pH/Thermosensitive Hydrogels Formed at Low pH by a PMMA‐PAA‐P2VP‐PAA‐PMMA Pentablock Terpolymer

A poly(methyl methacrylate)‐block‐poly(acrylic acid)‐block‐poly(2‐vinyl pyridine)‐block‐poly(acrylic acid)‐block‐poly(methyl methacrylate) (PMMA‐PAA‐P2VP‐PAA‐PMMA), pentablock terpolymer has been synthesized by anionic polymerization with sequential addition of monomers and studied in aqueous media at low pH. The system exhibits combined properties and adopts the behavior of ‘telechelic’ polyelectrolytes and that of double hydrophilic polyampholytes. This complex behavior leads to the pentablock terpolymer forming a pH and temperature sensitive reversible hydrogel at very low polymer concentration.

     

Photothermal hydrogen sensor: the technique, experimental process, and physicochemical analysis

The kinetics of hydrogen adsorption and desorption on palladium thin films was studied via photomodulated thermoreflectance measurements. The subsequent analysis based on a Langmuirian isothermal model supports dissociative adsorption of hydrogen on palladium followed by molecular desorption. Furthermore, the rate constants of adsorption and desorption were determined and their values are discussed. The response and recovery times of the sensor were measured and their dependence on hydrogen concentration is also explored and discussed.     

Cotransport of Graphene Oxide Nanoparticles and Kaolinite Colloids in Porous Media

Optimising production from heterogeneous and anisotropic reservoirs challenges the modern hydrocarbon industry because such reservoirs exhibit extreme inter-well variability making them very hard to model. Reasonable reservoir models can be obtained using modern geostatistical techniques, but all of them rely on significant variability in the reservoir only occurring at a scale at or larger than the inter-well spacing. In this paper we take a different, generic approach. We have developed a method for constructing realistic synthetic heterogeneous and anisotropic reservoirs which can be made to represent the reservoir under test. The main physical properties of these synthetic reservoirs are distributed fractally. The models are fully controlled and reproducible and can be extended to model multiple facies reservoir types. This paper shows how the models can be constructed and how they have been tested. Reservoir simulation results of a number of generated 3-D heterogeneous and anisotropic models show that heterogeneity, in terms of only the geometric distribution of reservoir properties, has a little effect on oil production from high and moderate quality reservoirs. However, if the effect of heterogeneity on capillary pressure is taken into account, the effect becomes striking, where varying the heterogeneity of reservoirs properties can lead to a 70 % change in the predicted oil production rate and a significant early shift of water breakthrough time. Hence, it is the heterogeneity consequences that are really substantial if not taken into account. These are very significant uncertainties for a hydrocarbon company if the heterogeneity of their reservoir is not well defined.     

Heteroarm Star‐Like Micelles Formed from Polystyrene‐block‐poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) ABC Triblock Copolymers in Toluene

Polystyrene‐block‐poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) ABC triblock copolymers were synthesized by sequential living anionic polymerization. Their solution properties were investigated in toluene, which is a bad solvent for the middle block. Spherical micelles are formed, which consist of a poly(2‐vinyl pyridine) dense core bearing polystyrene and poly(methyl methacrylate) soluble chains at the corona. These micelles exhibit the architecture of heteroarm star copolymers obtained by “living” polymerization methods. The aggregation numbers strongly depend on the length of the insoluble P2VP middle block, thus remarkably affecting the size of the micelles.     

Synthesis of coil‐rod‐coil block copolymers with the aid of anionic polymerization

A two step synthetic procedure towards model coil‐rod‐coil triblock copolymers was developed. In the first step, α,ω‐bromo‐functionalized oligophenylenes (rod part) were modified to anionic bifunctional initiators. In the second step, flexible chains were grown from both ends of the rod part by an anionic polymerization procedure leading to polystyrene‐rod‐polystyrene and/or poly(2‐vinyl pyridine)‐rod‐poly(2‐vinyl pyridine) triblock copolymers. Characterization of the final products by gel permeation chromatography, NMR spectroscopy, light scattering, Raman spectroscopy and differential scanning calorimetry demonstrated that well‐defined coil‐rod‐coilblock copolymers can be synthesized.     

Multi‐Compartment Unimolecular Micelles from (ABC)n Multi‐Arm Star Triblock Terpolymers

Four linear and four star equimolar terpolymers based on non‐ionic hydrophilic methoxy hexa(ethylene glycol) methacrylate, ionizable hydrophilic 2‐(dimethylamino)ethyl methacrylate and neutral hydrophobic methyl methacrylate were synthesized using group transfer polymerization and investigated in aqueous dilute solutions. It was found that the (ABC)_n multi‐arm star terpolymers formed unimolecular micelles comprising three centrosymmetric compartments. The position of each compartment could be determined by the block sequence (ABC, ACB or BAC) at will. On the other hand, the ABC linear counterparts formed loose associates with very low aggregation numbers. It was shown that the polymer architecture (linear versus star) greatly affected the micellization phenomena of the terpolymers in selective media.

     

Multifunctional Stimuli Responsive ABC Terpolymers: From Three‐Compartment Micelles to Three‐Dimensional Network

Summary: A highly asymmetric P2VP₅₈‐PAA₉₂₄‐PBMA₄₈ double hydrophilic block terpolymer exhibits a rich phase behavior as a function of pH. In acidic media (pH 1) three compartment micelles with a positively charged outer corona are formed. At high pH, the above structure is transformed into a three‐dimensional transient network constituted of hydrophobic domains interconnected with negatively charged bridging chains (PAA chains). At even higher pH (14) the network is disrupted and finally exhibits a closed loop sol–gel–sol behavior.

AFM images of P2VP₅₈‐PAA₉₂₄‐PBMA₄₈ micellar self assemblies deposited on mica.     

Synthesis and Antiproliferative Activity of Novel Dehydroabietic Acid-Chalcone Hybrids

Dehydroabietic Acid (DHA, 1) derivatives are known for their antiproliferative properties, among others. In the context of this work, DHA was initially modified to two key intermediates bearing a C18 methyl ester, a phenol moiety at C12, and an acetyl or formyl group at C13 position. These derivatives allowed us to synthesize a series of DHA-chalcone hybrids, suitable for structure–activity relationship studies (SARS), following their condensation with a variety of aryl-aldehydes and methyl ketones. The antiproliferative evaluation of the synthesized DHA-chalcone hybrids against three breast cancer cell lines (the estrogen-dependent MCF-7 and the estrogen-independent MDA-MB-231 and Hs578T) showed that eight derivatives (33, 35, 37, 38, 39, 41, 43, 44) exhibit low micromolar activity levels (IC₅₀ 2.21–11.5 μΜ/MCF-7). For instance, some of them showed better activity compared to the commercial anticancer drug 5-FU against MCF-7 cells (33, 41, 43, 44) and against MDA-MB231 (33 and 41). Hybrid 38 is a promising lead compound for the treatment of MCF-7 breast cancer, exhibiting comparable activity to 5-FU and being 12.9 times less toxic (SI = 22.7). Thus, our findings suggest that DHA-chalcone hybrids are drug candidates worth pursuing for further development in the search for novel breast cancer therapies.     

Development and Validation of an Automated Zone Fluidics-Based Sensor for In Vitro Dissolution Studies of Captopril Using Total Error Concept

In the present research, a zone fluidics-based automated sensor for the analysis of captopril in in vitro dissolution samples is reported. Captopril is reacted under flow conditions with Ni(II) (10 mmol L⁻¹) in alkaline medium (0.15% v/v NH₃) to form a stable derivate, which is monitored spectrophotometrically at 340 nm. The chemical and instrumental parameters were carefully investigated and optimized. The validation of the developed method was performed in the range of 5 to 120% of the expected maximum concentration using the accuracy profiles as a graphical decision-making tool. The β-expectation tolerance intervals did not exceed the acceptance criteria of ±10%, which means that 95% of future results will be encompassed in the defined bias limits. The variation of the relative bias ranged between −2.3% and 3.5% and the RSD values for repeatability and intermediate precision were lower than 2.3% in all cases. The limit of detection (LOD), and the lower and the upper limit of quantification (LLOQ, ULOQ) were satisfactory and found to be 1%, 5% and 120% (corresponding to 0.6, 2.78 and 66.67 μg mL⁻¹ in dissolution medium). The developed method was successfully applied for the analysis of captopril in dissolution tests of two commercially available batches.