Search

Tuberculosis is the deadliest bacterial disease globally, threatening the lives of millions every year. New antibiotic therapies that can shorten the duration of treatment, improve cure rates, and impede the development of drug resistance are desperately needed. Here, we used polymeric micelles to encapsulate four second-generation derivatives of the antitubercular drug pretomanid that had previously displayed much better in vivo activity against Mycobacterium tuberculosis than pretomanid itself. Because these compounds were relatively hydrophobic, we expected that such micellar formulations would increase drug bioavailability, reduce toxicities, and improve therapeutic outcomes. The polymeric micelles were based on polypept(o)ides (PeptoMicelles) and were stabilized in their hydrophobic core by π-π interactions, allowing the efficient encapsulation of aromatic pretomanid derivatives. The stability of these π-π-stabilized PeptoMicelles was demonstrated in water, blood plasma, and lung surfactant by fluorescence cross-correlation spectroscopy and was further supported by prolonged circulation times of several days in the vasculature of zebrafish larvae. The pretomanid derivative with the best in vitro potency against Mycobacterium marinum (“drug D”) was also the most efficacious PeptoMicelle formulation tested in the zebrafish larvae infection model, almost completely eradicating the bacteria at non-toxic doses. This lead formulation was further assessed against Mycobacterium tuberculosis in the susceptible C3HeB/FeJ mouse model, which develops human-like necrotic granulomas. Following intravenous administration, the drug D micellar formulation significantly reduced bacterial burden and inflammatory responses in the lungs and spleens of infected mice.

International audience; This investigation reports on the thermomechanical properties of Poly-tripropyleneglycoldiacrylate (Poly-TPGDA)/liquid crystal (LC) blends, developed via free radical polymerization processes, which are induced by Electron Beam (EB) and Ultraviolet (UV) radiation. The EB-cured Poly-TPGDA network exhibits a higher glass transition temperature (Tg), a higher tensile storage, and Young moduli than the corresponding UV-cured sample, indicating a lower elasticity and a shorter distance between the two adjacent crosslinking points. Above Tg of Poly-TPGDA/LC blends, the LC behaves as a plasticizing agent, whereas, for EB-cured networks, at temperatures below Tg, the LC shows a strong temperature dependence on the storage tensile modulus: the LC reinforces the polymer due to the presence of nano-sized phase separated glassy LC domains, confirmed by electron microscopy observations. In the case of the UV-cured TPGDA/LC system, the plasticizing effect of the LC remains dominant in both the whole composition and the temperature ranges explored. The rubber elasticity and Tg of Poly-TPGDA/LC films were investigated using mechanical measurements.; Cette étude rend compte des propriétés thermomécaniques des mélanges de poly-tripropylèneglycoldiacrylate (Poly-TPGDA)/cristaux liquides (LC), développés via des processus de polymérisation radicalaire, qui sont induits par un faisceau d'électrons (EB) ou un rayonnement ultraviolet (UV). Le réseau Poly-TPGDA durci par EB présente une température de transition vitreuse (Tg) plus élevée, un stockage en traction plus élevé et des modules d'Young que l'échantillon durci aux UV correspondant, indiquant une élasticité plus faible et une distance plus courte entre les deux points de réticulation adjacents. Au-dessus de la Tg des mélanges Poly-TPGDA/LC, la LC se comporte comme un agent plastifiant, alors que, pour les réseaux durcis à l'EB, à des températures inférieures à la Tg, la LC montre une forte dépendance de la température au module de traction de stockage : la LC renforce le polymère en raison de à la présence de domaines LC vitreux séparés en phase de taille nanométrique, confirmés par des observations de microscopie électronique. Dans le cas du système TPGDA/LC polymérisé aux UV, l'effet plastifiant du LC reste dominant à la fois dans l'ensemble de la composition et dans les plages de température explorées. L'élasticité du caoutchouc et la Tg des films Poly-TPGDA/LC ont été étudiées à l'aide de mesures mécaniques.

We present an experimental approach to studying the kinetics of polymer nanoparticle formation using molecular rotor molecules as fluorescence probes. By combining fluorescence lifetime analysis and fluorescence correlation spectroscopy, it is possible to simultaneously monitor the evolution of the local environment in the nanoparticles and their size. To assess the generality of the method, we select two common but very different methods for nanoparticle preparation: emulsion-solvent evaporation and miniemulsion polymerization. In both cases, three stages of the nanoparticle formation process were identified on the basis of their polymer content. In the initial stage of the process, the polymer content is low. Then it increases rapidly because of solvent evaporation or polymerization during the second stage. Finally, it reaches a plateau value. Furthermore, significant heterogeneities in the final nanoparticles were found that can be attributed to remaining solvent or monomer and the spatial variation of the polymer-free volume.

The generation of specific humoral and cellular immune responses plays a pivotal role in the development of effective vaccines against tumors. Especially the presence of antigen-specific, cytotoxic T cells influences the outcome of therapeutic cancer vaccinations. Different strategies, ranging from delivering antigen-encoding mRNAs to peptides or full antigens, are accessible but often suffer from insufficient immunogenicity and require immune-boosting adjuvants as well as carrier platforms to ensure stability and adequate retention. Here, we introduce a pH-responsive nanogel platform as a two-component antitumor vaccine that is safe for intravenous application and elicits robust immune responses

12C fusion reactions are among the most important in stellar evolution since they determine the destiny of massive stars. Over the past fifty years, massive efforts have been done to measure these reactions at low energies. However, existing data present several discrepancies between sets and large uncertainties specially at the lowest energies. Factors such as beam/environmental backgrounds, extremely low cross sections and insufficient knowledge of the reaction mechanism contribute to these problems. Recently, the ERNA collaboration measured the 12C+12C reactions at Ec.m. = 2.51 - 4.36 MeV with energy steps between 10 and 25 keV in the centre of mass. Representing the smallest energy steps to date. In these measurements, beam induced background was minimised and S-factors for the proton and alpha channels were calculated. Results indicate that a possible explanation for the discrepancies between data sets is the wrongly assumed constant branching ratios and isotropical angular distributions. Given the excellent performance of the detectors for low energy measurements, a collaboration with the LUNA group (LNGS) has started. Background measurements underground are being performed and results indicate it could be possible to measure the 12C+12C reactions directly into the Gamow Window.

Polycrystalline thin films and single crystals of hybrid perovskites – a material group successfully used for photovoltaic and optoelectronic applications – reportedly display heterogeneous charge carrier dynamics often attributed to grain boundaries or crystalline strain. Here, we locally resolved the carrier diffusion in large, isolated methylammonium lead iodide (MAPbI3) grains via spatial- and time-resolved photoluminescence microscopy. We found that the anisotropic carrier dynamics directly correlate with the arrangement of ferroelastic twin domains. Comparing diffusion constants parallel and perpendicular to the domains showed carriers diffuse around 50–60% faster along the parallel direction. Extensive piezoresponse force microscopy experiments on the nature of the domain pattern suggest that the diffusion anisotropy most likely originates from structural and electrical anomalies at ferroelastic domain walls. We believe that the domain walls act as shallow energetic barriers, which delay the transversal diffusion of carriers. Furthermore, we demonstrate a rearrangement of the domains via heat treatment above the cubic-tetragnal phase transition. Together with the previously reported strain engineering via external stress, our findings promise additional routes to tailor the directionality of the charge carrier diffusion in MAPbI3-based photovoltaics and optoelectronics as well as other ferroelastic materials for optoelectronic applications.

In applications superhydrophobic surfaces are often irregular and nanostructured. On such a surface, it has been found that only a part of the surface is homogeneously wetted, i.e. wetting and slippage corresponding to that of a regularly structured surface. On the remaining part, large air inclusions occurred that possess a comparatively large slip length. In order to measure the velocity profile at distances below 1\textmu{}m close to the surface, an enhanced evaluation method for fluorescence correlation spectroscopy is developed in this work.

12C+12C reactions are crucial in the evolution of massive stars and explosive scenarios. The measurement of these reactions at astrophysical energies is very challenging due to their extremely small cross sections, and the presence of beam induced background originated by the natural 1,2H contaminants in the C targets. In addition, the many discrepancies between different data sets and the complicated resonant structure of the cross sections make the extrapolation to low energies very uncertain. Recently, we performed a direct measurement of the 12C+12C reactions at the CIRCE Laboratory in Italy. Results from a study on target contamination were used, allowing us to measure cross sections at Ec.m. =2.51 − 4.36 MeV with 10-25 keV energy steps. Two stage ΔE-Erest detectors were used for unambiguous particle identification. Branching ratios of individual particle groups were found to vary significantly with energy and angular distributions were also found to be anisotropic, which could be a potential explanation for the discrepancies observed among different data sets.

Neutron capture reactions are the main contributors to the synthesis of the heavy elements through the s-process. Together with 13C(α, n)16O, which has recently been measured by the LUNA collaboration in an energy region inside the Gamow peak, 22Ne(α, n)25Mg is the other main neutron source in stars. Its cross section is mostly unknown in the relevant stellar energy (450 keV < Ecm < 750 keV), where only upper limits from direct experiments and highly uncertain estimates from indirect sources exist. The ERC project SHADES (UniNa/INFN) aims to provide for the first time direct cross section data in this region and to reduce the uncertainties of higher energy resonance parameters. High sensitivity measurements will be performed with the new LUNA-MV accelerator at the INFN-LNGS laboratory in Italy: the energy sensitivity of the SHADES hybrid neutron detector, together with the low background environment of the LNGS and the high beam current of the new accelerator promises to improve the sensitivity by over 2 orders of magnitude over the state of the art, allowing to finally probe the unexplored low-energy cross section. Here we present an overview of the project and first results on the setup characterization.

The detection of neutrons in low energy astrophysics poses two main problems: low cross section measurement requires high detection efficiency and ideally, beam-induced and external neutron backgrounds should be identified through an energy sensitive detector. In recent years, capture-gated neutron spectroscopy has found new opportunities to grow through new materials and better availability of modern data acquisition systems. In this work we will present the design, expected capabilities and preliminary characterization of the hybrid neutron detector array SHADES. Its purpose is the first direct measurement of the reaction 22Ne(α, n)25Mg in the Gamow window for s-process nucleosynthesis with LUNA-MV in the deep underground environment of the LNGS.

The removal of hydrophobic polymer coatings from artistic surfaces is a ubiquitous challenge in art restoration. Over the years, nanostructured fluids (NSFs), aqueous surfactant solutions containing a good solvent for the polymer, have been successfully applied in polymer removal interventions; however, the precise role of the surfactant in promoting polymer film dewetting is not fully understood. This contribution addresses the interaction of a NSF of water/propylene carbonate containing a nonionic surfactant with an acrylic polymer film commonly used in art conservation. Combining confocal microscopy and fluorescence correlation spectroscopy, we monitored the penetration of the fluid into the polymer film, defining its compositional changes and following the polymer swelling. The ensemble of results highlights that the surfactant role is twofold: (i) at the polymer-support interface, it promotes the detachment of the polymer film from the underlying support; (ii) inside the polymer film, it accelerates polymer swelling by increasing the chains' mobility.

Giant unilamellar vesicles (GUVs) are model membrane systems consisting of a single lipid bilayer separating an inner lumen from the outer solution, with dimensions comparable to that of eukaryotic cells. The importance of these biomimetic systems has recently grown with the development of easy and safe methods to assemble GUVs from complex biorelevant compositions. However, size and position control is still a key challenge for GUV formation and manipulation. Here, a gel-assisted formation method is introduced, able to produce arrays of giant unilamellar anchored vesicles (GUAVs) with a predetermined narrow size distribution. The approach based on micropatterned gel substrates of cross-linked poly(N-isopropylacrylamide) allows performing parallel measurements on thousands of immobile unilamellar vesicles. Such power and flexibility will respond to the growing need for developing platforms of biomimetic constructs from cell-sized single bilayers.

In this work, we present a method to pattern liquid crystal elastomers (LCEs) in the micrometer range without using any mechanical processing steps to prepare micron sized LCE actuators compatible with microelectromechanical system (MEMS) technology. Multi-layer spin-coating processes are developed to synthesise and structure 300–3500 nm thick LCE films. A water soluble sacrificial layer, a photoalignment layer and a LCE formulation, which is polymerised and crosslinked in its liquid crystal phase, are spin-coated successively onto a substrate. A fluorinated photoresist layer is used to structure LCE films with thicknesses up to 700 nm in a photolithographic and etching process. For thicker LCE films a hard mask process, using hydrogen silsesquioxane (HSQ) as hard mask, is used. Film thicknesses and homogeneities are analysed with profilometry. Actuation motions of LCE layers are investigated before and after patterning and LCE patterns are investigated via (polarised optical) microscopy (POM), scanning electron microscopy (SEM) and profilometry. A resolution of 1.5–2.0 microns is achieved with the described techniques, which make deformable micron sized LCE actuators of variable shape and director orientation accessible. The presented results demonstrate the potential of LCEs in MEMS devices.

Nanocomposites of polystyrene-block-polyisoprene-block-polystyrene triblock copolymer (SIS) and various types of neat and polystyrene-modified carbon nanotubes (CNT-PS) were prepared and distribution of the CNT-PS throughout the polymer matrix was evaluated using confocal laser scanning microscopy (CLSM). The Nanoamor MWCNT-PS with highest thickness of 25–60 nm were readily visualized using both reflection mode without necessity of fluorescent labelling and fluorescent mode after addition of free dye to the nanocomposite. Visualization of Nanocyl MWCNT-PS with thickness of 8–18 nm and SWCNT-PS was achieved after covalent labelling of the CNT-PS with benzothioxanthene fluorescent dye. The CLSM can serve as a non-invasive method for evaluation of quality of dispersion of nanofillers on quite large area and at various depth of polymer film.

Nanocarrier-based drug delivery is a promising therapeutic approach that offers unique possibilities for the treatment of various diseases. However, inside the blood stream, nanocarriers’ properties may change significantly due to interactions with proteins, aggregation, decomposition or premature loss of cargo. Thus, a method for precise, in situ characterization of drug nanocarriers in blood is needed. Here we show how the fluorescence correlation spectroscopy that is a well-established method for measuring the size, loading efficiency and stability of drug nanocarriers in aqueous solutions can be used to directly characterize drug nanocarriers in flowing blood. As the blood is not transparent for visible light and densely crowded with cells, we label the nanocarriers or their cargo with near-infrared fluorescent dyes and fit the experimental autocorrelation functions with an analytical model accounting for the presence of blood cells. The developed methodology contributes towards quantitative understanding of the in vivo behavior of nanocarrier-based therapeutics., While nanocarrier-based drug delivery is a promising therapeutic approach, in situ characterization of drug nanocarriers in blood remains difficult. Here, the authors demonstrate how the fluorescence correlation spectroscopy can be used to directly characterize drug nanocarriers in flowing blood.

The size control of nanomedicines for tumor diagnosis and therapy is of high importance, since it enables or disables deep and sufficient tumor penetration. Amphiphilic star-shaped block copolypept(o)ides offer substantial promise to precisely adjust the hydrophobic core and the hydrophilic corona, independent of each other, and therefore simultaneously control the size dimension in the interesting size range from 10 to 30 nm. To gain access to core-shell structures of such sizes, 3-arm and 6-arm PeptoStars, based on poly(gamma-tert-butyloxycarbonyl-L-glutamate)-b-polysarcosine (pGlu(OtBu)-b-pSar), were prepared via controlled living ring-opening polymerization (ROP) of the corresponding N-carboxyanhydrides. Moreover, size exclusion chromatography (SEC) proves the presence of well-defined star shaped polymers with molecular weights from 38 to 88 kg/mol with low polymer dispersities of 1.16 to 1.23. By varying the alpha-helical peptide core and maintain a constant polysarcosine corona, hydrodynamic size analyses revealed the importance of using a sufficiently large and dense hydrophilic shielding corona to prevent aggregation of the hydrophobic core and obtain uniform-sized spherical-shaped particles with hydrodynamic diameters below 24 nm. Fluorescence correlation spectroscopy (FCS) additionally demonstrates the absence of protein adsorption in human plasma for 6-arm polypept(o)ide stars and thus confirms polysarcosine as stealthlike material.

Controlling the organization of particles at liquid–gas interfaces usually relies on multiphasic preparations and external applied forces. Here, we show that micromolar amounts of a conventional cationic surfactant induce, in a single step, both adsorption and crystallization of various types of nanometer- to micrometer-sized anionic particles at the air–water interface, without any additional phase involved or external forces other than gravity. Contrary to conventional surfactant-induced particle adsorption through neutralization and hydrophobization at a surfactant concentration close to the critical micellar concentration (CMC), we show that in our explored concentration regime (CMC/1000-CMC/100), particles adsorb with a low contact angle and maintain most of their charge, leading to the formation of two-dimensional assemblies with different structures, depending on surfactant (Cs) and particle (Cp) concentrations. At low Cs and Cp, particles are repulsive and form disordered assemblies. Increasing Cp...

Degradable synthetic crosslinking is a versatile strategy to harness nanomaterials against disassembly in a complex physiological medium prompted by dilution effects or competitive interaction. In particular, chemical bonds such as ketals that are stable at physiological conditions but are cleaved in response to disease-mediated or intracellular conditions (e.g., a mildly acidic pH) are of great relevance for biomedical applications. Despite the range of spectroscopic or chromatographic analyses methods that allow chemical degradation in solution to be assessed, it is much less straightforward to interrogate synthetic nanomaterials for their degradation state when located inside a living organism. We demonstrate a method based on FRET analysis to monitor intracellular disassembly of block-copolymer-derived nanoparticles engineered with a FRET couple on separate polymer chains, which after self-assembly are covalently crosslinked with a pH-sensitive ketal-containing crosslinker.

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.

Mesoporous silica coated upconverting nanoparticles are loaded with the anticancer drug doxorubicin and grafted with ruthenium complexes as photoactive molecular valves. Drug release was triggered by 974 nm light with 0.35 W cm(-2). Such low light intensity minimized overheating problems and prevented photodamage to biological samples.

International audience; It was recently suggested that the electrostatic double-layer force between colloidal particles might weaken at high hydrostatic pressure encountered, for example, in deep seas or during oil recovery. We have addressed this issue by means of a specially designed optical trapping setup that allowed us to explore the interaction of a micrometer-sized glass bead and a solid glass wall in water at hydrostatic pressures of up to 1 kbar. The setup allowed us to measure the distance between bead and wall with a subnanometer resolution. We have determined the Debye lengths in water for salt concentrations of 0.1 and 1 mM. We found that in the pressure range from 1 bar to 1 kbar the maximum variation of the Debye lengths was

There is a growing interest in the development of stable nanocapsules that could deliver the bioactive compounds within the living organism, and to release them without causing any toxic effects. Here the miniemulsion droplets were first used as "nanoreactors" for the amplification of single-molecule dsDNA template (476 and 790 base pairs) through PCR. Afterwards, each droplet was surrounded with a biodegradable PBCA shell by interfacial anionic polymerization, enabling therefore to deliver the PCR products into the cells. The size of the initial miniemulsion droplets and the final polymeric capsules was in the range of 250 and 320 nm, mainly depending on the type of the continuous phase and presence of dsDNA template molecules. The formation of PCR products was resolved with gel electrophoresis and detected with fluorescence spectroscopy in the presence of DNA specific dye (SYBRGreen). TEM studies were performed to prove the formation of the polymeric shell. The shell thickness was measured to be within 5-15 nm and the average molecular weight of the formed PBCA polymer was around 75000 g · mol(-1) . For the cell uptake experiments, the obtained nanocapsules were transferred from the organic phase into aqueous medium containing a water-soluble surfactant. The effect of the surfactant type (anionic, cationic or non-ionic) on the HeLa cell viability and nanocapsule uptake behavior was studied by CLSM and FACS. Confocal analysis demonstrated that nanocapsules stabilized with cationic (CTMA-Cl) and non-ionic (Lutensol AT50) surfactants show almost the same uptake, whereas capsules redispersed in anionic (SDS) surfactant possess a 30% higher uptake. The release of the encapsulated material within the cell was studied on the example of Cy5-labeled oligonucleotides showing the colocalization with mitochondria of MSCs cells.

Carbon nanoparticles become photoluminescent upon surface passivation with oligomeric polymer chains. In this work, the dependence of the carbon dots photoluminescent properties on the passivation polymer selection has been demonstrated by conjugating polyethylene glycol (PEG) chains, polyethylenimide-co-polyethylene glycol-co-polyethylenimide copolymer, and 4-armed PEG molecules, respectively. The cytotoxicity and cellular internalization of the resulting three types of photoluminescent nanoformulations of carbon dots, named CD2, CD3, and CD4, were evaluated. These nanoformulations exhibited no apparent cytotoxicity on their own and were shown to successfully target cancer cells by conjugation with transferrin. The implication to the use of carbon dots as biocompatible optical nanoprobes for in vitro cancer diagnostics is discussed.

Results of Pressure-Volume-Temperature measurement on Poly(methyl methacrylate) : Lead Titanate, PMMA : PbTiO3, composite system in the pressure and temperature range 0–200 MPa and 300–473 K, respectively, are presented. The thermal expansion coefficient in PMMA : PbTiO3 composite is expected to be quite complex because the polymer has positive thermal expansion coefficient, whereas the filler has a negative thermal expansion coefficient. In this present article, the effect of pressure on the volumetric thermal expansion coefficient in PMMA : PbTiO3 composite system is presented. It is shown that thermal expansion coefficient of the polymer can be tailored by adding filler which has negative thermal expansion coefficient. Theoretically, a simple additive rule is formulated which can predict the variation of expansion coefficient in the PMMA : PbTiO3 composite system. The limitation of the additive rule is also discussed. It is also shown that the glass transition temperature depends on filler concentration and also has strong pressure dependence. The reasons for large pressure dependence are discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Two cyanate ester monomers (CEMs) based on oligomeric aryl ether (OAE) derivatives of bisphenol AF and bisphenol A, with multiple reactive cyanate groups, were developed as technologically highly relevant thermosets. These CEMs are liquids processable at room temperature and can be crosslinked by cyclotrimerization of the cyanate groups to form extended polycyanurate (PC) networks at lower temperatures ( 2808C), with excellent thermal, mechanical, and dielectric properties. PC nanorods with diameters of 65 or 380 nm could be moulded in porous alumina templates from the OAE-CEMs. The high aspect ratio nanorods with a length in the order of 100 mm were hydrolytically stable upon extended exposure to boiling water.

Well-defined statistical, gradient and block copolymers consisting of isobornyl acrylate (IBA) and n-butyl acrylate (nBA) were synthesized via atom transfer radical polymerization (ATRP). To investigate structure–property correlation, copolymers were prepared with systematically varied molecular weights and compositions. Thermomechanical properties of synthesized materials were analyzed via differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA) and small-angle X-ray scattering (SAXS). Glass transition temperature (Tg) of the resulting statistical poly(isobornyl acrylate-co-n-butyl acrylate) (P(IBA-co-nBA)) copolymers was tuned by changing the monomer feed. This way, it was possible to generate materials which can mimic thermal behavior of several homopolymers, such as poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). Although statistical copolymers had the same thermal properties as their homopolymer equivalents, DMA measurements revealed that they are much softer materials. While statistical copolymers showed a single Tg, block copolymers showed two Tgs and DSC thermogram for the gradient copolymer indicated a single, but very broad, glass transition. The mechanical properties of block and gradient copolymers were compared to the statistical copolymers with the same IBA/nBA composition.

Large positive thermal expansion in polymers is one of the major drawbacks in using polymers in applications where the sample dimensions play an important role. In this paper, we report a method to vary the thermal expansion of PMMA-based polymer composites by blending with a negative thermal expansion material, PbTiO 3 . It is shown that the thermal expansion coefficient of the composite can be tailored by suitably adjusting the ratio of polymer and ceramic filler. The coefficient of thermal expansion has been measured using temperature-dependent step-height measurements via confocal microscopy. Using SEM, it is shown that the ceramic particles are homogeneously dispersed in the polymer matrix if the composite is obtained by the polymerization of the suspension of PbTiO 3 in the monomer MMA. Composite formation is confirmed using XRD and Raman spectroscopy. To estimate the technological viability of such composite films, preliminary results of stress-strain measurements are also presented.

This paper discusses static and dynamic mechanical properties of electron beam-cured mixtures made of the nematic liquid crystal (LC) E7 and either tripropyleneglycol diacrylate (TPGDA) or propoxylated glycerol triacrylate (GPTA) as monomers differing essentially by their functionnality. Dilution of the initial mixture with LC leads to a significant weakening of the film mechanical strength. Strong effects were found on Young modulus and rubbery state modulus. As the concentration of LC increases, these mechanical parameters drop significantly together with the glass transition temperature of the polymer showing a plasticizing effect. The results for the glass transition temperatures for the polymer and the LC were confirmed by thermograms obtained by differential scanning calorimetry.

Experimental control over cellular polarity in a neuronal network is a promising tool to study synapse formation and network behavior. We aimed to exploit a mechanism described by Stenger et al. [J. Neurosci. Methods 82 (1998) 167] to manipulate the direction of axonal versus dendritic outgrowth on a micropattern. The group had used laser ablation to create patterns of aminated silanes for cell attachment on a background of repellent fluorinated silanes. The pattern offered continuous adhesive pathways for axonal and interrupted pathways for dendritic outgrowth. By microcontact printing, we created similar patterns containing continuous and interrupted pathways consisting of extracellular matrix proteins on a background of polystyrene. Neuronal polarity was determined on the functional level through double patch clamp measurements, detecting synapses and their orientation. Although our pattern reproduced the properties that were assumed to be critical for the described effect, namely contrasting pathways of different adhesiveness, we failed to reproduce the above results. It is indicated that other qualities of alternative pathways than mere differences in adhesiveness are required to orient neuronal polarity in vitro. We suggest that the effect observed by Stenger et al. has to be attributed to less universal characteristics of the micropattern, e.g. to the specific chemical groups that were utilized.

This paper reports a study of static and dynamic mechanical properties of electron beam (EB) cured polymer dispersed liquid crystals. These systems consist of micron-sized droplets dispersed in a solid polymer matrix. They are prepared according to the polymerization induced phase separation process initiated by exposure to electron radiation. A difunctional monomer Tripropylene Glycol Diacrylate in short TPGDA is used with the eutectic liquid crystal mixture E7 having a nematic to isotropic transition temperature at 60°C. Strong effects are found on Young modulus and rubbery state modulus in terms of the EB dose and the liquid crystal concentration. As the concentration of small molecules increases, these mechanical parameters drop significantly together with the glass transition temperature Tg of the polymer showing a plasticizing effect. The results for Tg are confirmed by DSC thermograms in terms of liquid crystal concentration and EB dose.

A static light scattering study of monomeric (uncured) and Electron Beam (EB) cured Tripropyleneglycoldiacrylate (TPGDA) and E7 (a nematic Liquid Crystal) systems is reported. This study includes a detailed investigation of the structural properties in terms of temperature, composition and scattering angle. Knowledge of the phase diagrams helps us to achieve a better understanding of the scattering curves and rationalize data in terms of the LC configuration inside droplets. The depolarized component of the scattered intensity measured under cross polarizers exhibits patterns reminiscent of anisotropic objects. The results can be correlated to the electro-optical responses of the investigated systems relevant to applications in display technology and smart windows.

Pressure–volume–temperature measurements in phenylphthalein-dimethylether (PDE) are reported, in combination with recently published dynamic light scattering data obtained under high pressure. We discuss the role that volume and thermal effects play in controlling the dynamics in the vicinity of the glass transition. Although volume is not the unique thermodynamical parameter characterizing the relaxation dynamics in PDE, its contribution to the super-Arrhenius behavior of the relaxation times in the vicinity of the glass transition is remarkable. The contribution of volume to the temperature dependence of the relaxation times has been characterized by means of the ratio of the activation energy at constant volume to the enthalpy of activation at constant pressure, EV/HP. We point out that this quantity is correlated with the temperature behavior of the nonexponentiallity parameter, βKWW. Moreover, the τ(T,P) values were analyzed in terms of an extension of the Adam–Gibbs model. It was shown that this model gives a satisfactory interpretation of the pressure sensitivity of the dynamics (d log10(τ)/dP)|T in terms of thermodynamic properties of the material.

From pressure–volume–temperature measurements, in combination with published dielectric spectroscopy results, we assess the volume dependence of structural relaxation in cresolphthalein–dimethylether (KDE). Structural relaxation in KDE cannot be described as either a volume activated or thermally activated process, and unlike results for some other molecular glass formers, temperature is not the dominant control variable. The inflection point of the PVT data yields a glass temperature, Tg, that corresponds to a dielectric relaxation time equal to 10 s. There is a marked variation with pressure, dTg/dP=307 K/GPa at low pressure. We also carried out dynamic mechanical measurements on KDE near Tg. The shape of the mechanical and dielectric relaxation functions, as well as both the magnitude and temperature dependence of the respective relaxation times, are the same. Such equivalence is not generally expected, and arises herein due to the rigid structure of the KDE molecule.

We study the slow dynamics of salol by varying both temperature and pressure using photon correlation spectroscopy and pressure-volume-temperature measurements, and compare the behavior of the structural relaxation time with equations derived within the Adam-Gibbs entropy theory and the Cohen-Grest free volume theory. We find that pressure-dependent data are crucial to assess the validity of these model equations. Our analysis supports the entropy-based equation, and estimates the configurational entropy of salol at ambient pressure approximately 70% of the excess entropy. Finally, we investigate the evolution of the shape of the structural relaxation process, and find that a time-temperature-pressure superposition principle holds over the range investigated.

The phase separation of the polymer blend polystyrene/poly(methyl phenyl siloxane) (PS/PMPS) is studied in situ by laser scanning confocal microscopy (LSCM) and by fluorescence correlation spectroscopy (FCS) at macroscopic and microscopic length scales, respectively. It is shown for the first time that FCS when combined with LSCM can provide independent information on the local concentration within the phase-separated domains as well as the interfacial width.

Total internal reflection-fluorescence correlation spectroscopy (TIR-FCS) is a powerful method for studying dynamic processes at liquid-solid interfaces that may have numerous applications in biology, physics, and material science. Despite of its power and versatility, however, the use of TIR-FCS is still rather limited. The main reason for this is the need of a complex, in-house constructed optical setup whose assembly and adjustment is a quite difficult task. Clearly, the availability of ready to use, commercial TIR-FCS setups will strongly boost the application of this important method in many research areas. In this note we show that although such setups are still not available in the market, a proper combination of commercial devices for confocal fluorescence correlation spectroscopy and for total internal reflection microscopy may enable TIR-FCS in a way that do not require any special optical alignments. Furthermore, we demonstrate the capabilities of the setup by measuring the diffusion coefficient of single dye molecule and quantum dots in the very proximity of a water-glass interface.

There is a growing interest in the development of stable nanocapsules that could deliver the bioactive compounds within the living organism, and to release them without causing any toxic effects. Here the miniemulsion droplets were first used as "nanoreactors" for the amplification of single-molecule dsDNA template (476 and 790 base pairs) through PCR. Afterwards, each droplet was surrounded with a biodegradable PBCA shell by interfacial anionic polymerization, enabling therefore to deliver the PCR products into the cells. The size of the initial miniemulsion droplets and the final polymeric capsules was in the range of 250 and 320 nm, mainly depending on the type of the continuous phase and presence of dsDNA template molecules. The formation of PCR products was resolved with gel electrophoresis and detected with fluorescence spectroscopy in the presence of DNA specific dye (SYBRGreen). TEM studies were performed to prove the formation of the polymeric shell. The shell thickness was measured to be within 5-15 nm and the average molecular weight of the formed PBCA polymer was around 75000 g · mol(-1) . For the cell uptake experiments, the obtained nanocapsules were transferred from the organic phase into aqueous medium containing a water-soluble surfactant. The effect of the surfactant type (anionic, cationic or non-ionic) on the HeLa cell viability and nanocapsule uptake behavior was studied by CLSM and FACS. Confocal analysis demonstrated that nanocapsules stabilized with cationic (CTMA-Cl) and non-ionic (Lutensol AT50) surfactants show almost the same uptake, whereas capsules redispersed in anionic (SDS) surfactant possess a 30% higher uptake. The release of the encapsulated material within the cell was studied on the example of Cy5-labeled oligonucleotides showing the colocalization with mitochondria of MSCs cells.

We present a new method for three-dimensional imaging of the inversed ferroelectric domains hidden inside nonlinear photonic structures. The method is based on Cerenkov-type second harmonic generation laser scanning microscopy and offers sub-micrometer resolution.

We employed fluorescence correlation spectroscopy (FCS) to study the diffusion of molecular and macromolecular tracers in polystyrene solutions over a broad range of concentrations (c) and molecular weights (M(w,m)) of the matrix polymer. Molecular tracer diffusion scales only with the matrix concentration and superimposes on a single, nonpolymer specific, curve. On the contrary, the diffusion of macromolecular tracers in solutions of matrix polymers with M(w,m) sufficiently larger than the tracer molecular weight scales with c/c(p)*, where c(p)* is the tracer overlap concentration. We further demonstrate that FCS can address local and global dynamics simultaneously.