactate dehydrogenase release, and the quantification of the inflammatory response generated by cell exposure to nanoparticles have indicated an absence of overt toxicity. Overall, the results suggest good indications on the application of CS/CHS nanoparticles in respiratory transmucosal protein delivery, but the set of assays should be widened to clarify obtained results.
| S-EPMC5512620 | biostudies-other