pH Modulated Formation of Complexes with Various Stoichiometry between Polymer Network and Fe(III) in Thermosensitive Gels Modified with Gallic Acid.

Thermoresponsive gels based on N-isopropylacrylamide functionalized with amino groups were modified with gallic acid, with gallate (3,4,5-trihydroxybenzoic) groups being introduced into the polymer network. We investigated how the properties of these gels were affected at varying pH, by the formation of complexes between the polymer network of the gels and Fe3+ ions (which form stable complexes with gallic acid, exhibiting 1:1, 1:2, or 1:3 stoichiometry, depending on pH). The formation of complexes with varying stoichiometry within the gel was confirmed using UV-Vis spectroscopy, and the influence of such complexes on swelling behavior and volume phase transition temperature were investigated. In the appropriate temperature range, complex stoichiometry was found to strongly affect the swelling state. Changes in the pore structure and mechanical properties of the gel caused by the formation of complexes with varying stoichiometry were investigated using scanning electron microscopy and rheological measurements, respectively. The volume changes exhibited by p(NIPA-5%APMA)-Gal-Fe gel were found to be greatest at close to human body temperature (~38 °C). Modification of thermoresponsive pNIPA gel with gallic acid opens new opportunities for the development of pH- and thermosensitive gel materials.

Nanocomposite Organogel for Art Conservation─A Novel Wax Resin Removal System.

We describe a new, safe, and effective method for removing wax resin adhesive from the canvases of paintings conserved by the once widely used Dutch Method, which involved attaching a new canvas to the back of a painting using an adhesive made of beeswax and natural resin. First, a low-toxicity cleaning mixture for dissolving the adhesive and removing it from the canvases was developed, and then a nanocomposited organogel was obtained. The ability of the organogel to remove the adhesive from canvases was investigated on the lining of the 1878 painting "Battle of Grunwald" by Jan Matejko, with promising results. Additionally, we found that the organogel can be used several times with no visible loss of cleaning ability. Finally, the effectiveness and safety of the method were confirmed on two oil paintings (one from the National Museum in Warsaw): all the wax resin adhesive was removed and the painting regained its original brightness and vivid colors.

Temperature-Modulated Changes in Thin Gel Layer Thickness Triggered by Electrochemical Stimuli.

A series of thermoresponsive hydrogels containing positively charged groups in the polymeric network were synthesized and modified with the electroactive compound 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS). ABTS, which forms a dianion in aqueous solutions, acts as an additional physical cross-linker and strongly affects the swelling ratio of the gels. The influence of the amount of positively charged groups and ABTS oxidation state on the volume phase transition temperature was investigated. A hydrogel that possesses a relatively wide and well-defined temperature window (the temperature range where changes in the ABTS oxidation state affects the swelling ratio significantly) was found. The influence of the presence and oxidation state of ABTS on mechanical properties was investigated using a tensile machine and a rheometer. Then, a very thin layer of the gel was deposited on an Au electrochemical quartz crystal microbalance with dissipation (EQCM-D) electrode using the electrochemically induced free radical polymerization method. Next, chronoamperometry combined with quartz crystal microbalance measurements, obtained with an Au EQCM-D electrode modified by the gel, showed that the size of the thin layer could be controlled by an electrochemical trigger. Furthermore, it was found that the electrosensitivity could be modulated by the temperature. Such properties are desired from the point of view construction of electrochemical actuators.

Implication and Inhibition Boolean Logic Gates Mimicked with Enzyme Reactions.

The enzyme system mimicking Implication (IMPLY) and Inhibition (INHIB) Boolean logic gates has been designed. The same enzyme system was used to operate as the IMPLY or INHIB gate simply by reformulating the input signals. The optical analysis of the logic operation confirmed the output generation as expected for the studied logic gates. The conceptual approach to the IMPLY and INHIB logic gates allows their construction with many other enzymes operating in a similar way.

Changes in the volume phase transition temperature of hydrogels for detection of the DNA hybridization process.

A simple biosensing platform which involves the application of thermoresponsive hydrogels (p(NIPA-co-AA)) for detection of target DNA sequences is presented. For this aim the hydrogel based on N-isopropylacrylamide grafted with carboxyl groups was modified with H2N-ssDNA via the amide bond. The detection of target DNA sequences was achieved successfully by monitoring the volume phase transition temperature (VPTT). It was found that the dependence between the VPTT and the concentration of the target complementary DNA is linear in the concentration range from 10-12 to 10-6 M. The proposed DNA detection method is characterized by high sensitivity and good reproducibility. The detection limit obtained (∼1 pM) is a substantial improvement over DNA biosensor labelling with tags, because the detection is based on a physical parameter (VPTT). Circular dichroism (CD) and inductively coupled plasma mass spectrometry with laser ablation (LA-ICP-MS) proved that the hybridization process took place in the hydrogel matrix without any restrictions.

Electrochemical Examination of the Structure of Thin Hydrogel Layers Anchored to Regular and Microelectrode Surfaces.

For the examination of hydrogel structure, thin layers of thermoresponsive gels based on poly(N-isopropylacrylamide) (pNIPA) and copolymer poly(N-isopropylacrylamide-co-sodium acrylate) (p(NIPA-co-AS)) were successfully anchored to microelectrode and regular electrode surfaces using the electrochemically induced free radical polymerization. The obtained layers were stable and covered the entire surface of the electrodes. Electroactive probes 1,1'-ferrocenedimethanol (Fc(CH2OH)2) and synthesized derivatives of ferrocene modified with polyethylene glycol units (Fc-PEGn) of various length (n = 4, 9, 75, and 135) were employed for studying the volume phase transition of the thin hydrogel layers and for the determination of their structural parameters. The quantitative information on the structural parameters of the hydrogel layers was derived from the obstruction model for diffusion using the voltammetrically determined diffusion coefficients for the model redox probe Fc(CH2OH)2. An approach to the determination of the effective radii of the gel openings (channels) for pNIPA and p(NIPA-co-AS) microlayers was developed. The obtained results were matched with the experimental results and allowed derivation of quantitative conclusions. The voltammograms obtained with modified electrodes in solutions containing Fc-PEG4, Fc-PEG9, and Fc-PEG75 were well defined and of appropriate height. However, the voltammograms recorded for Fc-PEG135, the hydrodynamic radius of which exceeded the size of the gel channels, were at the baseline level.

Stable and degradable microgels linked with cystine for storing and environmentally triggered release of drugs.

Environmentally sensitive, degradable microgels based on poly(N-isopropylacrylamide) (pNIPA) cross-linked with the diacryloyl derivative of cystine (BISS) were synthesized by applying surfactant-free emulsion polymerization. pNIPA contributed the sensitivity to temperature to the microgels and the cross-linker made them degradable and sensitive to pH. The morphology of the microgels was investigated by using scanning and transmission electron microscopies (SEM and TEM). The gels formed spherical particles with a narrow size distribution. The influence of temperature, pH and ionic strength on the swelling behavior and the stability of new microgels with various contents of BISS (0, 1 and 3%) were investigated by dynamic light scattering (DLS). It was found that microgels with 3% content of amino acid were highly stable over a wide range of investigated temperatures, pH values and ionic strengths, including the physiological conditions (pH = 7.4, IS = 0.15 M, and 37 °C). The reduction-induced degradation of these microgels by 0.01 M solution of dithiothreitol (DTT) or glutathione (GSH) was studied by means of SEM and TEM; the obtained micrographs showed the destruction of spherical microgel particles. The microgels containing 3% of BISS could be loaded with doxorubicin (DOX) by employing the electrostatic interactions between the DOX amine group and the ionized carboxyl group from BISS. A significant increase in the cumulative release of DOX was observed after changing pH from that characteristic to blood (∼7.4) to that existing in affected cells (∼5.0) and in the presence of GSH (CGSH∼ 10 mM). The cytotoxicity tests proved that the obtained microgels are interesting as useful carriers in directed drug delivery systems.