This review discusses recent progress in physicochemical understanding of the action of the saponin β -aescin (also called β -escin), the biologically active component in the seeds of the horse ...chestnut tree
. β -Aescin is used in pharmacological and cosmetic applications showing strong surface activity. In this review, we outline the most important findings describing the behavior of β -aescin in solution (e.g., critical micelle concentration ( c m c ) and micelle shape) and special physicochemical properties of adsorbed β -aescin monolayers at the air-water and oil-water interface. Such monolayers were found to posses very special viscoelastic properties. The presentation of the experimental findings is complemented by discussing recent molecular dynamics simulations. These simulations do not only quantify the predominant interactions in adsorbed monolayers but also highlight the different behavior of neutral and ionized β -aescin molecules. The review concludes on the interaction of β -aescin with phospholipid model membranes in the form of bilayers and Langmuir monolayers. The interaction of β -aescin with lipid bilayers was found to strongly depend on its c m c . At concentrations below the c m c , membrane parameters are modified whereas above the c m c , complete solubilization of the bilayers occurs, depending on lipid phase state and concentration. In the presence of gel-phase phospholipids, discoidal bicelles form; these are tunable in size by composition. The phase behavior of β -aescin with lipid membranes can also be modified by addition of other molecules such as cholesterol or drug molecules. The lipid phase state also determines the penetration rate of β -aescin molecules into lipid monolayers. The strongest interaction was always found in the presence of gel-phase phospholipid molecules.
The internal structure of nanometric microgels in water has been studied as a function of temperature, cross-linker content, and level of deuteration. Small-angle neutron scattering from ...poly(N-isopropylmethacrylamide) (volume phase transition ≈ 44 °C) microgel particles of radius well below 100 nm in D2O has been measured. The intensities have been analyzed with a combination of polymer chain scattering and form-free radial monomer volume fraction profiles defined over spherical shells, taking polydispersity in size of the particles determined by atomic force microscopy into account. A reverse Monte Carlo optimization using a limited number of parameters was developed to obtain smoothly decaying profiles in agreement with the experimentally scattered intensities. The results are compared to the swelling curve of microgel particles in the temperature range from 15 to 55 °C obtained from photon correlation spectroscopy (PCS). In addition to hydrodynamic radii measured by PCS, our analysis provides direct information about the internal water content and gradients, the strongly varying steepness of the density profile at the particle–water interface, the total spatial extension of the particles, and the visibility of chains. The model has also been applied to a variation of the cross-linker content, N,N′-methylenebisacrylamide, from 5 to 15 mol %, providing insight on the impact of chain architecture and cross-linking on water uptake and on the definition of the polymer–water interface. The model can easily be generalized to arbitrary monomer contents and types, in particular mixtures of hydrogenated and deuterated species, paving the way to detailed studies of monomer distributions inside more complex microgels, in particular core–shell particles.
In the present study, we show how acrylamide-based microgels can be employed for the uptake and release of the drug β-aescin, a widely used natural product with a variety of pharmacological effects. ...We show how aescin is incorporated into the microgel particles. It has an important influence on the structure of the microgels, by reducing their natural network-density gradient in the swollen state. Moreover, temperature-dependent measurements reveal how the incorporation of aescin stabilizes the microgel particles, while the volume phase transition temperature (VPTT) is almost constant, which is very important for the intended drug release. Finally, it is shown that upon increase of the temperature above the VPTT the particles are able to release aescin from their network, encouraging the use of this particular drug delivery system for hypothermia treatments.
Understanding and controlling 3D nanocrystal self‐assembly is a fundamental challenge in materials science. Assembly enables the unique optical and electronic properties of nanocrystals to be ...exploited in macroscopic materials, and also opens up the possibility to couple the optical response of nanocrystals to the optical modes of the superlattice. To date, assembly of such nanocrystal superlattices (NCSL) has focussed on fixed, close packed structures with particle separations of just 1–3 nm. To achieve highly crystalline structures with tunable optical response, the nanocrystal interparticle separation needs to be precise and easily variable but >50 nm. Here, we show the preparation of nanocrystal superlattices with spacings of 50–500 nm assembled from gold‐poly‐N‐isopropylacrylamide core‐shell particles and the characterization of their fascinating diffraction behavior by means of UV‐vis spectroscopy. These nanocrystal superlattices exhibit pronounced diffraction in the visible (440‐560 nm) with peak half‐widths of the order of 10 nm. The position of the Bragg peak is simply tuned by adjusting the particle volume fraction. Due to the thermoresponsive nature of the polymer shell, temperature is used to initiate crystallization or melting of the superlattice. Heating and cooling cycles cause highly reversible melting/recrystallization in less than a minute.
Nanocrystal superlattices from gold‐poly‐N‐isopropylacrylamide (Au‐PNIPAM) core– shell particles are prepared within a broad range of concentrations in aqueous dispersions. These superlattices show strong Bragg diffraction in the visible, tunable by the particle volume fraction as well as temperature. Structural changes (melting/recrystallization) upon changes in temperature are highly reversible.
In this study we present novel core–shell microgels, with a shell made of poly(N-n-propylacrylamide) (pNNPAM) and a core consisting of poly(N-iso-propylmethacrylamide) (pNIPMAM), exhibiting a unique ...linear temperature response. The effect is produced by the large LCST gap of 23 °C between the shell- and the core-forming polymer. We demonstrate that the shell exhibits a temperature induced de-swelling process that is almost independent of the swelling properties of the core. Furthermore the active collapse of the shell forces a collapse of the core (which is known as the so-called “corset-effect”). In a region between 25 °C and 41 °C the response of the particles is directly proportional to the temperature. Moreover, the core properties were systematically varied, revealing the possibility to linearly change the magnitude of the linear swelling. Hence, these particles are very promising as piezo-like linear nano-actuators.
Display omitted
While cationic microgels are potentially useful for the transfection or transformation of cells, their synthesis has certain drawbacks regarding size, polydispersity, yield, and incorporation of the ...cationic comonomers. In this work, a range of poly(
-isopropylacrylamide) (PNIPAM) microgels with different amounts of the primary amine
-(3-aminopropyl)methacrylamide hydrochloride (APMH) as the cationic comonomer were synthesized. Moreover, the pH-value during reaction was varied for the synthesis of microgels with 10 mol% APMH-feed. The microgels were analyzed by means of their size, thermoresponsive swelling behavior, synthesis yield, polydispersity and APMH-incorporation. The copolymerization of APMH leads to a strong decrease in size and yield of the microgels, while less than one third of the nominal APMH monomer feed is incorporated into the microgels. With an increase of the reaction pH up to 9.5, the negative effects of APMH copolymerization were significantly reduced. Above this pH, synthesis was not feasible due to aggregation. The results show that the reaction pH has a strong influence on the synthesis of pH-responsive cationic microgels and therefore it can be used to tailor the microgel properties.
CBD is a promising candidate for treatment of many diseases and plays a major role in the growing trend to produce high-end drugs from natural, renewable resources. In the present work, we ...demonstrate a way to incorporate the anti-inflammatory drug CBD into smart microgel particles. The copolymer microgels that we chose as carrier systems exhibit a volume phase transition temperature of 39 ∘C, which is just above normal body temperature and makes them ideal candidates for hyperthermia treatment. While a simple loading route of CBD was not successful due to the enormous hydrophobicity of CBD, an alternative route was developed by immersing the microgels in ethanol. Despite the expected loss of thermoresponsive behaviour of the microgel matrix due to the solvent exchange, a temperature-dependent release of CBD was detected by the material, creating an interesting question of interactions between CBD and the microgel particles in ethanol. Furthermore, the method developed for loading of the microgel particles with CBD in ethanol was further improved by a subsequent transfer of the loaded particles into water, which proves to be an even more promising approach due to the successful temperature-dependent release of the drug above the collapse temperature of the microgels.
Highly uniform, core−shell microgels consisting of single gold nanoparticle cores and cross-linked poly-N-isopropylacrylamide (PNIPAM) shells were prepared by a novel, versatile protocol. The ...synthetic pathway allows control over the polymer shell thickness and its swelling behavior. The core−shell structure was investigated by electron microscopy and atomic force microscopy, whereas the swelling behavior of the shell was studied by means of dynamic light scattering and UV−vis spectroscopy. Furthermore, the latter method was used to investigate the optical properties of the hybrid particles. By modeling the scattering contribution from the PNIPAM shells, the absorption spectra of the gold nanoparticle cores could be recovered. This allows the particle concentration to be determined, and this in turn permits the calculation of the molar mass of the hybrid particles as well as the refractive index of the shells.
In the present paper, thermosensitive coatings are prepared by deposition of P(NIPAM-co-AAc) microgel particles on precoated silicon wafers. The effect of pH, substrate precoating, and preparation ...technique is studied. The pH value is found to significantly influence the adsorption density, while the substrate surface charge is less important. Hence, the electrostatic contribution of the particle−particle interaction seems to play a more pronounced role for the adsorption density than at least the electrostatic part of the particle−surface interaction. For the latter, also nonelectrostatic contributions like hydrogen bonding and surface roughness play an important role. Immersion of the prepared polyelectrolyte/microgel layers in buffers leads to a reorganization of the adsorbed particles at the surface.
PDF
