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Surface-imprinted polymer particles facilitate the accessibility of synthetic selective binding sites for proteins. Given their volume-to-surface ratio, submicron particles offer a potentially large surface area facilitating fast rebinding kinetics and high binding capacities, as investigated herein by batch rebinding experiments. Polymer particles were prepared with (3-acrylamidopropyl)trimethylammonium chloride as functional monomer, and ethylene glycol dimethacrylate as cross-linker in the presence of pepsin as template molecule via miniemulsion polymerization. The obtained polymer particles had an average particle diameter of 623 nm, and a specific surface area of 50 m2 g−1. The dissociation constant and maximum binding capacity were obtained by fitting the Langmuir equation to the corresponding binding isotherm. The dissociation constant was 7.94 μM, thereby indicating a high affinity; the binding capacity was 0.72 μmol m−2. The binding process was remarkably fast, as equilibrium binding was observed after just 1 min of incubation. The previously determined selectivity of the molecularly imprinted polymer for pepsin was for the first time confirmed during competitive binding studies with pepsin, bovine serum albumin, and β-lactoglobulin. Since pepsin has an exceptionally high content in acidic amino acids enabling strong interactions with positively charged quaternary ammonium groups of the functional monomers, another competitive protein, i.e., α1-acid glycoprotein, was furthermore introduced. This protein has a similarly high content in acidic amino acids, and was used for demonstrating the implications of ionic interactions on the achieved selectivity. [ABSTRACT FROM AUTHOR]

Phenoxazine is a commonly used molecular building block, for example in optoelectronic applications and pharmaceuticals. However, it is highly susceptible to rapid photodegradation, especially in halogenated solvents. In the present study, we identify the degradation products in both halogenated and non-halogenated solvents by UV/Vis absorption, NMR spectroscopy and mass spectrometry. We also propose a substitution strategy aimed at effectively suppressing the high photoreactivity. Kinetic studies show that the quantum yield of photodegradation φ differs by a factor of more than 1000 between trisubstituted derivatives and N-substituted phenoxazine., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

The synthesis of two different series of donor-acceptor (D-A) molecules is reported, consisting of a series of four structurally related donors and two different acceptors. The subtle differences in the electron density of these D-A-D and D-A compounds are clearly reflected in the different chemical shifts of certain donor protons in the 1 H NMR spectra. These shifts show a cosine squared correlation of the dihedral angle between the donor units and the neighbouring phenyl unit of the acceptor. This correlation is also related to optical properties such as the photoluminescence quantum yield, which shows a similar trend due to the different degree of charge transfer during excitation and relaxation processes. In this way, it is possible to directly correlate a molecular structural parameter with a material property on a purely experimental basis, which should be applicable to many donor-acceptor systems., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

A new carbazole-substituted bisterpyridine with pronounced delayed fluorescence is presented. While the molecular donor-acceptor-donor design suggests the origin of this to be thermally activated delayed fluorescence (TADF), results from various photophysical characterizations, OLED characteristics, temperature-dependent NMR spectroscopy, and DFT calculations all point against the involvement of triplet states. The molecule exhibits blue emission at about 440 nm with two or more fast decay channels in the lower nanosecond range in both solution and thin films. The delayed emission is proposed to be caused by rotational vibrational modes. We suggest that these results are generally applicable, especially for more complex molecules, and should be considered as alternative or competitive emissive relaxation pathways in the field of organic light emitting materials., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

In a highly efficient and reproducible process, bovine serum albumin (BSA) nanogels are prepared from inverse nanoemulsions. The concept of independent nanoreactors of the individual droplets in the nanoemulsions allows high protein concentrations of up to 0.6% in the inverse total system. The BSA gel networks are generated by the 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride coupling strategy widely used in protein chemistry. In a robust work-up protocol, the hydrophobic continuous phase of the inverse emulsion is stepwise replaced by water without compromising the colloidal stability and non-toxicity of the nanogel particles. Further, the simple process allows the loading of the nanogels with various cargos like a dye (Dy-495), a drug (ibuprofen), another protein [FMN-binding fluorescent protein (EcFbFP)], and oligonucleotides [plasmid DNA for enhanced GFP expression in mammalian cells (pEGFP c3) and a synthetic anti- Pseudomonas aeruginosa aptamer library]. These charged nanoobjects work efficiently as carriers for staining and transfection of cells. This is exemplarily shown for a phalloidin dye and a plasmid DNA as cargo with adenocarcinomic human alveolar basal epithelial cells (A549), a cell revertant of the SV-40 cancer rat cell line SV-52 (Rev2), and human breast carcinoma cells (MDA-MB-231), respectively.

In a previous contribution we described the formation of silica nanostructures in dye-stabilized nanoemulsions from tetraethyl orthosilicate droplets in water. Depending on the type of dye, either capsules (crystal violet, CV) or nanoparticles (congo red, CR) are formed. The thorough study of the sol-gel process uses a combination of time- and/or temperature-resolved small-angle X-ray scattering, transmission electron microscopy, and 1 H NMR spectroscopy to elucidate the detailed kinetics and mechanism of structure formation. In both cases, small nuclei of 1.5-2 nm are formed, followed by either a fast cluster-cluster (CV) or a much slower monomer-cluster aggregation (CR). The former leads to a cross-linked network and finally to patchy capsules, while the latter leads to individual nanoparticles (SNPs). From an Avrami plot it can be deduced that the SNPs are formed by an interface-controlled one-dimensional growth process. The mechanisms are based on the different local environments at the oil-water interface, which is either slightly acidic (CV) or fairly basic (CR). The kinetics differ by a factor between 3 and 20 and are presumably caused by the different mobility of the catalyzing species H + or OH - .

Supramolecular polymerization of a donor-acceptor bisterpyridine (BTP) equipped with an electron-rich carbazole unit is observed by scanning tunneling microscopy (STM) at the highly oriented pyrolytic graphite (HOPG)|solution interface. It is shown that two-dimensional crystals of supramolecular (co)polymers are formed by chain growth polymerization, which in turn can be described by copolymerization statistics. From concentration-dependent measurements, derived copolymerization parameters and DFT calculations, a mechanism for self-assembly is developed that suggests a kinetically driven polymerization process in combination with thermodynamically controlled crystallization., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Protein hydrogels represent ideal materials for advanced cell culture applications, including 3D-cultivation of even fastidious cells. Key properties of fully functional and, at the same time, economically successful cell culture materials are excellent biocompatibility and advanced fabrication processes allowing their easy production even on a large scale based on affordable compounds. Chemical crosslinking of bovine serum albumin (BSA) with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) in a water-in-oil emulsion with isoparaffinic oil as the continuous phase and sorbitan monooleate as surfactant generates micro-meter-scale spherical particles. They allow a significant simplification of an indispensable and laborious step in traditional cell culture workflows. This cell passaging (or splitting) to fresh culture vessels/flasks conventionally requires harsh trypsinization, which can be omitted by using the "trans-ferry-beads" presented here. When added to different pre-cultivated adherent cell lines, the beads are efficiently boarded by cells as passengers and can be easily transferred afterward for the embarkment of novel flasks. After this procedure, cells are perfectly viable and show normal growth behavior. Thus, the trans-ferry-beads not only may become extremely affordable as a final product but also may generally replace trypsinization in conventional cell culture, thereby opening new routes for the establishment of optimized and resource-efficient workflows in biological and medical cell culture laboratories.

Systemic blood stream infections are a major threat to human health and are dramatically increasing worldwide. Pseudomonas aeruginosa is a WHO-alerted multi-resistant pathogen of extreme importance as a cause of sepsis. Septicemia patients have significantly increased survival chances if sepsis is diagnosed in the early stages. Affinity materials can not only represent attractive tools for specific diagnostics of pathogens in the blood but can prospectively also serve as the technical foundation of therapeutic filtration devices. Based on the recently developed aptamers directed against P. aeruginosa , we here present aptamer-functionalized beads for specific binding of this pathogen in blood samples. These aptamer capture beads (ACBs) are manufactured by crosslinking bovine serum albumin (BSA) in an emulsion and subsequent functionalization with the amino-modified aptamers on the bead surface using the thiol- and amino-reactive bispecific crosslinker PEG 4 -SPDP. Specific and quantitative binding of P. aeruginosa as the dedicated target of the ACBs was demonstrated in serum and blood. These initial but promising results may open new routes for the development of ACBs as a platform technology for fast and reliable diagnosis of bloodstream infections and, in the long term, blood filtration techniques in the fight against sepsis.

The human pathogenic bacterium Clostridioides difficile produces two exotoxins TcdA and TcdB, which inactivate Rho GTPases thereby causing C. difficile-associated diseases (CDAD) including life-threatening pseudomembranous colitis. Hypervirulent strains produce additionally the binary actin ADP-ribosylating toxin CDT. These strains are hallmarked by more severe forms of CDAD and increased frequency and severity. Once in the cytosol, the toxins act as enzymes resulting in the typical clinical symptoms. Therefore, targeting and inactivation of the released toxins are of peculiar interest. Prompted by earlier findings that human α-defensin-1 neutralizes TcdB, we investigated the effects of the defensin on all three C. difficile toxins. Inhibition of TcdA, TcdB, and CDT was demonstrated by analyzing toxin-induced changes in cell morphology, substrate modification, and decrease in transepithelial electrical resistance. Application of α-defensin-1 protected cells and human intestinal organoids from the cytotoxic effects of TcdA, TcdB, CDT, and their combination which is attributed to a direct interaction between the toxins and α-defensin-1. In mice, the application of α-defensin-1 reduced the TcdA-induced damage of intestinal loops in vivo. In conclusion, human α-defensin-1 is a specific and potent inhibitor of the C. difficile toxins and a promising agent to develop novel therapeutic options against C. difficile infections., (© 2020 The Authors. The FASEB Journal published by Wiley Periodicals, Inc. on behalf of Federation of American Societies for Experimental Biology.)

Well-defined raspberry-like poly(styrene- co-4-vinylpyridine)-SiO 2 nanocomposite particles with a diameter of around 200 nm were easily prepared by a double in situ process in nanoemulsion with the water-soluble dye Eosin Y as the stabilizer. During radical polymerization of the nanodroplets comprising styrene, 4-vinylpyridine (4-VP), and tetraethoxysilane (TEOS), the silane phase is expelled from the polymer phase to the oil/water (o/w) interface. In the later polymerization stage, SiO 2 nanoparticles with a size of around 25 nm were produced via the in situ sol-gel reaction of TEOS at the o/w interface promoted by the negatively charged dye. The pyridine moieties in the copolymer fix the SiO 2 nanoparticles on the surface of the polymer particles by electrostatic interactions without any sign of free unbound silica particles as proven by transmission electron microscopy.

Oligothiophenes with branched alkyl end groups show distinct aggregation in organic solvents. The process of supramolecular polymerization is assessed by three different methods (UV-vis absorption and fluorescence emission spectroscopy and dynamic light scattering) to exclude artifacts. An apparent dependence of the degree of aggregation on the concentration of the oligomers is observed. Above the upper limit of concentration (a lower micromolar range for the present class of compounds), experimental data delivered conflicting results and the concentration should not therefore be exceeded. Scanning force microscopy and molecular dynamics simulations confirm the formation of one-dimensional aggregates with presumably helical arrangement of the achiral monomers.

Bisterpyridine-based grid complexes can serve as supramolecular three-dimensional scaffolds for the construction of larger molecular assemblies. Through functionalization of the ligand with azide groups, followed by self-assembly and metal-free Huisgen reactions, eight pyrene molecules can be attached to the grid structure in a single reaction step. The orientation and proximity provided by the scaffold allows for tuning the fluorescence properties of the dye molecules., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dye stabilized nanoemulsions offer the unique possibility of creating both silica capsules and sub-20-nm particles with precise control of particle size and narrow dispersity from the same system by the choice of the proper dye. The large o/w interface enhances the kinetics of particle formation significantly over macroscopic interfaces which enables the synthesis of silica nanoparticles without any catalyst or elevated temperatures under static conditions. This is in contrast to syntheses for sub-20-nm silica nanoparticles described until now which can normally not be conducted at neutral pH and/or room temperature without stirring. Furthermore, the synthesis can be run without any additional organic solvent and the dyes can be easily removed from the dispersion which opens the pathway to silica dispersions containing only particles, traces of ethanol and water at neutral pH without centrifugation, washing, or redispersion in accordance with the idea of "green chemistry".

Hypothesis: Many solid particles have been used in Pickering stabilized (mini)emulsions. Stabilizing "particles" can be also formed in situ e.g. by aggregation of dye molecules as reported recently. Among the dyes sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate (Alizarin Yellow R, (AYR)) is one of the best stabilizers. It is assumed to act as sole stabilizer also in heterophase polymerizations and offers a great potential for applications., Experiments: Aqueous solutions of AYR in varying concentrations (0.3, 0.5, 1.0, 1.5, 2.0mg/mL (dye/water)) were employed as continuous phase in direct miniemulsions. The oil phase comprised ethenylbenzene (styrene) and hexadecane. The effects of AYR concentration and ultrasonication time on size and distribution of the droplets were investigated. The miniemulsions were polymerized with a water-soluble azo-initiator (2,2'-azobis[n-(2-carboxyethyl)-2-methylpropionamidine] n-hydrate, VA-057) and conversion and kinetics were determined., Findings: The AYR is successfully employed as stabilizer in Pickering-like miniemulsion polymerizations of styrene. The higher the AYR concentrations the more stable the miniemulsions, the smaller the droplet sizes and the narrower the distributions are, ranging from ca. 450 to 180nm and 0.38 to 0.15, respectively. The nucleation mechanism of the polymer particles could be revealed by the number ratio of droplets and particles and follows droplet nucleation. This is confirmed by polymerization kinetics, which is in accordance with classical miniemulsion polymerization, too., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Self-assembly in situ, where synthetic molecules are programmed to organize in a specific and complex environment i.e., within living cells, can be a unique strategy to influence cellular functions. Here we present a small series of rationally designed oligothiophene analogues that specifically target, locate and dynamically self-report their supramolecular behavior within the confinement of a cell. Through the recognition of the terminal alkyl substituent and the amphiphilic pyridine motif, we show that the cell provides different complementary pathways for self-assembly that can be traced easily with fluorescence microscopy as their molecular organization emits in distinct fluorescent bands. Importantly, the control and induction of both forms are achieved by time, temperature and the use of the intracellular transport inhibitor, bafilomycin A1. We showcase the importance of both intrinsic (cell) and extrinsic (stimulus) factors for self-organization and the potential of such a platform toward developing synthetic functional components within living cells.

Pickering emulsions with a remarkable transmittance of up to 86% across the visible spectrum have been prepared without adjusting the refractive index (RI) of the stabilizing particles to those of the aqueous and oil phases. Commercially available hydrophilic silica particles with a diameter of 20 nm, which are hydrophobized partially in situ, were used to stabilize water droplets with diameters below 400 nm in IsoparM. In this system, the stabilizing particles and the emulsion droplets act as one single scattering object, which renders RI-matching of the particles unnecessary. By either evaporation of some water from the droplets or addition of an appropriate organic liquid to the oil phase, it is possible to match the RI of the droplets (aqueous phase + particles) with that of the continuous phase, which minimizes scattering and results in highly transparent emulsions.

Water-soluble organic dyes such as fluorescein are widely used, mainly for coloration of, e.g., biological samples and groundwater tracing, and they are not obviously amphiphilic by molecular structure like surfactants. Here, we show that the dyes alone stabilize oil-in-water emulsions. Exemplarily, fluorescein is compared with the classical surfactant sodium dodecyl sulfate (SDS) by means of surface/interfacial tension, concentration of stabilizer and electrolyte, as well as pH. The principle can be extended to further classes of water-soluble dyes, which keep up with or exceed SDS by efficiency. Various organic liquids of different polarities can be employed and be polymerized in the case of styrene as disperse phase. Thus, surfactant free latex solely stabilized by water-soluble dyes is accessible. The emulsions can be destabilized by absorption of the dyes to hydrogels, and their complete removal is easily followed visually. The stabilization mechanisms are different for SDS and the dyes: The latter stabilize droplets not as monomers but by their aggregates as molecular scale Pickering stabilizers, which is a new concept of stabilization.

Peptide drugs delivered orally need to be protected from degradation for achieving their functions. To fulfill the complicated task of oral drug delivery, we present a hierarchically structured drug-delivery system that can undertake structural changes, so multiple functions can be triggered by a sequence of stimuli. Such hierarchical system is achieved in a nanoparticle-in-nanofiber configuration, in which both the nanofibers and the nanoparticles are pH-responsive and biocompatible. A model peptide is efficiently encapsulated under mild condition, and the nanocarriers are further electrospun with a pH-responsive mucoadhesive polymer. The nanoparticles are released from the nanofibers, and thereafter the peptides are released from the nanoparticles in a pH-responsive manner. The nanoparticles are compatible with caco-2 cells, and the endocytosis of the nanoparticles is described in detail.

Microencapsulation of hydrophilic therapeutic agents such as proteins or nucleotides into a nanocarrier is frequently accomplished in inverse (water-in-oil) emulsions. However, the redispersion of the nanocarriers in aqueous media often involves a complicated purification process, and the redispersion usually requires additional surfactants for its colloidal stability, which is not favored for biological applications. We propose a simple, fast, and mild method to recover hydrophilic nanocarriers prepared in inverse emulsions by temporary coating of the nanocarriers with biocompatible small molecules, so that the final aqueous dispersion of the nanocarriers can be dispersed with high recovery rate, minimal aggregation, and no additional surfactants. Such a method is termed the "cushion method" and was adopted in the preparation of chitosan nanocarriers. The nanocarriers recovered with the cushion method release encapsulated peptides in a pH-responsive manner and do not require surfactants for colloidal stabilization.

We report on three different liquid crystalline compounds with a central septithiophene core and alkylated end groups of strongly increasing bulkiness. In principle, the thiophene cores prefer to pack parallel to optimize their π-π interactions, which becomes sterically impossible for the bulkier end groups. Using X-ray diffraction, we find that the way out of this packing dilemma is toward liquid-crystal phases of higher dimensionality in the order smectic → columnar ↔ bicontinuous cubic. For the smectic phase, packing in a monolayer is no problem; for the other ones packing considerations become more stringent in films due to the boundaries. Surface X-ray techniques and atomic force microscopy indicate an appreciable difference between monolayer and three-layer films, in which the monolayers appear to escape from packing frustration by generating superstructures. We propose a basic structure of columns parallel to the substrate that provides a compromise between preserving some π-π interactions and packing the bulky alkyl groups.

Inverse Pickering emulsions with droplet diameters between 180 and 450 nm, a narrow droplet size distribution, and an outstanding stability were prepared using a miniemulsion technique. Commercially available hydrophilic silica nanoparticles were used to stabilize the emulsions. They were hydrophobized in situ by the adsorption of various neutral polymeric surfactants. The influence of different parameters, such as kind and amount of surfactant as hydrophobizing agent, size and charge of the silica particles, and amount of water in the dispersed phase, as well as the kind of osmotic agent (sodium chloride and phosphate-buffered saline), on the emulsion characteristics was investigated. The systems were characterized by dynamic light scattering, transmission electron microscopy, cryo-scanning electron microscopy (cryo-SEM), thermogravimetric analysis, and semiquantitative attenuated total reflection infrared spectroscopy. Cryo-SEM shows that some silica particles are obviously rendered hydrophilic and form a three-dimensional network inside the droplets.

The hydrophilic peptide YY (PYY) is a promising hormone-based antiobesity drug. We present a new concept for the delivery of PYY from pH-responsive chitosan-based nanocarriers. To overcome the drawbacks while retaining the merits of the polyelectrolyte complex (PEC) method, we propose a one-pot approach for the encapsulation of a hydrophilic peptide drug in cross-linked PEC nanocarriers. First, the hydrophilic peptide is encapsulated via polyelectrolyte complexation within water-in-oil miniemulsion droplets. In a second step, the PEC surface is reinforced by controlled interfacial cross-linking. PYY is efficiently encapsulated and released upon pH change. Such nanocarriers are promising candidates for the fight against obesity and, in general, for the oral delivery of protein drugs.

In the present study, superparamagnetic Fe3O4/poly(N-isopropyl acrylamide) nanocomposites were synthesized by one-step inverse miniemulsion copolymerization of N-isopropyl acrylamide and N,N'-methylene diacrylamide. The loading of Fe3O4 nanoparticles in the nanocomposites was 27 wt%, and the saturation moment of the nanocomposites was 12.4 emu x g(-1). Fe3O4 nanoparticles were prepared through a coprecipitation method. The amount of stabilizer (poly(acrylic acid)) significantly influenced the size and size distribution of the Fe3O4 nanoparticles, and, therefore, their magnetic properties. Superparamagnetism of the Fe3O4 nanoparticles was preserved in the nanocomposites. The effects of synthetic parameters on the particle properties, namely surfactant loading, concentration of ferrofluid, type of lipophobe and initiator, and amount of cross-linker were investigated. Nanocomposites of Fe3O4/poly(N-isopropyl acrylamide) displayed a guava-like morphology, which they could retain after being redispersed in polar solvents.

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET-ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.

Janus Pd/SiO2 nanocomposite particles (NCPs) were successfully synthesized through a combination of the sol-gel process of tetramethoxysilane in inverse miniemulsions and in situ reduction of Pd salts via a gas diffusion process of hydrazine. The formation of Pd nanoparticles (NPs) was verified by X-ray diffraction. The Janus morphology of the Pd/SiO2 NCPs was confirmed by microscopic observation. The Pd/SiO2 NCPs displayed a mesoporous structure. The content of Pd NPs in the NCPs could be conveniently adjusted by the K2PdCl4 loading. A formation mechanism of the Janus Pd/SiO2 NCPs was proposed. The mesoporous Janus Pd/SiO2 NCPs show good catalytic activity toward the reduction of p-nitrophenol with NaBH4.

Ag/TiO2 nanocomposites were prepared through combination of a sol-gel process of a titanium precursor in inverse miniemulsions and in situ reduction of silver ions in the "nanoreactors". The morphological investigation shows that Ag nanoparticles are mainly located on the surface of TiO2 nano-supports because of the fast reduction rate of Ag ions by hydrazine. Ag/TiO2 nanocomposites with amorphous or anatase TiO2 phase displayed high visible-light catalytic activity for degradation of Rhodamine B. The photoactivity of Ag/anatase TiO2 nanocomposites could be influenced by the Ag content that could be conveniently tuned by the loading of silver salts. The influence of the loading of silver salts on the particle properties of the Ag/TiO2 nanocomposites was investigated systematically., (Copyright © 2014 Elsevier Inc. All rights reserved.)

The synthesis of a novel nanocapsule-based carrier system is described, possessing a triggered release in remote-controlled fashion upon application of an external magnetic field in combination with the possibility to use the capsules as contrast agents for magnetic resonance imaging (MRI). Therefore, polymeric nanocontainers containing a high amount of superparamagnetic MnFe2 O4 nanoparticles and a thermo-degradable shell are fabricated via a miniemulsion route. The process allows the facile encapsulation of hydrophilic compounds, as demonstrated for a model dye. Release of the encapsulated dye is achieved upon application of an external alternating magnetic field. While the magnetic nanoparticles here act as heat generators to stimulate the decomposition of the shell and subsequently a release of the payload, they additionally enable the use of the nanocapsules as imaging agents for MRI. Due to the encapsulated magnetic nanoparticles, the nanocapsules possess high r2 relaxivity values of 96-120 Hz mmol(-1) , which makes them suitable for MRI. In toxicity experiments, the nanocapsules show no cell toxicity up to fairly high concentrations (600 µg mL(-1) ). Due to their dual-functionality, the nanocapsules possess high potential as nanocarriers with combined magnetic-field-induced release capability and as contrast agents for MRI., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this review, we summarize recent advances in the synthesis of hybrid nanoparticles in miniemulsions since 2009. These hybrid nanoparticles include organic-inorganic, polymeric, and natural macromolecule/synthetic polymer hybrid nanoparticles. They may be prepared through encapsulation of inorganic components or natural macromolecules by miniemulsion (co)polymerization, simultaneous polymerization of vinyl monomers and vinyl-containing inorganic precursors, precipitation of preformed polymers in the presence of inorganic constituents through solvent displacement techniques, and grafting polymerization onto, from or through natural macromolecules. Characterization, properties, and applications of hybrid nanoparticles are also discussed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We present a structural comparison of monolayers on a SiO2 substrate of two asymmetrically substituted sexithiophenes (6T). Molecule 1 consists of 6T with a branched alkyl chain at one end only and shows a crystalline structure. In molecule 2, the bifunctional 6T has in addition at the other end a linear alkyl chain. It displays thermotropic liquid crystalline (LC) behavior. Both compounds form readily single molecular layers from solution. Remarkably, full monolayer coverage can be achieved before multilayer growth starts. LC properties promote preordering near the interface as well as exchange of molecules between the growing domains, thus regulating the domain sizes. As a result, the LC compound 2 forms single-molecule islands with larger domain sizes compared to compound 1. Surface X-ray investigations indicate that the 6T cores are tilted relative to the layer normal. The tilt angle is as large as 54° for compound 2 compared to 28° for compound 1. For molecule 2, interfacial constraints and packing requirements because of the asymmetric substitution cause a rather loosely organized core structure.

Polymeric nanogels, inorganic nanoparticles, and organic-inorganic hybrid nanoparticles can be prepared via the inverse miniemulsion technique. Hydrophilic functional cargos, such as proteins, DNA, and macromolecular fluoresceins, may be conveniently encapsulated in these nanostructured materials. In this review, the progress of inverse miniemulsions since 2000 is summarized on the basis of the types of reactions carried out in inverse miniemulsions, including conventional free radical polymerization, controlled/living radical polymerization, polycondensation, polyaddition, anionic polymerization, catalytic oxidation reaction, sol-gel process, and precipitation reaction of inorganic precursors. In addition, the applications of the nanostructured materials synthesized in inverse miniemulsions are also reviewed.

Surface imprinted polymers allow accessibility of the selective binding sites to large molecules such as proteins. In this work, small polymer particles offering a large surface area were prepared via miniemulsion polymerization in the presence of pepsin serving as a template molecule. The influence of four different functional monomers and of the amount of the template on the imprinting effect of pepsin was investigated. After the miniemulsion polymerization and a washing step, stable polymer suspensions with an average particle diameter of 400-600 nm and a specific surface area of 30-65 m 2 g -1 were obtained. The results of detailed rebinding experiments revealed that the highest imprinting effect was achieved with (3-acrylamidopropyl)trimethylammonium chloride as a functional monomer and a high amount of the template. These polymer particles also showed selectivity for pepsin against various proteins. This approach provides a fundamental step towards the development of synthetic protein receptors and protein scavenger materials useful in biomimetic assays and for clean-up in biotechnology.

Nanogel (hydrophilic polymer nanoparticles) core-silica shell nanoparticles were successfully fabricated via hydrolysis and condensation reaction of tetraethoxysilane (TEOS). Transition-metal tetrafluoroborate-containing nanogels were used as templates for fabrication in inverse systems (cyclohexane as continuous phase). Magnetic, hollow silica particles were subsequently formed by removing the polymer core and converting iron salts to iron oxides via heat treatment. We propose that the formation of the core-shell morphology is induced by the promoted precipitation of silica species at the surface of nanogels due to the interaction between silica species and transition-metal tetrafluoroborate. The influence of the synthesis parameters (type and amount of salts, pH of the nanogels, and amount of TEOS) on the particle morphology was systematically investigated. The pore properties and specific surface area of the hollow silica particles could be modified by the varying the amount of salt., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The preparation of nanoparticles in a soap-free system is highly attractive, as surfactants may influence and deteriorate subsequent applications. Thereby, the assembly of solid particles on droplets/particles is well known as Pickering-type stabilization. The resulting hybrid nanocomposites offer in general a rough surface and are highly intriguing for potential drug delivery systems, coating applications, and so forth. This review highlights developments in production and application of Pickering-type nanoparticles synthesized via heterophase polymerization techniques in emulsion, miniemulsion, dispersion, and suspension. We will focus our discussion on systems, wherein stabilization of the final nanometer-sized hybrids is exclusively accomplished via particle stabilizers. In case surfactants are used during preparation, they only serve as pre-treating agents to modify the surface properties of the particle stabilizer, and not being employed for the purpose of droplet/particle stabilization.

Aqueous core-silica shell nanocapsules were successfully prepared using liquid droplets containing transition-metal salt as templates in inverse miniemulsions. The formation of the silica shell was attributed to the interfacial deposition of silica species induced by the presence of the transition-metal salt. In addition to the control of the particle morphology, the incorporated transition-metal salts could be used to derivatize the particles and confer additional functionalities to the hollow silica particles. To demonstrate the derivatization, the magnetic hollow silica particles were prepared by converting iron salts to magnetic iron oxides by heat treatment. The particle morphology, size, and size distribution were characterized by transmission electron microscopy and scanning electron microscopy. The results show that the particle properties strongly depend on the type and the amount of salts, the amount of tetraethoxysilane (TEOS), the pH of the droplets, and the ratios of 2-hydroxyethyl methacrylate to aqueous HCl solution. The specific surface area and pore properties were characterized by N2 sorption measurements. The pore properties and specific surface area could be tuned by varying the amount of salt. Levels of elements and of iron oxides in the magnetic hollow particles were measured by energy-dispersive X-ray spectroscopy. Iron was distributed homogenously with silicon and oxygen in the sample. The magnetization measured by a magnetic property measurement system confirmed the successful conversion of the iron salts to magnetic iron oxides.

Cross-linked chitosan (CS) nanohydrogels were successfully prepared via cross-linking CS nanodroplets in inverse miniemulsions. The cross-linker was transferred to the CS nanodroplets via the evaporation from its aqueous solution and diffusion through the continuous phase. The formation of cross-linked CS nanohydrogels was confirmed by the morphological investigation during the reaction and the successful preparation of acidic aqueous dispersion of CS nanohydrogels. The size and size distribution of the CS nanodroplets and nanohydrogels were characterized by dynamic light scattering (DLS). The particle morphology of CS nanohydrogels was observed by transmission electron microscopy (TEM). The influence of the synthetic parameters on the particle properties and colloidal stability was investigated with respect to sonication time, surfactant type and amount, type of low polarity solvent, and concentration of CS solution. The cross-linked CS nanohydrogels could be easily re-dispersed in water, and showed a pH sensitivity.

The antibacterial (bioactive) and antifouling (biopassive) properties of stable, uniform, high surface coverage films of poly(hydroxyethyl methacrylate-co-2-methacryloyloxyethyl phosphorylcholine) (p(HEMA-co-MPC)) with embedded, non-leaching silver nanoparticles (AgNPs) are reported. Based on the experimental findings, a mechanism of action of AgNPs in antibacterial activity in combination with antifouling characteristics is discussed. Long-term antifouling studies of E. coli determine little to no adhesion on p(HEMA-co-MPC)/Ag films at 2.5 × 10 6 CFU mL -1 for 7 d, measured using live/dead staining assays. Agar diffusion tests indicate that there is no leaching of Ag from the films and SEM and EDX analyses of the films before and after incubation with E. coli show no attachment of E. coli and no visible change in film morphology or AgNP dispersal. Antibacterial studies are investigated using E. coli K-12 as a model bacterial strain and are tested in static (CFUs) and dynamic contact assays. Antibacterial efficacy of the films containing extremely low AgNP concentration (3.8 ng cm -2 ) is shown with growth suppression of E. coli in culture medium for 4 h at 1.35 × 10 5 CFU mL -1 and killing greater than 99% of E. coli in only 1 h of exposure to concentrations up to 1 × 10 5 CFU mL -1 . These hybrid films may propose an exciting direction to long-term antibacterial and antifouling films in clinical applications.

The influence of surface roughness and charge on the cellular uptake of nanoparticles in HeLa cells is investigated with fluorescent, oppositely charged, rough, and smooth nanoparticles. Flow cytometry, cLSM, and TEM reveal that rough nanoparticles are internalized by the cells more slowly and by an unidentified uptake route as no predominant endocytosis route is blocked by a variety of inhibitory drugs, while the uptake of smooth nanoparticles is strongly dependent on dynamin, F-actin, and lipid-raft. Negatively charged nanoparticles are taken up to a higher extent than positively charged ones, independent of the surface roughness., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dual fluorescently labeled polymer particles were prepared in a downscaled Pickering-type miniemulsion system. Stable dispersions were obtained and the size of the hybrid particles could be varied between ca. 180 and 430 nm. Silica nanoparticles were employed as sole emulsifier, which were labeled by a fluorescein dye (FITC) or (encapsulated) quantum dots, and the polymer core was labeled by a perylene derivative. Downscaling of the Pickering-type miniemulsion system is intriguing by itself as it allows the use of precious nanoparticles as emulsifiers. Here, silica particles with a fluorescent core and an overall diameter between 20 and 40 nm were prepared and employed as stabilizer. The dual excitation and emission of both dyes was tested by fluorescence measurements and confocal laser scanning microscopy (cLSM).

Mesoporous silica capsules with submicrometer sizes were successfully prepared via the interfacial hydrolysis and condensation reactions of tetraethoxysilane (TEOS) in inverse miniemulsion by using hydrophilic liquid droplets as template. The inverse miniemulsions containing pH-controlled hydrophilic droplets were first prepared via sonication by using poly(ethylene-co-butylene)-b-poly(ethylene oxide) (P(E/B)-PEO) or SPAN 80 as surfactant. TEOS was directly introduced to the continuous phase of an inverse miniemulsion. The silica shell was formed by the deposition of silica on the surface of droplets. The formation of capsule morphology was confirmed by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The mesoporous structure was verified by nitrogen sorption measurements. The specific surface area could be tuned by the variation of the amount of cetyltrimethylammonium bromide (CTAB) and TEOS, and the pore size by the amount of CTAB. The influences of synthetic parameters on the particle size and morphology were investigated in terms of the amount of CTAB, pH value in the droplets, TEOS amount, surfactant amount, and type of solvent with low polarity. A formation mechanism of silica capsules was proposed.

The synthesis of stable dispersions of hybrid colloids comprising copolymers of biocompatible 2-hydroxyethyl methacrylate (HEMA) and zwitterionic, biomimetic 2-methacryloyloxyethyl phosphorylcholine (MPC) incorporating antibacterial AgBF(4) by inverse miniemulsion is described. The prepared hybrid colloids were designed to provide both antibacterial and antifouling properties for the formation of interesting, multifunctional films. The obtained particles had sizes in the range of 130-160 nm with two different weight ratios of MPC to HEMA (1:10 and 2:5) and AgBF(4) contents between 0% and 15%. The silver salt takes on the role of the lipophobe in stabilizing the miniemulsion droplets against Ostwald ripening and is reduced after polymerization to Ag nanoparticles by gaseous hydrazine. Subsequently, the hybrid particles are transformed into smooth and stable films with thicknesses between 145 and 225 nm by simple drop casting and solvent annealing. The dispersions and films were thoroughly characterized by DLS, TEM, SEM, EDX, TGA, UV-vis spectroscopy, ICP-OES, XRD, AFM, and contact angle measurements. After immersion into water, the films did not show detectable leakage of silver, so they could be employed as dual-functional antifouling and antibacterial coatings.