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Carbon nanostructures-silica aerogel composites were synthesized and characterized to assess the effect of carbon nanotubes (CNTs) or graphene oxide (GO) on the silica aerogel properties. The sol-gel chemistry was based on methyltrimethoxysilane (MTMS) and 3-aminopropyltrimethoxysilane (APTMS) as silica precursor system, with varying amounts of APTMS (0–20% mol of Si). APTMS significantly impacted the materials' physical properties. The chemistry and microstructure were investigated by FTIR, NMR, TEM, SEM, SAXS and BET. The addition of CNTs induced the growth of the silica matrix around them; thus, an elongated shape was observed in the silica structural units. APTMS and CNTs have a synergistic effect on the mechanical properties, increasing the Young's modulus up to 14 MPa. Small amounts of carbon materials (∼1 wt%) in the MTMS-matrix improved its thermal insulation property, particularly for temperatures above 50 °C. In terms of electrochemical properties, the carbon nanostructures lead to higher specific capacitances and a reduction in resistance. The characterizations here performed allowed a better understanding of the interactions between the silica and carbon phases. The possibility to obtain materials with tailored properties demonstrates their application potential in several areas, such as thermal insulation and energy storage.

Nanoparticle (NP) colloidal stability plays a crucial role in biomedical application not only for human and environmental safety but also for NP efficiency and functionality. NP agglomeration is considered as a possible process in monodispersed NP colloidal solutions, which drastically affects colloidal stability. This process is triggered by changes in the physicochemical properties of the surrounding media, such as ionic strength (IS), pH value, or presence of biomolecules. Despite different available characterization methods for nanoparticles (NPs), there is a lack of information about the underlying mechanisms at the early stage of dynamic behaviors, namely changing in NP size distribution and structure while placing them from a stable colloidal solution to a new media like biological fluids. In this study, an advanced in situ approach is presented that combines small angle X-ray scattering (SAXS) and microfluidics, allowing label-free, direct, time-resolved, and dynamic observations of the early stage of NP interaction/agglomeration initiated by environmental changes. It is shown for silica NPs that the presence of protein in the media enormously accelerates the NP agglomeration process compared to respective changes in IS and pH. High IS results in a staring agglomeration process after 40 min, though, in case of protein presence in media, this time decreased enormously to 48 s. These time scales show that this method is sensitive and precise in depicting the dynamics of fast and slow NP interactions in colloidal conditions and therefore supports understanding the colloidal stability of NPs in various media concluding in safe and efficient NP designing for various applications.

Non-surfactant-induced synthesis of mesoporous silica nanoparticles (MSNPs) is gaining increasing interest because of their low toxicity and simple purification compared to conventional surfactant-...

A simple one-pot synthesis process for functionalized mesostructured silica nanoparticles (MSNP) is reported. The novel process demonstrated the possibility to achieve MSNP with a surface area up to 501 m2.g−1 using a phosphonate based nonsilane precursor such as N, N´-bis[4,6-bis(diethylphosphono)-1,3,5-triazin-yl]-1,2-diaminoethane (ED). MSNP obtained by using 20 mol% of ED achieved a surface area of 80 m2.g−1 and increasing the ED content to 30 mol% resulted in a surface area of 501 m2.g−1. Zeta potential of novel MSNPs (−65.5 and 70.0 mV) were much higher than the nanoparticle (NP) prepared from only TEOS (−49 mV), indicating the presence of a large number of –SiOH and phosphonic acid surface functional groups, as confirmed by Fourier-transform infrared spectroscopy (FT-IR) and Nuclear magnetic resonance (NMR) analysis. The functionalized MSNPs were used as an adsorbent for the removal of cationic pollutants like methylene blue (MB). The MSNP with the highest porosity displayed favorable MB adsorption behavior with ~380 mg.g−1 of MB adsorption capacity. Facile regeneration in an acidic medium (~pH 4.5) with easy recyclability (10 cycles) confirmed the practical applicability of this novel functionalized MSNPs.

We introduce the design and study of a hybrid electrospun membrane with a dedicated nanoscale structural hierarchy for controlled functions in the biomedical domain. The hybrid system comprises submicrometer-sized internally self-assembled lipid nanoparticles (ISAsomes or mesosomes) embedded into the electrospun membrane with a nanofibrous polymer network. The internal structure of ISAsomes, studied by small-angle X-ray scattering (SAXS) and electron microscopy, demonstrated a spontaneous response to variations in the environmental conditions as they undergo a bicontinuous inverse cubic phase (cubosomes) in solution to a crystalline lamellar phase in the polymer membrane; nevertheless, this phase reorganization is reversible. As revealed by in situ SAXS measurements, if the membrane was put in contact with aqueous media, the cubic phase reappeared and submicrometer-sized cubosomes were released upon dissolution of the nanofibers. Furthermore, the hybrid membranes exhibited a specific anisotropic feature and morphological response under an external strain. While nanofibers were aligned under external strain in the microscale, the semicrystalline domains from the polymer phase were positioned perpendicular to the lamellae of the lipid phase in the nanoscale. The fabricated membranes and their spontaneous responses offer new strategies for the development of structure-controlled functions in electrospun nanofibers for biomedical applications, such as drug delivery or controlled interactions with biointerfaces.

International audience; Quercetin and rutin, two widely studied flavonoids with applications foreseen in the sectors of pharmaceutical and cosmetic industries, have been chosen as model compounds for a detailed structural and dynamical investigation onto their influence on fluid lipid bilayers. Combining global small angle X-ray scattering analysis with molecular dynamics, various changes in the properties of dioleoyl-phosphatidylcholine (DOPC) bilayers have been determined. The solubility of quercetin in DOPC membranes is assured up to 12 mol %, whereas rutin, with additional glucose and rhamnose groups, are fully soluble only up to 6 mol %. Both flavonoids induce an increase in membrane undulations and thin the bilayers slightly (

Supercritical drying is widely considered as the gold standard to produce aerogels that preserve the microstructure of the gels, but we have found this is not always the case. Chitosan aerogel, one of the emerging biopolymer aerogels, was prepared by chemical cross-linking gelation, followed by solvent exchange with methanol and supercritical drying using CO2. Small-angle X-ray scattering analysis shows that the structure of the wet gel, which consists of Gaussian chains of individual molecular strands, converts into a nanofibrous network during CO2 processing. In situ observation reveals a drastic shrinkage of the gel in CO2, demonstrating that physical coagulation caused by the low affinity between chitosan and CO2 is the main structure-forming step. These results challenge the common perception of supercritical drying: it is no longer an inactive drying method, but rather an active nanostructure forming a tool to produce porous biopolymer materials with tailored structure and properties.

Supramolecular assemblies with controlled morphology are of paramount importance for energy transport in organic semiconductors. Despite considerable freedom in molecular design, the preparation of dyes that form one dimensional J-aggregates is challenging. Here, we demonstrate a simple and effective route to functionalize dendronized polymers (DPs) with J-aggregates to construct tubular DP/J-aggregate nanowires. When J-aggregates are adsorbed onto DPs anchored to glass substrates, they assemble into microcrystalline domains typical for J-aggregates adsorbed on functionalized surfaces. Differently, the complexation between the dendronized polymer and J-aggregates in solution leads to dense packing of J-aggregate strands on the periphery of the DPs. Using a layer-by-layer (LBL) technique, DPs loaded with J-aggregates can also be adsorbed onto a DP monolayer. In this case, the thin film absorption spectra are narrower and indicate higher ratios of J-aggregate to monomer and dimer absorption than bare J-aggregates deposited similarly. The demonstration of J-aggregate adsorption on filamentous polymeric templates is a promising step toward artificial 1D light harvesting antennas, with potential applications in opto-electronic devices.

Bile salts (BSs) are important for the digestion and absorption of fats and fat-soluble vitamins in the small intestine. In this work, we scrutinized, with small-angle X-ray scattering (SAXS), the crucial functions of bile salts beyond their capacity for the interfacial stabilization of submicrometer-sized lipid particles. By studying a wide compositional range of BS-lipid dispersions using two widely applied lipids for drug-delivery systems (one a monoglyceride being stabilizer-sensitive and the other an aliphatic alcohol being relatively stabilizer-insensitive), we identified the necessary BS to lipid ratios to guarantee full emulsification. A novel ad hoc developed global small-angle-X-ray scattering analysis method revealed that the addition of BS hardly changes the bilayer thicknesses in bicontinuous phases, while significant membrane thinning is observed in the coexisting fluid lamellar phase. Furthermore, we show that a BS strongly decreases the average critical packing parameter. At increasing BS concentration, the order of phases formed is (i) the bicontinuous diamond cubic ( Pn3 m), (ii) the bicontinuous primitive cubic ( Im3 m), and (iii) the fluid lamellar phase ( L ). These distinctive findings on BS-driven "emulsification" and "membrane curvature reduction" provide new molecular-scale insights for the understanding of the interfacial action of bile salts on lipid assemblies.

In this study, we investigated whether ZnO coating on Ag nanoparticles (NPs) tunes electron flux and hole figuration at the metal-semiconductor interface under UV radiation. This effect triggers the photoactivity and generation of reactive oxygen species from Ag@ZnO NPs, which results in enhanced cytotoxic effects and apoptotic cell death in human breast cancer cells (MDA-MB231). In this context, upregulation of apoptotic cascade proteins (i.e., Bax/Bcl2 association, p53, cytochrome c, and caspase-3) along with activation of oxidative stress proteins suggested the occurrence of apoptosis by Ag@ZnO NPs in cancer cells through the mitochondrial pathway. Also, preincubation of breast cancer cells with Ag@ZnO NPs in dark conditions muted NP-related toxic effects and consequent apoptotic fate, highlighting biocompatible properties of unexcited Ag@ZnO NPs. Furthermore, the diagnostic efficacy of Ag@ZnO NPs as computed tomography (CT)/optical nanoprobes was investigated. Results confirmed the efficacy of the photoactivated system in obtaining desirable outcomes from CT/optical imaging, which represents novel theranostic NPs for simultaneous imaging and treatment of cancer.

Design and synthesis of nanostructured responsive gels have attracted increasing attention, particularly in the biomedical domain. Polymer chain configurations and nanodomain sizes within the network can be used to steer their functions as drug carriers. Here, a catalyst-free facile one-step synthesis strategy is reported for the design of pH-responsive gels and controlled structures in nanoscale. Transparent and impurity free gels were directly synthesized from trivinylphosphine oxide (TVPO) and cyclic secondary diamine monomers via Michael addition polymerization under mild conditions. NMR analysis confirmed the consumption of all TVPO and the absence of side products, thereby eliminating post purification steps. The small-angle X-ray scattering (SAXS) elucidates the nanoscale structural features in gels, that is, it demonstrates the presence of collapsed nanodomains within gel networks and it was possible to tune the size of these domains by varying the amine monomers and the nature of the solvent. The fabricated gels demonstrate structure tunability via solvent–polymer interactions and pH specific drug release behavior. Three different anionic dyes (acid blue 80, acid blue 90, and fluorescein) of varying size and chemistry were incorporated into the hydrogel as model drugs and their release behavior was studied. Compared to acidic pH, a higher and faster release of acid blue 80 and fluorescein was observed at pH 10, possibly because of their increased solubility in alkaline pH. In addition, their release in phosphate buffered saline (PBS) and simulated body fluid (SBF) matrix was positively influenced by the ionic interaction with positively charged metal ions. In the case of hydrogel containing acid blue 90 a very low drug release (

The heat protective performance of thermal protective fabrics is related to the multiscale structure of the fibrous material and the composite design of a multilayered fabric system. In this study, a molecular interpretation is provided to explain the structural changes within fibers to correlate with the mechanical properties of the outermost layer fabric made up of m-aramid blended with (5–10) % p-aramid upon various radiant heat exposures. An increase in crystallinity due to limited polymer chain movement but no change in lamellar spacing was observed when fabrics were exposed below the glass transition temperature which resulted in no change in mechanical properties. A noticeable increase in lamellar spacing and crystallinity was obtained when the temperature during the heat exposures is in the proximity of 375 °C of the fabric layer due to the fibrillar-to-lamellar transformation. Even though no visible changes were observed by scanning electron microscopy (SEM) in the fabric exposed to the aforementioned thermal conditions, we found that their mechanical properties are compromised due to the structural changes within fibers of the fabrics. Therefore, further use of fabrics could be potentially dangerous for the user. Furthermore, for expoheat exposures where the temperature of the fabrics reaches above the degradation point, thermal decomposition occurs which is noticed by its hard and brittle behavior. The inner layers of both the fabric systems mostly remain intact until the thermal degradation of the outermost layers. This study provides an in-depth understanding of molecular mechanisms of structural changes that are in line with changes in the mechanical properties. The understanding of the structure-mechanical property relationship could serve as basic knowledge for the design and fabrication of high-performance fabrics for various fire environments.

Spray-dried detergent granules have a complex and multi-scale structure, in which submicron sized crystals of inorganic salts along with multi-lamellar stacks of surfactant molecules are dispersed within a matrix phase. In this study, two model formulations based on sodium linear alkylbenzene sulphonate (NaLAS) and sodium sulphate were used to investigate the molecular structure of stacked lamellae. The parameters of lamellar d-spacing, bilayer thickness (dHH) and water layer thickness (dW) were determined using small-angle X-ray scattering. Four sets of lamellae were detected in nil-silicate detergent powders conditioned at 33 % RH (relative humidity). The exposure of these samples to a higher RH level (75 %) resulted in a reduced number of coexisting lamellar phases by two. This was accompanied by an increase in lamellar d-spacings and a considerable reduction in bilayer thicknesses (dHH). The reduction in number of sets of lamellae was explained by an increase in the fluidity of the lamellar phases and disappearance of water-poor solid polymorphs. This was consistent with the results of FTIR for nil-silicate samples, indicating an increase in the conformational disorder of the alkyl chains at a higher RH value. Interestingly, in the presence of sodium silicate the lamellar phases display a greater degree of swelling at a relatively low RH value (33 % RH) as compared with those in the absence of sodium silicate. Nonetheless, the thickness of water layer was found to slightly decrease at a higher RH (75 %), which was attributed to the moisture-induced glass transition and kosmotropic effect of sodium silicates.

Associative electrostatic interactions between two oppositely charged globular proteins, lactoferrin (LF) and pea protein isolate (PPI), the latter being a mixture of vicilin, legumin, and convicilin, was studied with a specific PPI/LF molar ratio at room temperature. Structural aspects of the electrostatic complexes probed at different length scales were investigated as a function of pH by means of different complementary techniques, namely, with dynamic light scattering, small-angle X-ray scattering (SAXS), turbidity measurements, and atomic force microscopy (AFM). Irrespective of the applied techniques, the results consistently displayed that complexation between LF and PPI did occur. In an optimum narrow range of pH 5.0-5.8, a viscous liquid phase of complex coacervate was obtained upon mild centrifugation of the turbid LF-PPI mixture with a maximum Rh, turbidity and the zeta-potential being close to zero observed at pH 5.4. In particular, the SAXS data demonstrated that the coacervates were densely assembled with a roughly spherical size distribution exhibiting a maximum extension of similar to 80 nm at pH 5.4. Equally, AFM image analysis showed size distributions containing most frequent cluster sizes around 40-80 nm with spherical to elliptical shapes (axis aspect ratio

A versatile strategy for the fabrication of functional and nanostructured poly(N-alkyl acrylamide)-based amphiphilic polymer conetworks (APCNs) from hydrophobic precursor networks is presented. The active ester monomer pentafluorophenyl acrylate (PFPA) fulfills a dual role: it provides miscibility with hydrophobic macromonomer cross-linkers and activates the acrylate for amidation reactions. Thereby, it acts as a general hydrophobic masking group for N-alkyl acrylamides, and enables the transformation of PFPA-based hydrophobic precursor networks into a multitude of different poly(N-alkyl acrylamide)-l-PDMS APCNs. These optically transparent APCNs possess nanophase-separated morphologies with domain sizes in the nanometer range. Variation of the amide results in different types of APCNs, despite them being derived from the same precursor network and having identical network structures. Accordingly, the properties of these APCNs can be tailored to the desired application by simple variation of the amide functionality. Furthermore, the combination of PFPA with another hydrophobically masked monomer allows for the fabrication of APCNs with small yet precisely defined amounts of functional amide units in the hydrophilic phase. A controlled functionalization of APCNs with pendant groups such as pH-responsive imidazole, fluorescent dyes, and biotin for specific protein binding is achieved, greatly expanding the functionality of the APCNs. Such functionalized APCNs could find application as stimuli-responsive drug delivery membranes, smart hydrogels, biosensors, or matrices for biocatalysis.

The development and application of nanofibres requires a thorough understanding of the mechanical properties on a single fibre level including respective modelling tools for precise fibre analysis. This work presents a mechanical and morphological study of poly-l-lactide nanofibres developed by needleless electrospinning. Atomic force microscopy (AFM) and micromechanical testing (MMT) were used to characterise the mechanical response of the fibres within a diameter range of 200–1400 nm. Young’s moduli E determined by means of both methods are in sound agreement and show a strong increase for thinner fibres below a critical diameter of 800 nm. Similar increasing trends for yield stress and hardening modulus were measured by MMT. Finite element analyses show that the common practice of modelling three-point bending tests with either double supported or double clamped beams is prone to significant bias in the determined elastic properties, and that the latter is a good approximation only for small diameters. Therefore, an analytical formula based on intermediate boundary conditions is proposed that is valid for the whole tested range of fibre diameters, providing a consistently low error in axial Young’s modulus below 10%. The analysis of fibre morphology by differential scanning calorimetry and 2D wide-angle X-ray scattering revealed increasing polymer chains alignment in the amorphous phase and higher crystallinity of fibres for decreasing diameter. The combination of these observations with the mechanical characterisation suggests a linear relationship between Young’s modulus and both crystallinity and molecular orientation in the amorphous phase., Acta Biomaterialia, 81, ISSN:1742-7061, ISSN:1878-7568

Four novel amino acid-functionalised triphenylenes have been prepared with glycine, L-alanine, L-phenylalanine and L-tryptophan ethyl ester side-chains. The glycine derivative is a good gelator of chloroform, the alanine derivative gels ethanol and toluene, and the phenylalanine derivative gels benzene and toluene. The tryptophan derivative does not gel any of the solvents tested, most probably due to its more bulky structure, but forms microspheres by evaporation-induced self-assembly. The self-assembly properties of the π-gelators have been investigated using infrared, UV-absorption and fluorescence spectroscopy, concentration- and temperature-dependent NMR, and X-ray scattering experiments on dried xerogel as well as the wet organogel. The latter experiments suggest the glycine gel in chloroform includes columnar aggregates, with an overall disordered columnar oblique mesophase. These compounds are of interest because of the well-known hole-transporting properties of triphenylene liquid crystals: 1-D columnar assemblies of these compounds may find applications in organic electronic devices.

Colloidal stability and charging behavior of amidine latex particles in the presence of multivalent oligomers of acrylic acid was investigated by electrophoresis and light scattering. The data were interpreted quantitatively with the theory of Derjaguin, Landau, Verwey and Overbeek (DLVO) whereby the surface potentials were estimated from electrophoresis. Monomer leads to slow aggregation at low concentrations and to rapid aggregation at high concentrations, as characteristic for simple salts. The oligomers induce a charge reversal of the particles. Close to the isoelectric point (IEP) aggregation is rapid while the suspension becomes stable away from this point. At high oligomer concentrations, the aggregation becomes rapid again. The agreement between DLVO theory and experiment is good close to the IEP. At higher oligomer concentrations, the theory predicts larger stabilities than observed experimentally. While inter-particle forces seem to be well described by DLVO theory near the IEP, additional attractive non-DLVO forces are becoming relevant at higher concentrations.

The transfer kinetics of lipids between internally self-assembled droplets of O/W emulsions is studied. The droplets (isasomes) consist of various liquid-crystalline phases or W/O microemulsions stabilized by a polymeric stabilizer F127. The various internal phases were identified by the relative peak positions in the small-angle X-ray scattering (SAXS) curves. An arrested system composed of isasomes embedded in a gel matrix actually provides an additional possibility to control these systems in terms of the release of various host molecules. These experiments have been applied to examine the kinetics of the internal phase reorganization imposed by the lipids' release and uptake by the droplets embedded in a κ-carrageenan (KC) hydrogel network. Increasing the concentration of the gelling agent slows down the transfer from one droplet to the other through the aqueous phase. We examined the region where the free diffusion is stopped. i.e., the point where the system changes from the ergodic to the nonergodic state and the kinetics is essentially slowed down. This effect can be balanced by the addition of small amounts of free polymeric stabilizer, which speeds up the kinetics. This is even possible in the case of highly arrested dynamics of the emulsion droplets, as found for the highest KC hydrogel concentrations forming nonergodic systems.

Oil-water Pickering emulsions of about 200 nm were stabilized by nanosized hydrophilic silica after a simple surface treatment method. We have modified the aqueous silica nanoparticle dispersions by simple adsorption of oleic acid to their surfaces, improving the hydrophobicity of the particles while maintaining their charge and stability. The adsorption was monitored by small-angle X-ray scattering and electrophoretic measurements to estimate the interparticle interactions and surface charges. The effect of various parameters, such as nanoparticle concentration, amount of oleic acid, ionic strength, and pH, on the droplets' size and stability was investigated by dynamic light scattering. Furthermore, the ability of these modified silica nanoparticles to stabilize long-chain alkanes, liquid paraffin, and liquid-crystalline phases was examined.

The destabilization of charged colloidal suspensions is studied in the presence of polyelectrolytes and the corresponding oligomers. Two different systems are investigated, namely, negatively charged particles in the presence of polyamines and positively charged ones in the presence of polycarboxylates. Multivalent oligomers of low valence destabilize the particles by screening according to the Schulze-Hardy rule. Polyelectrolytes induce destabilization by overcharging. Both regimes can be observed for oligomers of intermediate valence. The stability data of any valence can be rather well described by the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), indicating that the interactions are mainly governed by van der Waals and electrostatic double-layer forces.

Artificial neural networks were used to predict the oxidation peaks potentials of 7 monosaccharides under linear sweep voltammetry regime. Two sets of descriptors, one based on molecular properties calculated through DFT and another based on simple geometric distributions of hydroxyl groups and asymmetric carbon atoms along molecular chains, were employed to introduce the molecules to networks. Relatively, simple networks of (3,3,1) and (3,3,3,1) structures with the number of epochs not exceeding 15 through training process were capable of correctly predicting the peaks positions with R values in the range of 0.97–0.99.

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled (functionalized) CNTs are used as stabilizers to produce Pickering type oil-in-water (O/W) emulsions. Lipids namely, Dimodan U and Phytantriol are used as emulsifiers, which in excess water self-assemble into the bicontinuous cubic Pn3m phase. This highly viscous phase is fragmented into smaller particles using a probe ultrasonicator in presence of conventional surfactant stabilizers or CNTs as done here. Initially, the CNTs (powder form) are dispersed in water followed by further ultrasonication with the molten lipid to form the final emulsion. During this process the CNTs get coated with lipid molecules, which in turn are presumed to surround the lipid droplets to form a particulate emulsion that is stable for months. The average size of CNT- stabilized nanostructured lipid particles is in the submicron range, which compares well with the particles stabilized using conventional surfactants. Small angle X-ray scattering data confirms the retention of the original Pn3m cubic phase in the CNT-stabilized lipid dispersions as compared to the pure lipid phase (bulk state). Blue shift and lowering of the intensities in characteristic G and G’ bands of CNTs observed in Raman spectroscopy characterize the interaction between CNT surface and lipid molecules. These results suggest that the interactions between the CNTs and lipids are responsible for their mutual stabilization in aqueous solutions. As the concentrations of CNTs employed for stabilization are very low and lipid molecules are able to functionalize the CNTs, the toxicity of CNTs is expected to be insignificant while their biocompatibility is greatly enhanced. Hence the present approach finds a great potential in various biomedical applications, for instance, for developing hybrid nanocarrier systems for the delivery of multiple functional molecules as in combination therapy or polytherapy.

The coupling of fullerene (C60) to the structure and elasticity of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine bilayers has been explored by synchrotron small angle X-ray scattering. Multilamellar vesicles were loaded with 0, 2 and 10 mol.% of C60 and studied in a temperature range from 15 to 65 °C. The addition of C60 caused an increase in the bilayer undulations (∼20%), in the bilayer separation (∼15%), in the linear expansion coefficient and caused a drop in the bending rigidity of the bilayers (20–40%). Possible damaging effects of fullerene on biomembranes are mainly discussed on the basis of altered bilayer fluidity and elasticity changes.

Repulsive electrostatic double-layer forces are responsible for the stabilization of charged colloidal particles in the presence of adsorbed polyelectrolytes of opposite and high line charge densities. This mechanism is revealed by studies of electrophoretic mobility and colloidal stability performed with dynamic light scattering as a function of the polyelectrolyte dose and the ionic strength for two different types of latex particles and four different types of polyelectrolytes. The dependence of these quantities is very similar for bare charged latex particles and the same particles in the presence of the different oppositely charged polyelectrolytes. Positively charged particles in the presence of anionic polyelectrolytes behave analogously to negatively charged particles in the presence of cationic polyelectrolytes.

The present article reviews recent progress in the measurement of aggregation rates in colloidal suspensions by light scattering. Time-resolved light scattering offers the possibility to measure absolute aggregation rate constants for homoaggregation as well as heteroaggregation processes. We further discuss the typical concentration dependencies of the aggregation rate constants on additives. Addition of simple salts containing monovalent counterions leads to screening of the electrostatic repulsion of the charged particles and a transition from slow to rapid aggregation. Addition of salts containing multivalent counterions may lead to a charge reversal, which results in a sequence of two instability regions. Heteroaggregation rates between oppositely charged particles decrease with increasing salt level. This decrease is caused by screening of the electrostatic attraction between these particles.

In recent years, continuous-flow/microreactor processing for the preparation of colloidal nanocrystals has received considerable attention. The intrinsic advantages of microfluidic reactors have opened new opportunities for the size-controlled synthesis of nanocrystals either in the laboratory or on a large scale. Herein, an experimentally simple protocol for the size-tunable continuous-flow synthesis of rather monodisperse CdSe quantum dots (QDs) is presented. CdSe QDs are manufactured by using cadmium oleate as cadmium source, selenium dioxide as selenium precursor, and 1-octadecene as solvent. Exploiting selenium dioxide as selenium source and 1-octadecene as solvent allows execution of the complete process in open air without any requirement for air-free manipulations using a glove box or Schlenk line. Continuous-flow processing is performed with a stainless steel coil of 1.0 mm inner diameter pumping the combined precursor solution through the reactor by applying a standard HPLC pump. The effect of different reaction parameters, such as temperature, residence time, and flow rate, on the properties of the resulting CdSe QDs was investigated. A temperature increase from 240 to 260 °C or an extension of the residence time from 2 to 20 min affords larger nanocrystals (range 3–6 nm) whereas the size distribution does not change significantly. Longer reaction times and higher temperatures result in QDs with lower quantum yields (range 11–28 %). The quality of the synthesized CdSe QDs was confirmed by UV/Vis and photoluminescence spectroscopy, small-angle X-ray scattering, and high-resolution transmission electron microscopy. Finally, the potential of this protocol for large-scale manufacturing was evaluated and by operating the continuous-flow process for 87 min it was possible to produce 167 mg of CdSe QDs (with a mean diameter of 4 nm) with a quantum yield of 28 %.

Charging and aggregation of negatively charged carboxyl latex particles in the presence of positively charged linear oligoamines containing 1-6 amine groups were investigated by electrophoretic mobility and dynamic light scattering. The oligoamines of low valence resemble simple inert salts and destabilize the suspensions by screening their charge. The oligoamines of higher valence induce overcharging at low concentrations, whereby destabilization is triggered by charge neutralization. At higher concentrations, destabilization is also induced by screening. The onset of first fast aggregation regime scales with the inverse six power of the valence in agreement with the Schulze-Hardy rule. The aggregation rates can be relatively well described by the DLVO theory which indicates that the interactions are governed by van der Waals and electrostatic double layer forces.

Positively charged amidine latex particles are studied in the presence of poly(acrylic acid) (PAA) with different molecular masses under neutral and acidic conditions by electrophoresis and time-resolved dynamic light scattering. Under neutral conditions, where PAA is highly charged, the system is governed by the charge reversal induced by the quantitatively adsorbing polyelectrolyte and attractive patch–charge interactions. Under acidic conditions, where PAA is more weakly charged, the following two effects come into play. First, the lateral structure of the adsorbed layers becomes more homogeneous, which weakens the attractive patch–charge interactions. Second, polyelectrolyte adsorption is no longer quantitative and partitioning into the solution phase is observed, especially for PAA of low molecular mass.

Highly charged polyelectrolytes adsorbed on oppositely charged colloidal particles are investigated by electrophoresis and dynamic light scattering. The dependence of the adsorbed amount and of the hydrodynamic layer thickness on the molecular mass and the salt level is analyzed. The adsorbed amount increases with increasing salt level and decreases with increasing molecular mass. The hydrodynamic layer thickness is independent of the molecular mass at low salt levels, but increases with the molecular mass as a power law with an exponent 0.10 ± 0.01 at high salt. The same behavior was observed for different polyelectrolytes and substrates and therefore is suspected to be generic. Due to semi-quantitative agreement with computer simulations carried out by Kong and Muthukumar in 1998, the observed behavior is interpreted with conformational changes of single adsorbed polyelectrolyte chains.

Charging of poly(acrylic acid) (PAA) in the presence of different alkali metal counterions was studied by precision potentiometric titration. The charging behavior can be described with a novel cylinder Stern model quantitatively. This model is based on the Poisson–Boltzmann equation in the cylinder geometry and a constant Stern capacitance. One finds an increasing cylinder radius with increasing mass of the alkali metal ion and a correspondingly decreasing Stern capacitance. The intrinsic ionization constants for the uncharged polymer are found to decrease with ionic strength, similarly to weak acids of low molecular mass.

Nonspecific interactions of flavonoids with lipids can alter the membrane's features (e.g., thickness and fluctuations) as well as influence their therapeutic potentials. However, relatively little is known about the details of how flavonoids interact with lipid components. Structure-dependent interactions of a variety of flavonoids with phospholipid monolayers on a mercury (Hg) film electrode were established by rapid cyclic voltammetry (RCV). The data revealed that flavonoids adopting a planar configuration altered the membrane properties more significantly than nonplanar flavonoids. Quercetin, rutin, and tiliroside were selected for follow-up experiments with Langmuir monolayers, Brewster angle microscopy (BAM), and small-angle X-ray scattering (SAXS). Relaxation phenomena in DOPC monolayers and visualization of the surface with BAM revealed a pronounced monolayer stabilization effect with both quercetin and tiliroside, whereas rutin disrupted the monolayer structure rendering the surface entirely smooth. SAXS showed a monotonous membrane thinning for all compounds studied associated with an increase in the mean fluctuations of the membrane. Rutin, quercetin, and tiliroside decreased the bilayer thickness of DOPC by ∼0.45, 0.8, and 1.1 Å at 6 mol %, respectively. In addition to the novelty of using lipid monolayers to systematically characterize the structure-activity relationship (SAR) of a variety of flavonoids, this is the first report investigating the effect of tiliroside with biomimetic membrane models. All the flavonoids studied are believed to be localized in the lipid/water interface region. Both this localization and the membrane perturbations have implications for their therapeutic activity.

The renin–angiotensin–aldosterone system (RAAS) plays a key role in the regulation of blood pressure. Renin is the rate limiting enzyme of the RAAS and aliskiren is a highly potent and selective inhibitor of the human renin. Renin is known to be active both in the circulating blood stream as well as locally, when bound to the (pro)-renin receptor ((P)RR). In this study we have investigated a possible mechanism of action of aliskiren, in which its accumulation in the plasma membrane is considered as an essential step for effective inhibition. Aliskiren's interactions with model membranes (cholesterol rich and poor) have been investigated by applying different complementary techniques: differential scanning calorimetry (DSC), Raman spectroscopy, magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and small- and wide-angle X-ray scattering (SAXS and WAXS). In addition, in silico molecular dynamics (MD) calculations were applied for further confirmation of the experimental data. Aliskiren's thermal effects on the pre- and main transition of dipalmitoyl-phosphatidylcholine (DPPC) membranes as well as its topographical position in the bilayer show striking similarities to those of angiotensin II type 1 receptor (AT1R) antagonists. Moreover, at higher cholesterol concentrations aliskiren gets expelled from the membrane just as it has been recently demonstrated for the angiotensin receptor blocker (ARB) losartan. Thus, we propose that both the AT1R and the (P)RR-bound renin active sites can be efficiently blocked by membrane-bound ARBs and aliskiren when cholesterol rich membrane rafts/caveolae are formed in the vicinity of the receptors.