Anomalous diffusion in thermoresponsive polymer-clay composite hydrogels probed by wide-field fluorescence microscopy.

Thermoresponsive materials exhibit an enormous potential for tissue engineering, separation systems, and drug delivery. We investigated the diffusion of laponite clay nanoparticles, which serve as physical cross-linkers to achieve improved material properties in poly(N-isopropylacrylamide) (PNIPAM)-clay composite hydrogels close to the gel point. The networks are formed through physical interactions between PNIPAM chains and clay nanoparticles after these two components are mixed. In contrast to previous studies, a covalent labeling strategy was chosen to minimize the amount of free dyes in solution. Single-particle tracking of the labeled clay nanoparticles showed that their diffusion is anomalous at all temperatures used in this study, reflecting the viscoelastic behavior as a cross-linker. Stepwise heating from 24 to 38 °C resulted in a slight increase of the diffusion coefficient and the anomality parameter α up to the volume phase transition temperature of ca. 31 °C, which was followed by a significant drop of both parameters, reflecting strongly hindered motion of the collapsed nanoparticle aggregates.

Hyperbranched PEI with various oligosaccharide architectures: synthesis, characterization, ATP complexation, and cellular uptake properties.

We present a rapid synthetic method for the development of hyperbranched PEIs decorated with different oligosaccharide architectures as carrier systems (CS) for drugs and bioactive molecules for in vitro and in vivo experiments. Reductive amination of hyperbranched PEI with readily available oligosaccharides results in sugar functionalized PEI cores with oligosaccharide shells of different densities. These core-shell architectures were characterized by NMR spectroscopy, elemental analysis, SLS, DLS, IR, and polyelectrolyte titration experiments. ATP complexation of theses polycations was examined by isothermal titration calorimetry to evaluate the binding energy and ATP/CS complexation ratios under physiological conditions. In vitro experiments showed an enhanced cellular uptake of ATP/CS complexes compared to those of the free ATP molecules. The results arise to initiate further noncovalent complexation studies of pharmacologically relevant molecules that may lead to the development of therapeutics based on this polymeric delivery platform.

Hydrogel-based piezoresistive pH sensors: investigations using FT-IR attenuated total reflection spectroscopic imaging.

The strong swelling ability of the pH-responsive poly(acrylic acid)/poly(vinyl alcohol) (PAA/PVA) hydrogel makes the development of a new type of sensor possible, which combines piezoresistive-responsive elements as mechanoelectrical transducers and the phase transition behavior of hydrogels as a chemomechanical transducer. The sensor consists of a pH-responsive PAA/PVA hydrogel and a standard pressure sensor chip. However, a time-dependent sensor output voltage mirrors only the physical swelling process of the hydrogel but not the corresponding chemical reactions. Therefore, an investigation of the swelling behavior of this hydrogel is essential for the optimization of sensor design. In this work, Fourier transform infrared (FT-IR) spectroscopic imaging was used to study the swelling of the hydrogel under in situ conditions. In particular, laterally and time-resolved FT-IR images were obtained in the attenuated total reflection mode and the entire data set of more than 80,000 FT-IR spectra was evaluated by principal component analysis (PCA). The first and third principal components (PCs) indicate the swelling process. Molecular changes within the carboxyl groups were observed in the second and fourth PC and identified as key processes for the swelling behavior. It was found that time-dependent molecular changes are similar to the electrical sensor output signal. The results of the FT-IR spectroscopic images render an improved chemical sensor possible and demonstrate that in situ FT-IR imaging is a powerful method for the characterization of molecular processes within chemical-sensitive materials.

Review on Hydrogel-based pH Sensors and Microsensors.

Stimuli-responsive hydrogels are materials with great potential for development of active functionalities in fluidics and micro-fluidics. Based on the current state of research on pH sensors, hydrogel sensors are described qualitatively and quantitatively for the first time. The review introduces the physical background of the special properties of stimuli-responsive hydrogels. Following, transducers are described which are able to convert the non-electrical changes of the physical properties of stimuli-responsive hydrogels into an electrical signal. Finally, the specific sensor properties, design rules and general conditions for sensor applications are discussed.

Rolled-up magnetic sensor: nanomembrane architecture for in-flow detection of magnetic objects.

Detection and analysis of magnetic nanoobjects is a crucial task in modern diagnostic and therapeutic techniques applied to medicine and biology. Accomplishment of this task calls for the development and implementation of electronic elements directly in fluidic channels, which still remains an open and nontrivial issue. Here, we present a novel concept based on rolled-up nanotechnology for fabrication of multifunctional devices, which can be straightforwardly integrated into existing fluidic architectures. We apply strain engineering to roll-up a functional nanomembrane consisting of a magnetic sensor element based on [Py/Cu](30) multilayers, revealing giant magnetoresistance (GMR). The comparison of the sensor's characteristics before and after the roll-up process is found to be similar, allowing for a reliable and predictable method to fabricate high-quality ultracompact GMR devices. The performance of the rolled-up magnetic sensor was optimized to achieve high sensitivity to weak magnetic fields. We demonstrate that the rolled-up tube itself can be efficiently used as a fluidic channel, while the integrated magnetic sensor provides an important functionality to detect and respond to a magnetic field. The performance of the rolled-up magnetic sensor for the in-flow detection of ferromagnetic CrO(2) nanoparticles embedded in a biocompatible polymeric hydrogel shell is highlighted.

Gelation mechanism of poly(N-isopropylacrylamide)-clay nanocomposite hydrogels synthesized by photopolymerization.

The gelation process of poly-(N-isopropylacrylamide)-clay nanocomposite hydrogels (PNIPAAm-clay NC gels) was investigated by dynamic and static light scattering (DLS and SLS), as well as by fluorescence correlation spectroscopy (FCS). The photopolymerization method chosen for the radical polymerizing system ensured that, when the irradiation is removed, the reaction stopped immediately. Experiments showed that shortly before the gelation threshold is reached, no changes in the DLS autocorrelation functions appear, while the monomer conversion can be observed by 1H NMR spectroscopy. These results correspond to the formation of microparticles, in which the PNIPAAm chains are closely attached to the clay platelets. During the further polymerization process, clay clusters are developed before the sol-gel threshold is reached. FCS measurements were performed to obtain information on the motion of the clay platelets inside the NC gel. The DLS method gives only an average of the motions in the gel. In a time window between 10 micros and 1 s, the clay sheets labeled with Rhodamine B show no characteristic motions.

Chain dynamics in microgels: poly(N-vinylcaprolactam-co-N-vinylpyrrolidone) microgels as examples.

Microgels are highly swollen colloids built up of flexible cross-linked chains. We studied the static and dynamic light scattering (LS) behavior of thermosensitive microgels based on N-vinylcaprolactam and N-vinylpyrrolidone prepared by precipitation copolymerization in H2O (CP-1) and D2O (CP-2). Striking differences in behavior were observed in the two solvents. In both cases the angular dependence of static LS could reasonably well be described by a soft sphere model (J. Polym. Sci., Polym. Phys. Ed. 1982, 20, 157) with small deviations at large qRg. At temperatures larger than the collapse temperatures, the CP-1 sample in water started to aggregate whereas the CP-2 sample in D2O showed no association and developed the expected change toward hard sphere behavior. Dynamic LS permitted the determination of internal or segmental mobility. A remarkable shift toward large qRg was found for CP-1 compared to the behavior of linear chains. The dynamic behavior is clearly displayed in a plot of Gamma*(q) = (Gamma1(q)/q3)(eta0/kT), with Gamma1(q) the first cumulant of the field time correlation function and the common meaning of the other parameters. A long range of hard sphere behavior indicated the suppression of internal modes, but at large qRg the swollen microgel CP-1 in water displayed internal motions with a spectrum similar to that of Zimm relaxations. No internal mobility could be detected with the CP-2 sample in D2O. The behavior is in agreement with observations in the literature. The differences in the two similar solvents were attributed to the poorer solvent quality of D2O.

Electron beam irradiation of poly(vinyl methyl ether) films. 2. Temperature-dependent swelling behavior.

Temperature-sensitive hydrogel films were synthesized by electron beam irradiation of poly(vinyl methyl ether) (PVME) on silicon (Si/SiO(2)) substrates and gold (Au) coated glass slides. The temperature-dependent swelling behavior of the films in aqueous solution was characterized by in situ spectroscopic ellipsometry and a combination of surface plasmon resonance (SPR) and optical waveguide spectroscopy (OWS). The results of both techniques are compared. The suitability of both techniques for the characterization of the swelling behavior of thin hydrogel films is demonstrated. The volume swelling degree in the swollen state decreases with increasing radiation dose D. This is explained by the fact that the number of formed polymeric radicals, and hence cross-linking density, increases with D. Above the phase-transition temperature, the swelling degrees were independent of D, slightly above 1. The swelling/deswelling process was fully reversible and is mainly directed perpendicular to the substrate surface. The phase-transition temperature was determined to be T(cr) approximately 33 degrees C. However, T(cr) slightly decreases with increasing D and increasing film thickness d.

Electron beam irradiation of poly(vinyl methyl ether) films: 1. Synthesis and film topography.

Temperature-sensitive hydrogel layers on silicon (Si) substrates were synthesized by electron beam irradiation of spin-coated poly(vinyl methyl ether) (PVME) films. The influences of the used solvent, the polymer concentration, and the spinning velocity on the homogeneity and the thickness of the PVME film were investigated. In the range of concentration c(p) = 1-15 wt% PVME in ethanol solution, homogeneous films with a thickness between d = 50 nm and 1.7 mum were obtained. The films were cross-linked by electron beam irradiation under inert atmosphere and analyzed by sol-gel-analysis. The results were compared with bulkgels formed by electron beam irradiation of PVME in the dry state. The film topography was analyzed by high-resolution field emission scanning electron microscopy and atomic force microscopy. An islandlike structure in the dry, swollen, and shrunken state of the hydrogel films was observed.

Characterization of structural changes of poly(vinyl methyl ether) gamma-irradiated in diluted aqueous solutions.

An aqueous deoxygenated dilute PVME solution (cP = 0.5 mass %) was irradiated with gamma-rays at different radiation doses (D = 0.2-10 kGy). At these concentrations and doses contracted molecules are formed but no macroscopic networks. For the analysis of the structural changes, the irradiated samples were analyzed by size exclusion chromatography (SEC) with a triple detector system, static light scattering, and viscometry. SEC measurements necessitate for the application of the universal calibration principle the knowledge of the Kuhn-Mark-Houwink (KMH) parameters. To obtain these parameters commercially available poly(vinyl methyl ether) was fractionated and analyzed by the same means. We found at 30 degrees C a KMH relationship to [eta] = 0.0226 (mL/g) x Mw(0.67) in THF. We observed an increase in molar masses without any significant structural changing for D < 0.5 kGy. With increasing radiation dose, the intramolecular cross-linking reaction becomes more and more important. The results of viscosity measurements show a slight increase in contraction for 1.0 kGy. For irradiation dose higher than D > 1.5 kGy, a strong contraction occurs. For D > 5.0 kGy, the favored intramolecular reactions lead to the formation of microgels.