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Biomedical subjects

Helmuth Möhwald

Publications and source records attributed to Helmuth Möhwald.

At least 37 records · Page 2Linked to original sources
PubMed2006

Complexes of poly(ethylene oxide)-block-poly(L-glutamate) and diminazene.

Nanoparticles with a mean hydrodynamic radius of 16 nm and low polydispersity (P.I. = 0.1) were spontaneously formed by the complexation of poly(ethylene oxide)-block-poly(L-glutamate) (PEO-b-PLGlu) with diminazene. Only one of two possible binding sites of each diminazene molecule was involved in complexation. As determined by UV-vis difference spectra measurements, the complex binding constant is on the order of 1-2 x 10(4) M(-1). Circular dichroism measurements showed that the highly water-soluble diminazene can induce and stabilize the alpha-helical secondary structure of a PLGlu block.

Journal Article↗
PubMed2006

Polyoxometalate-based electro- and photochromic dual-mode devices.

Molecular or supramolecular systems capable of electro- and photostimulated color changes are still rare. We present a device design based on an electrostatic complex of a nanoscopic polyoxometalate cluster and a polyelectrolyte. The coating reversibly changes color from transparent to blue by photo- and/or electroinduced stimulation. The choice of the components results in perfect transparency over the entire visible range, a large optical response, reversible operation, and excellent stability.

Journal Article↗
PubMed2006

Maghemite nanoparticles protectively coated with poly(ethylene imine) and poly(ethylene oxide)-block-poly(glutamic acid).

Superparamagnetic iron oxide particles (SPIO) of maghemite were prepared in aqueous solution and subsequently stabilized with polymers in two layer-by-layer deposition steps. The first layer around the maghemite core is formed by poly(ethylene imine) (PEI), and the second one is formed by poly(ethylene oxide)-block-poly(glutamic acid) (PEO-PGA). The hydrodynamic diameter of the particles increases stepwise from D(h) = 25 nm (parent) via 35 nm (PEI) to 46 nm (PEI plus PEO-PGA) due to stabilization. This is accompanied by a switching of their zeta-potentials from moderately positive (+28 mV) to highly positive (+50 mV) and finally slightly negative (-3 mV). By contrast, the polydispersity indexes of the particles remain constant (ca. 0.15). Mössbauer spectroscopy revealed that the iron oxide, which forms the core of the particles, is only present as Fe(III) in the form of superparamagnetic maghemite nanocrystals. The magnetic domains and the maghemite crystallites were found to be identical with a size of 12.0 +/- 0.5 nm. The coated maghemite nanoparticles were tested to be stable in water and in physiological salt solution for longer than 6 months. In contrast to novel methods for magnetic nanoparticle production, where organic solvents are necessary, the procedure proposed here can dispense with organic solvents. Magnetic resonance imaging (MRI) experiments on living rats indicate that the nanoparticles are useful as an MRI contrast agent.

Animals↗
PubMed2006

Ionization state and structure of l-1,2-dipalmitoylphosphatidylglycerol monolayers at the liquid/air interface.

Phosphatidylglycerols are components of biological membranes. The phase behavior of these phospholipids was extensively investigated. However, there is still no definite picture about the dependence of the ionization state and monolayer structure on subphase composition. The major problem of previous investigations is that none of the methods used allow obtaining the ionization degree directly. In the present work we apply techniques developed in the past decades for Langmuir monolayers: infrared reflection absorption spectroscopy (IRRAS) as well as X-ray diffraction and reflectivity techniques, which provide straightforward information about structure and ionization state of a L-1,2-dipalmitoylphosphatidylglycerol (DPPG) monolayer. The Gouy-Chapman model is applied to evaluate the intrinsic pKa. Therewith, the ionization degree can be determined even at low pH values. The experimental titration curves are in good agreement with theoretical curves based on the Gouy-Chapman model. The obtained instrinic pKa amounts to 1. The ionization degree of a DPPG monolayer is independent of the monovalent cation size. In contrast, the structure of a DPPG monolayer is strongly affected by the type of divalent cations.

Air↗
PubMed2006

Adsorption of novel thermosensitive graft-copolymers: Core-shell particles prepared by polyelectrolyte multilayer self-assembly.

The adsorption properties of thermosensitive graft-copolymers are investigated with the aim of developing self-assembled multilayers from these copolymers. The copolymers consist of a thermoreversible main chain of poly(N-isopropylacrylamid) and a weak polyelectrolyte, poly(2-vinylpyridine), as grafted side chains. Zeta-potential, single particle light scattering and adsorption isotherms monitor the adsorption of the thermoreversible copolymers to precoated colloidal particles. The results show a smaller surface coverage for a larger density of grafted chains. The surface coverage is discussed in terms of surface charge density in the adsorbed monolayer. Taking into account the monolayer adsorption properties, conditions are developed for the multilayer formation from these copolymers. A low pH provides a sufficient charge density of the grafted chains to achieve a surface charge reversal of the colloids upon adsorption. The charge reversal after each adsorbed layer is monitored by zeta-potential and the increase of the thickness is determined by light scattering. Stable and reproducible multilayers are obtained. The results imply that the conformation of the thermosensitive component in multilayers depends strongly on the grafting density, where the polymer with a higher grafting density adsorbs in a flat conformation while that with a lower grafting density adsorbs with more loops.

Journal Article↗
PubMed2006

Redox processes of cytochrome c immobilized on solid supported polyelectrolyte multilayers.

The heme protein cytochrome c (Cyt-c), immobilized on polyelectrolyte multilayers on a silver electrode, was studied by stationary and time-resolved surface-enhanced resonance Raman (SERR) spectroscopy to probe the redox site structure and the mechanism and dynamics of the potential-dependent interfacial processes. The layers were built up by sequential adsorption of polycations (poly[ethylene imine] (PEI); polyallylamine hydrochloride (PAH)) and polyanions (poly[styrene sulfonate] (PSS)). All multilayers terminated by PSS electrostatically bind Cyt-c. On PEI/PSS coatings, Cyt-c is peripherally bound and fully redox-active. Due to the interfacial potential drop, the apparent redox potential is lowered by 40 mV compared to that in solution. The rate constant for the heterogeneous electron transfer (ET) of ca. 0.1 s(-1) is consistent with electron tunneling through largely ordered PEI/PSS layers. ET is coupled to a reversible conformational transition of Cyt-c that involves a change of the coordination pattern of the heme. Additional (PAH/PSS) double layers cause a broadening of the redox transition and a drastic negative shift of the redox potential, which is attributed to the formation of PSS/Cyt-c complexes. It is concluded that Cyt-c can effectively compete with PAH for binding of PSS, resulting in a rearrangement of the layered structure and a penetration of the PSS-bound Cyt-c into the PAH/PSS double layers. This conclusion is consistent with SERR intensity and quartz microbalance measurements. ET was found to be overpotential-independent and faster than that for PEI/PSS coatings, which is interpreted in terms of specific PSS/Cyt-c complexes serving as gates for the heterogeneous ET.

Cytochromes c↗
PubMed2006

pH controlled permeability of lipid/protein biomimetic microcapsules.

The permeability of lipid and protein microcapsules fabricated by alternating adsorption of human serum albumin (HSA) and L-alpha-dimyristoylphosphatidic acid (DMPA) on a template and subsequent removal of the core is studied as a function of pH value and supplementary layers. The capsules were permeable for macromolecules (FITC-labeled dextran, M(w) 40 kDa) at pH < 4.8 and impermeable at pH > 7.4. The assembly of supplementary DMPA bilayers rendered the capsules impermeable for small hydrophilic molecules such as 6-carboxyfluorescein (6-CF). Hence DMPA/HSA capsules can be resealed after fabrication by supplementary layers. This provides the opportunity of applying such biomimetic membrane capsules as drug carriers or model systems to study biological processes at membranes.

Adsorption↗
PubMed2006

Mechanical property of lipid-coated polyelectrolyte microcapsules.

The deformations of lipid coated polyelectrolyte capsules induced by osmotic pressure were determined in poly(styrene sulfonate, sodium salt) (PSS) solution by making use of the fact that PSS molecules with a molecular weight 70000 will not penetrate into the capsules. At a critical osmotic pressure the initial spherical capsules changed their shape and became an invagination. The measurements of single particle light scattering provided the wall thickness of the lipid-coated capsules with 25.6 nm while the thickness for pure polyelectrolyte capsules in solution is about 21.6 nm, indicating that the coating lipid layer has about 4 nm thickness. It demonstrates that DMPA forms a bilayer on the surface of polyelectrolyte capsules. With these data, that the elasticity coefficient of the lipid-coated capsules is about 426 Mpa can be obtained.

Adsorption↗
PubMed2005

Multilayer microcapsules as anti-cancer drug delivery vehicle: deposition, Sustained release, and in vitro bioactivity.

A drug delivery system based on spontaneous deposition of soluble, low-molecular-weight therapeutic agents has been developed for the purpose of sustaining drug release. Layer-by-layer assembly of oppositely charged polyelectrolytes onto melamine formaldehyde (MF) colloidal particles, followed by removal of the cores at low pH has yielded intact hollow microcapsules having the ability to induce deposition of various water-soluble substances. Dynamic observation by confocal laser scanning microscopy provided direct evidence of such deposition. Dependence of loading rate on molecular weight was investigated. Efficient loading of an anti-cancer drug, daunorubicin (DNR), was confirmed by transmission electron microscopy (TEM). Its release was quantified by fluorometry. The results indicated that loading, and subsequent release, could be tuned by factors such as feeding concentrations, temperature, and salt concentrations. The intrinsic mechanism of loading and release was discussed taking into account the interaction between the drugs and the poly(styrene sulfonate)/MF complex existing in the hollow capsules. With culture of the HL-60 cell line, a kind of human leukemia cell, the presence of DNR-loaded capsules was seen to steadily decrease the cyto-viability. Fluorescence intensity averaged from inside the circles as a function of incubation time.

Antibiotics, Antineoplastic↗
PubMed2005

Adsorption of amyloid beta-peptide at polymer surfaces: a neutron reflectivity study.

The adsorption of amyloid beta-peptide at hydrophilic and hydrophobic modified silicon-liquid interfaces was characterized by neutron reflectometry. Distinct polymeric films were used to obtain noncharged (Formvar), negatively (sodium poly(styrene sulfonate)) and positively charged (poly(allylamine hydrochloride)) hydrophilic as well as hydrophobic surfaces (polystyrene and a polysiloxane-dodecanoic acid complex). Amyloid beta-peptide was found to adsorb at positively charged hydrophilic and hydrophobic surfaces, whereas no adsorbed layer was detected on hydrophilic noncharged and negatively charged films. The peptide adsorbed at the positively charged film as patches, which were dispersed on the surface, whereas a uniform layer was observed at hydrophobic surfaces. The thickness of the adsorbed peptide layer was estimated to be approximately 20 A. The peptide formed a tightly packed layer, which did not contain water. These studies provide information about the affinity of the amyloid beta-peptide to different substrates in aqueous solution and suggest that the amyloid fibril formation may be driven by interactions with surfaces.

Adsorption↗
PubMed2005

Uronic acids functionalized polyethyleneimine (PEI)-polyethyleneglycol (PEG)-graft-copolymers as novel synthetic gene carriers.

In this study, we investigated galacturonic (GalAc)- and mannuronic (ManAc) acids as novel targeting ligands for receptor-mediated gene delivery. GalAc and ManAc were coupled to either polyethyleneimine (PEI) or PEI-polyethyleneglycol (PEG). Furthermore, lactobionic acid (LacAc), which comprises a GalAc-related carbohydrate ring, was coupled to each of the polymers through its open-chain gluconic acid moiety. The molar mass distributions of the polymers were characterized by analytical ultracentrifugation and size exclusion chromatography. PEI-conjugate-pDNA complexes were transfected into HepG2-, HeLa-, and 16HBE14o(-)-cells. Gene expression mediated by GalAc- and LacAc-functionalized PEI-conjugates was lower than for PEI. In contrast, gene expression mediated by ManAc-functionalized PEI-conjugates was up to three orders of magnitude higher than for the other tested PEI-conjugates, in particular for negatively charged gene vectors at low N/P ratios, independent of the cell line. Pre-incubation of cells with an excess of ManAc before transfection significantly inhibited transfection rates only for ManAc-functionalized PEI-conjugates. Coupling of methyl-alpha-d-mannuronic acid to PEI resulted in significantly lower transfection rates than for ManAc-PEI based complexes. Together with fluorescence microscopy images of fluorescein-labelled ManAc-functionalized dextrans and FACS analyses of cells, these results demonstrate that receptor-mediated endocytosis of ManAc-PEI-conjugate-pDNA complexes via ManAc-specific receptors was involved in gene transfer. In conclusion, ManAc-modification of PEI-polymers represents a novel strategy for receptor-mediated gene delivery which could be promising for in vivo application.

Animals↗
PubMed2005

pH-responsive capsules derived from nanocrystal templating.

In the current work we demonstrate a facile and versatile way to create hydrophilic polymeric capsules by integration of Au nanocrystal templating, surface-initiated atom-transfer radical polymerization, and selective chemical cross-linking of polymer shells. Capsules of the homopolymer of 2-(dimethylamino)ethyl methacrylate and its copolymers with 2-(diethylamino)ethyl methacrylate and poly(ethylene glycol) methyl ether methacrylate were constructed. They swell at low pH and shrink at high pH. On the basis of the pH sensitivity of the resulting capsules, encapsulation and release of a drug model, rhodamine 6G, were realized. Furthermore, by cleaving Au-S bonds between Au cores and polymer shells, capsules containing free Au cores were generated, paving a simple pathway to introduce more functionality to the polymeric capsules.

Journal Article↗
PubMed2005

Thermal behavior of polyelectrolyte multilayer microcapsules. 1. The effect of odd and even layer number.

The temperature-dependent behavior of hollow polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) with a different number of layers was investigated in aqueous media using confocal laser scanning microscopy, scanning and transmission electron microscopy, atomic force microscopy, and elemental analysis. Capsules with an even number of layers exhibited a pronounced shrinking at elevated temperature resulting in a transition to a dense sphere, whereas capsules with an odd number of layers swelled during heating to 5-fold of their initial size followed by their rupture. This effect increases for odd layer numbers and decreases for even layer numbers with increasing layer number. According to elemental analysis, an excess of PDADMAC monomers exists within the multilayers of capsules with an odd number of layers leading to a repulsion between the positive charges, whereas shells with an even number of layers have a balanced ratio between the oppositely charged polyions, so that the temperature-dependent behavior is controlled by the different interactions between polyelectrolytes and the bulk water. At a certain temperature, the polyelectrolyte material softens thus facilitating any rearrangement. Besides incubation temperature, the duration of heating has an influence on the restructuring of the multilayers.

Electrolytes↗
PubMed2005

Controlling ionic conductivity in lipid polyelectrolyte composite capsules by cholesterol.

The effect of cholesterol on the formation and properties of bilayer lipid membranes deposited on polyelectrolyte multilayered capsules was studied. The permeability of lipid/cholesterol coated capsules for NaCl was derived from osmotic response experiments and ranged from 1.45 x 10(-8) to 2.9 x 10(-8) m.s(-1), which corresponds to a lipid layer conductivity of (0.7-1.4) x 10(-8) S.m(-1). These conductivity values were in good agreement with the value of 0.8 x 10(-8) S.m(-1) obtained by electrorotation and were by 3 orders of magnitude lower than those found earlier for lipid layers on polyelectrolyte capsules in the absence of cholesterol.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2005

Fabrication of superhydrophobic surfaces from binary colloidal assembly.

In this work, superhydrophobic surfaces were derived from binary colloidal assemblies. CaCO(3)-loaded hydrogel spheres and silica or polystyrene ones were consecutively dip-coated on silicon wafers. The former assemblies were recruited as templates for the latter self-assembly. Due to the hydrophilicity difference between silicon wafers and CaCO(3)-loaded hydrogel spheres, the region selective localization of silica or polystyrene spheres leads to irregular binary structures with a hierarchical roughness. The subsequent modification with low surface energy molecules yields a superhydrophobic surface. The heating treatment may largely enhance the mechanical stability of the resulting binary structures, which allows regeneration of the surface superhydrophobicity, providing a good durability in practice.

Journal Article↗
PubMed2005

Formation of polyelectrolyte multilayer architectures with embedded DMPC studied in situ by neutron reflectometry.

The coupling of lipid molecules to polymer components in a planar biomimetic model membrane made of a lipid bilayer (dimyristoylphosphatidylcholine) supported by polyelectrolyte multilayers is studied. The polyelectrolyte support was prepared by layer-by-layer deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(sodium 4-styrenesulfonate) (PSS). Two polymer sample terminations were considered: positively charged (PAH-terminated) and negatively charged (PSS-terminated). Neutron reflectometry studies showed that, whereas positively charged samples did not favor the deposition of lipid, negatively charged samples allowed the deposition of a lipid bilayer with a thickness of approximately 5 nm. In the latter case, formation of polyelectrolyte layers after the deposition of the lipid layer was also possible.

Dimyristoylphosphatidylcholine↗