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1.
Soft Matter ; 20(9): 2141-2150, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38351843

RESUMO

Inkjet printing is a ubiquitous consumer and industrial process that involves concomitant processes of droplet impact, wetting, evaporation, and imbibement into a substrate as well as consequential substrate rearrangements and remodeling. In this work, we perform a study on the interaction between ink dispersions of different composition on substrates of increasing complexity to disentangle the motion of the liquid from the dynamic response of the substrate. We print three variations of pigmented inks and follow the ensuing dynamics at millisecond and micron time and length scales until complete drying using a multiple scattering technique, laser speckle imaging (LSI). Measurements of the photon transport mean free path, l*, for the printed inks and substrates show that the spatial region of information capture is the entire droplet volume and a depth within the substrate of a few µm beneath the droplet. Within this spatial confinement, LSI is an ideal approach for studying the solid-liquid transition at these small length and time scales by obtaining valid g2 and d2 autocorrelation functions and interpreting these dynamic changes under through kymographs. Our in situ LSI results show that droplets undergo delamination and cracking processes arising during droplet drying, which are confirmed by post mortem SEM imaging.

2.
Sci Rep ; 11(1): 17217, 2021 08 26.
Artigo em Inglês | MEDLINE | ID: mdl-34446774

RESUMO

Nanoparticles have been claimed to contribute efficiently to e.g. the mechanical strength of composite materials when present as individual particles. However, these particles tend to aggregate. In this paper we prepare nanocrystals from chitin, a product with high potential added value for application in bio-based materials, and investigate the effect of ultrasound on de-aggregation. Chitin nanocrystals with a length ~ 200 nm and a diameter ~ 15 nm, were obtained via acid hydrolysis of crude chitin powder. Freeze drying resulted in severe aggregation and after redispersion sizes up to ~ 200 µm were found. Ultrasound treatment was applied and break up behaviour was investigated using static light scattering, dynamic light scattering, and laser diffraction. Our results suggest that the cumulative energy input was the dominant factor for chitin nanocrystal aggregate breakup. When a critical energy barrier of ~ 100 kJ/g chitin nanocrystals was exceeded, the chitin nanocrystal aggregates broke down to nanometre range. The break up was mostly a result of fragmentation: the aggregation energy of chitin nanocrystal aggregates was quantified to be ~ 370 kJ/g chitin nanocrystals and we hypothesize that mainly van der Waals interactions and hydrogen bonds are responsible for aggregation.

3.
Soft Matter ; 17(8): 2132-2141, 2021 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-33439188

RESUMO

In this study, temperature dependent behavior of dense dispersions of core crosslinked flower-like micelles is investigated. Micelles were prepared by mixing aqueous solutions of two ABA block copolymers with PEG B-blocks and thermosensitive A-blocks containing PNIPAM and crosslinkable moieties. At a temperature above the lower critical solution temperature (LCST), self-assembly of the polymers resulted in the formation of flower-like micelles with a hydrophilic PEG shell and a hydrophobic core. The micellar core was stabilized by native chemical ligation (NCL). Above the LCST, micelles displayed a radius of ∼35 nm, while a radius of ∼48 nm was found below the LCST due to hydration of the PNIPAM core. Concentrated dispersions of these micelles (≥7.5 wt%) showed glassy state behavior below a critical temperature (Tc: 28 °C) which is close to the LCST of the polymers. Below this Tc, the increase in the micelle volume resulted in compression of micelles together above a certain concentration and formation of a glass. We quantified and compared micelle packing at different concentrations and temperatures. The storage moduli (G') of the dispersions showed a universal dependence on the effective volume fraction, which increased substantially above a certain effective volume fraction of φ = 1.2. Furthermore, a disordered lattice model describing this behavior fitted the experimental data and revealed a critical volume fraction of φc = 1.31 close to the experimental value of φ = 1.2. The findings reported provide insights for the molecular design of novel thermosensitive PNIPAM nanoparticles with tunable structural and mechanical properties.

4.
J Colloid Interface Sci ; 581(Pt B): 533-544, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32814184

RESUMO

HYPOTHESIS: Microbial extracellular polymeric substances (EPS) produced from wastewater are generally heterodispersed, which is expected to influence their flocculation performances and mechanism, particularly in mixed particle systems. The different molecular weight (MW) fractions should contribute to the overall adsorption affinity and flocculation mechanism of EPS in single and dual clay systems. EXPERIMENTS: EPS harvested from bioreactors were size-fractionated into high, medium and low MW fractions (HMW, MMW, LMW, respectively). The harvested mixed EPS and its fractions were characterised by diverse analytical techniques coupled with optical reflectometry to investigate the role of each EPS fraction in the overall flocculation mechanism of EPS in kaolinite and montmorillonite clay systems. FINDINGS: In single clay systems, both the harvested mixed EPS and the HMW-EPS fraction showed comparable flocculation performances. However, mixed EPS proved to be more efficient than the HMW-EPS fraction for dual clay flocculation. Site blocking effects were observed in mixed EPS: the LMW and MMW EPS first adsorbed to the surface due to higher diffusivities and faster mass transfer to the interface, while the HMW-EPS were slowly transported but were attached to the surface irreversibly and stronger than the LMW/MMW-EPS. We propose from this, a mixed EPS adsorption mechanism: extended anionic polymer tails in solution, thereby enhancing particle flocculation.


Assuntos
Matriz Extracelular de Substâncias Poliméricas , Águas Residuárias , Adsorção , Biopolímeros , Floculação , Esgotos
5.
RSC Adv ; 11(28): 16980-16988, 2021 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-35479723

RESUMO

The deposition behavior of lignin on a solid surface was studied using stagnation point adsorption reflectometry (SPAR) comprehensively. In this study, the light absorption coefficient of lignin (τ = 20 476 m-1) at 633 nm wavelength was considered to define a new imaginary refractive index (k) used in the SPAR technique for adsorption analysis. The inclusion of k in the adsorption model yielded an adsorbed amount (Γ) of 1.11 mg m-2, leading to the quality factor (Q f) of 31.71 mg m-2. At a lower concentration, the deposition of lignin on the surface was increased, and it generated a maximum sticking coefficient of ß = 0.71 at 25 mg L-1 on the surface. At the concentration range of 35 and 45 mg L-1, lignin formed clusters and its deposition dropped. The use of Quartz crystal microbalance (QCM) and SPAR techniques also confirmed that the proportion of water in the deposited lignin adlayer was greater when a lower concentration (5-25 mg L-1) of lignin solution was used for adsorption. The findings of this study revealed the potential use of the SPAR technique for evaluating the deposition performance of lignin-based materials on varied surfaces, which would facilitate the development of coating and composite applications for lignin.

6.
Sci Adv ; 6(37)2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32917701

RESUMO

The propagation of elastic waves in soft materials plays a crucial role in the spatiotemporal transmission of mechanical signals, e.g., in biological mechanotransduction or in the failure of marginal solids. At high Reynolds numbers Re ≫ 1, inertia dominates and wave propagation is readily observed. However, mechanical cues in soft and biological materials often occur at low Re, where waves are overdamped. Overdamped waves are not only difficult to observe experimentally, also theoretically their description remains incomplete. Here, we present direct measurements of the propagation and attenuation of mechanical signals in colloidal soft solids, induced by an optical trap. We derive an analytical theory for low Re wave propagation and damping, which is in excellent agreement with the experiments. Our results present both a previously unexplored method to characterize damped waves in soft solids and a theoretical framework showing how localized mechanical signals can provoke a remote and delayed response.

7.
Langmuir ; 36(29): 8494-8502, 2020 07 28.
Artigo em Inglês | MEDLINE | ID: mdl-32598154

RESUMO

Encapsulation of charged proteins into complex coacervate core micelles (C3Ms) can be accomplished by mixing them with oppositely charged diblock copolymers. However, these micelles tend to disintegrate at high ionic strength. Previous research showed that the addition of a homopolymer with the same charge sign as the protein improved the stability of protein-containing C3Ms. In this research, we used fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS) to study how the addition of the homopolymer affects the encapsulation efficiency and salt stability of the micelles. We studied the encapsulation of laccase spore coat protein A (CotA), a multicopper oxidase, using a strong cationic-neutral diblock copolymer, poly(N-methyl-2-vinyl-pyridinium iodide)-block-poly(ethylene oxide) (PM2VP128-b-PEO477), and a negatively charged homopolymer, poly(4-styrenesulfonate) (PSS215). DLS indeed showed an improved stability of this three-component C3M system against the addition of salt compared to a two-component system. Remarkably, FCS showed that the release of CotA from a three-component C3M system occurred at a lower salt concentration and over a narrower concentration range than the dissociation of C3Ms. In conclusion, although the addition of the homopolymer to the system leads to micelles with a higher salt stability, CotA is excluded from the C3Ms already at lower ionic strengths because the homopolymer acts as a competitor of the enzyme for encapsulation.


Assuntos
Micelas , Polietilenoglicóis , Cátions , Polímeros , Espectrometria de Fluorescência
8.
J Colloid Interface Sci ; 565: 278-287, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31978790

RESUMO

The use of polymeric nanoparticles (NPs) as therapeutics has been steadily increasing over past decades. In vivo imaging of NPs is necessary to advance the therapeutic performance. 19F Magnetic Resonance Imaging (19F MRI) offers multiple advantages for in vivo imaging. However, design of a probe for both biodistribution and degradation has not been realized yet. We developed polymeric NPs loaded with two fluorocarbons as promising imaging tools to monitor NP biodistribution and degradation by 19F MRI. These 200 nm NPs consist of poly(lactic-co-glycolic acid) (PLGA) loaded with perfluoro-15-crown-5 ether (PFCE) and PERFECTA. PERFECTA/PFCE-PLGA NPs have a fractal sphere structure, in which both fluorocarbons are distributed in the polymeric matrix of the fractal building blocks, which differs from PFCE-PLGA NPs and is unique for fluorocarbon-loaded colloids. This structure leads to changes of magnetic resonance properties of both fluorocarbons after hydrolysis of NPs. PERFECTA/PFCE-PLGA NPs are colloidally stable in serum and biocompatible. Both fluorocarbons show a single resonance in 19F MRI that can be imaged separately using different excitation pulses. In the future, these findings may be used for biodistribution and degradation studies of NPs by 19F MRI in vivo using "two color" labeling leading to improvement of drug delivery agents.


Assuntos
Cor , Imagem por Ressonância Magnética de Flúor-19 , Fluorocarbonos/metabolismo , Leucócitos Mononucleares/metabolismo , Nanopartículas/metabolismo , Sobrevivência Celular , Células Cultivadas , Fluorocarbonos/química , Humanos , Leucócitos Mononucleares/química , Leucócitos Mononucleares/citologia , Estrutura Molecular , Nanopartículas/química , Tamanho da Partícula , Propriedades de Superfície
9.
Adv Funct Mater ; 29(19)2019 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-32132881

RESUMO

Ultrasound is the most commonly used clinical imaging modality. However, in applications requiring cell-labeling, the large size and short active lifetime of ultrasound contrast agents limit their longitudinal use. Here, 100 nm radius, clinically applicable, polymeric nanoparticles containing a liquid perfluorocarbon, which enhance ultrasound contrast during repeated ultrasound imaging over the course of at least 48 h, are described. The perfluorocarbon enables monitoring the nanoparticles with quantitative 19F magnetic resonance imaging, making these particles effective multimodal imaging agents. Unlike typical core-shell perfluorocarbon-based ultrasound contrast agents, these nanoparticles have an atypical fractal internal structure. The nonvaporizing highly hydrophobic perfluorocarbon forms multiple cores within the polymeric matrix and is, surprisingly, hydrated with water, as determined from small-angle neutron scattering and nuclear magnetic resonance spectroscopy. Finally, the nanoparticles are used to image therapeutic dendritic cells with ultrasound in vivo, as well as with 19F MRI and fluorescence imaging, demonstrating their potential for long-term in vivo multimodal imaging.

10.
Macromolecules ; 51(20): 8316-8323, 2018 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-30405273

RESUMO

The synthesis of charged polymers often requires the polymerization of protected monomers, followed by a polymer-analogous reaction to the polyelectrolyte product. We present a mild, facile method to cleave tert-butyl groups from poly(tert-butyl acrylate) blocks that yields poly(acrylic acid) (pAA) blocks free of traces of the ester. The reaction utilizes a slight excess of HCl in hexafluoroisopropanol (HFIP) at room temperature and runs to completion within 4 h. We compare deprotection in HFIP with the common TFA/DCM method and show that the latter does not yield clean pAA. We show the effect of complete tert-butyl cleavage on a ABA triblock copolymer, where poly(N-isopropylacrylamide) (pNIPAM) is A and pAA is B, by means of viscosimetry, DLS, and SAXS on solutions above overlap. The pNIPAM blocks dehydrate, and their increased self-affinity above the lower critical solution temperature (LCST) results in network formation by the triblocks. This manifests itself as an increase in viscosity and a slowing down of the first-order correlation function in light scattering. However, this stickering effect manifests itself exclusively when the pAA block is tert-butyl-free. Additionally, SAXS shows that the conformational properties of tert-butyl-free pAA copolymers are markedly different from those with residual esters. Thus, we illustrate a surprising effect of hydrophobic impurities that act across blocks and assert the usefulness of HCl/HFIP in pAA synthesis.

11.
Soft Matter ; 14(47): 9542-9549, 2018 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-30357241

RESUMO

Micelles have been recognized as versatile platforms for different biomedical applications, from bioimaging to drug delivery. Complex coacervate core micelles present great advantages compared to traditional micelles, however controlling the number of charges per core-unit and the stability is still a challenge. We here present cyclodextrin-based complex coacervate core micelles where the charge per core-unit can be straightforwardly tuned by cyclodextrin host-guest interactions. By varying the ratio between two adamantane guest molecules, 1-adamantanecarboxylic acid and 1,3-adamantanediacetic acid, the charge of the monomeric core-units can be finely tuned from 6- to 9-. By adding an adamantane bislinker, monomeric core-units can be combined together in dimeric and polymeric structures, increasing the micelles' stability. The orthogonal supramolecular host-guest and coordination-chemistry allows for well-controlled cyclodextrin-based complex coacervate core micelles that offer a versatile platform for designing future, e.g., responsive systems.

12.
Biomacromolecules ; 19(9): 3766-3775, 2018 09 10.
Artigo em Inglês | MEDLINE | ID: mdl-30102855

RESUMO

In this study, native chemical ligation (NCL) was used as a selective cross-linking method to form core-cross-linked thermosensitive polymeric micelles for drug delivery applications. To this end, two complementary ABA triblock copolymers having polyethylene glycol (PEG) as midblock were synthesized by atom transfer radical polymerization (ATRP). The thermosensitive poly isopropylacrylamide (PNIPAM) outer blocks of the polymers were copolymerized with either N-(2-hydroxypropyl)methacrylamide-cysteine (HPMA-Cys), P(NIPAM- co-HPMA-Cys)-PEG-P(NIPAM- co-HPMA-Cys) (PNC) or N-(2-hydroxypropyl)methacrylamide-ethylthioglycolate succinic acid (HPMA-ETSA), P(NIPAM- co-HPMA-ETSA)-PEG-P(NIPAM- co-HPMA-ETSA) (PNE). Mixing of these polymers in aqueous solution followed by heating to 50 °C resulted in the formation of thermosensitive flower-like micelles. Subsequently, native chemical ligation in the core of micelles resulted in stabilization of the micelles with a Z-average of 65 nm at body temperature. Decreasing the temperature to 10 °C only affected the size of the micelles (increased to 90 nm) but hardly affected the polydispersity index (PDI) and aggregation number ( Nagg) confirming covalent stabilization of the micelles by NCL. CryoTEM images showed micelles with an uniform spherical shape and dark patches close to the corona of micelles were observed in the tomographic view. The dark patches represent more dense areas in the micelles which coincide with the higher content of HPMA-Cys/ETSA close to the PEG chain revealed by the polymerization kinetics study. Notably, this cross-linking method provides the possibility for conjugation of functional molecules either by using the thiol moieties still present after NCL or by simply adjusting the molar ratio between the polymers (resulting in excess cysteine or thioester moieties) during micelle formation. Furthermore, in vitro cell experiments demonstrated that fluorescently labeled micelles were successfully taken up by HeLa cells while cell viability remained high even at high micelle concentrations. These results demonstrate the potential of these micelles for drug delivery applications.


Assuntos
Reagentes de Ligações Cruzadas/química , Portadores de Fármacos/síntese química , Micelas , Resinas Acrílicas/química , Células HeLa , Humanos , Metacrilatos/química , Polietilenoglicóis/química , Coroa de Proteína/química , Temperatura , Tioglicolatos/química
13.
RSC Adv ; 8(12): 6460-6470, 2018 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-35540375

RESUMO

Poly(lactic-co-glycolic acid) (PLGA) particles are very widely used, particularly for drug delivery, including commercial clinical formulations. Adding perfluorocarbon (PFC) enables in vivo imaging and quantification of the PLGA particles through 19F NMR, MRS or MRI. PFCs are both hydrophobic and lipophobic at the same time. This property makes their encapsulation in particles challenging, as it requires the addition of a third immiscible phase during the emulsification process. Here we explore how different parameters affect the miniemulsion formation of particles loaded with perfluoro-15-crown-5-ether (PFCE). By changing the concentration of surfactant and type of solvent, we were able to control the radius of synthesized particles, between 85-200 nm. We assessed stability and release from the particles at different pH values, showing that hydrophobic agents are released from the particles by diffusion rather than degradation. With cell experiments, we show that primary human dendritic cells take up the particles without any apparent effect, including on cell migration. In summary, the control of synthesis conditions leads to particles with sufficient PFCE encapsulation, which are suitable for drug loading and cell labeling, and do not affect cell viability or functionality. Finally, these nanoparticles can be produced at GMP-grade for clinical use.

14.
Sci Rep ; 6: 34383, 2016 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-27682840

RESUMO

Drying and aging paint dispersions display a wealth of complex phenomena that make their study fascinating yet challenging. To meet the growing demand for sustainable, high-quality paints, it is essential to unravel the microscopic mechanisms underlying these phenomena. Visualising the governing dynamics is, however, intrinsically difficult because the dynamics are typically heterogeneous and span a wide range of time scales. Moreover, the high turbidity of paints precludes conventional imaging techniques from reaching deep inside the paint. To address these challenges, we apply a scattering technique, Laser Speckle Imaging, as a versatile and quantitative tool to elucidate the internal dynamics, with microscopic resolution and spanning seven decades of time. We present a toolbox of data analysis and image processing methods that allows a tailored investigation of virtually any turbid dispersion, regardless of the geometry and substrate. Using these tools we watch a variety of paints dry and age with unprecedented detail.

15.
Biomacromolecules ; 17(7): 2392-8, 2016 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-27250876

RESUMO

We investigated the growth of biosynthetic protein polymers with templated curvature on pluronic nanospheres. The protein has a central silk-like block containing glutamic residues (S(E)) and collagen-like end-blocks (C). The S(E) blocks stack into filaments when their charge is removed (pH <5). Indeed, at low pH curved and circular fibers are formed at the surface of the nanospheres, which keep their shape after removal of the pluronics. The data reveal the mechanism of the templated fibril-growth: The growth of protein assemblies is nucleated in solution; small protein fibrils adsorb on the nanospheres, presumably due to hydrogen bond formation between the silk-like blocks and the pluronic PEO blocks. The surface of the pluronic particles templates further growth. At relatively low protein/pluronic weight ratios, only a fraction of the nanospheres bears protein fibers, pointing to a limiting amount of nuclei in solution. Because the nanospheres capture fibrils at an early stage of growth, they can be used to separate growth and nucleation rates in protein fibril formation. Moreover, the nanoparticle-templated growth of stable curved fibers opens ways to build proteinaceous nanocapsules from designed protein polymers.


Assuntos
Colágeno/química , Nanosferas/química , Poloxâmero/química , Polímeros/química , Seda/química , Matriz Extracelular , Humanos , Propriedades de Superfície
16.
Environ Toxicol Chem ; 35(7): 1650-5, 2016 07.
Artigo em Inglês | MEDLINE | ID: mdl-26588181

RESUMO

Microplastic has become an emerging contaminant of global concern. Bulk plastic can degrade to form smaller particles down to the nanoscale (<100 nm), which are referred to as nanoplastics. Because of their high surface area, nanoplastic may bind hydrophobic chemicals very effectively, increasing their hazard when such nanoplastics are taken up by biota. The present study reports distribution coefficients for sorption of polycyclic aromatic hydrocarbons (PAHs) to 70 nm polystyrene in freshwater, and PAH adsorption isotherms spanning environmentally realistic aqueous concentrations of 10(-5) µg/L to 1 µg/L. Nanopolystyrene aggregate state was assessed using dynamic light scattering. The adsorption isotherms were nonlinear, and the distribution coefficients at the lower ends of the isotherms were very high, with values up to 10(9) L/kg. The high and nonlinear sorption was explained from π-π interactions between the planar PAHs and the surface of the aromatic polymer polystyrene and was higher than for micrometer-sized polystyrene. Reduction of nanopolystyrene aggregate sizes had no significant effect on sorption, which suggests that the PAHs could reach the sorption sites on the pristine nanoparticles regardless of the aggregation state. Pre-extraction of the nanopolystyrene with C18 polydimethylsiloxane decreased sorption of PAHs, which could be explained by removal of the most hydrophobic fraction of the nanopolystyrene. Environ Toxicol Chem 2016;35:1650-1655. © 2015 SETAC.


Assuntos
Água Doce/química , Nanopartículas/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Poliestirenos/análise , Poluentes Químicos da Água/análise , Adsorção , Interações Hidrofóbicas e Hidrofílicas , Nanopartículas/química , Tamanho da Partícula , Hidrocarbonetos Policíclicos Aromáticos/química , Poliestirenos/química , Propriedades de Superfície , Poluentes Químicos da Água/química
17.
J Phys Chem B ; 119(40): 12938-46, 2015 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-26368593

RESUMO

Polymer chains grafted onto nanoparticles may facilitate the dispersion of such particles in a polymer solution. We explore the optimal strategy for stabilizing polymer-grafted nanoparticles using self-consistent field theory and experiments. The best results are obtained for relatively low grafting densities and for chain lengths of the brush polymer NB larger than that of the freely floating polymers Nf. When Nf > NB, one finds a compatibilization gap and re-entrant stabilization: At both very low and very high polymer concentrations particles disperse in the polymer solution, while at intermediate concentrations the particles lose their colloidal stability. At low grafting densities the underlying surface is in contact with the solvent. Particles covered by a bidisperse brush can combine a low grafting outer region with full coverage of the surface by a densely grafted inner layer. Using classical colloid-chemical stabilization criteria the region in the phase diagram for which the particles are expected to mix with a concentrated polymer solution opens up. Now, also upon an increase in the length of the freely dispersed polymers, a re-entrant colloid-chemical stabilization is found for particles on the nanometer length scale: At both short and long polymer chains in solution the particles will not aggregate, whereas at intermediate lengths the colloidal stability is marginal. This multi re-entrant behavior is found from numerical self-consistent field calculations, and these predictions are consistent with corresponding experiments.

18.
Toxicol In Vitro ; 29(7): 1701-10, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26145586

RESUMO

To obtain insight in translocation of nanoparticles across the placental barrier, translocation was studied for one positively and two negatively charged polystyrene nanoparticles (PS-NPs) of similar size in an in vitro model. The model consisted of BeWo b30 cells, derived from a human choriocarcinoma grown on a transwell insert forming a cell layer that separates an apical from a basolateral compartment. PS-NPs were characterized with respect to size, surface charge, morphology and protein corona. Translocation of PS-NPs was not related to PS-NP charge. Two PS-NPs were translocated across the BeWo transwell model to a lower extent than amoxicillin, a model compound known to be translocated over the placental barrier to only a limited extent, whereas one PS-NP showed a slightly higher translocation. Studies on the effect of transporter inhibitors on the translocation of the PS-NPs indicated that their translocation was not mediated by known transporters and mainly dependent on passive diffusion. It is concluded that the BeWo b30 model can be used as an efficient method to get an initial qualitative impression about the capacity of NPs to translocate across the placental barrier and set priorities in further in vivo studies on translocation of NPs to the fetus.


Assuntos
Nanopartículas/metabolismo , Placenta/metabolismo , Poliestirenos/metabolismo , Transporte Biológico , Linhagem Celular Tumoral , Feminino , Humanos , Gravidez
19.
Biomacromolecules ; 16(5): 1542-9, 2015 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-25857527

RESUMO

Protein encapsulation with polymers has a high potential for drug delivery, enzyme protection and stabilization. Formation of such structures can be achieved by the use of polyelectrolytes to generate so-called complex coacervate core micelles (C3Ms). Here, encapsulation of enhanced green fluorescent protein (EGFP) was investigated using a cationic-neutral diblock copolymer of two different sizes: poly(2-methyl-vinyl-pyridinium)41-b-poly(ethylene-oxide)205 and poly(2-methyl-vinyl-pyridinium)128-b-poly(ethylene-oxide)477. Dynamic light scattering and fluorescence correlation spectroscopy (FCS) revealed a preferred micellar composition (PMC) with a positive charge composition of 0.65 for both diblock copolymers and micellar hydrodynamic radii of approximately 34 nm. FCS data show that at the PMC, C3Ms are formed above 100 nM EGFP, independent of polymer length. Mixtures of EGFP and nonfluorescent GFP were used to quantify the amount of GFP molecules per C3M, resulting in approximately 450 GFPs encapsulated per micelle. This study shows that FCS can be successfully applied for the characterization of protein-containing C3Ms.


Assuntos
Sistemas de Liberação de Medicamentos , Proteínas de Fluorescência Verde/química , Polímeros/química , Humanos , Concentração de Íons de Hidrogênio , Micelas , Polietilenoglicóis/química
20.
Proc Natl Acad Sci U S A ; 111(43): 15356-61, 2014 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-25319262

RESUMO

Stress relaxation in crystalline solids is mediated by the formation and diffusion of defects. Although it is well established how externally generated stresses relax, through the proliferation and motion of dislocations in the lattice, it remains relatively unknown how crystals cope with internal stresses. We investigate, both experimentally and in simulations, how highly localized stresses relax in 2D soft colloidal crystals. When a single particle is actively excited, by means of optical tweezing, a rich variety of highly collective stress relaxation mechanisms results. These relaxation processes manifest in the form of open strings of cooperatively moving particles through the motion of dissociated vacancy-interstitial pairs, and closed loops of mobile particles, which either result from cooperative rotations in transiently generated circular grain boundaries or through the closure of an open string by annihilation of a vacancy-interstitial pair. Surprisingly, we find that the same collective events occur in crystals that are excited by thermal fluctuations alone; a large thermal agitation inside the crystal lattice can trigger the irreversible displacements of hundreds of particles. Our results illustrate how local stresses can induce large-scale cooperative dynamics in 2D soft colloidal crystals and shed light on the stabilization mechanisms in ultrasoft crystals.

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