Effect of pH on Poly(acrylic acid) Solution Polymerization

The free-radical redox-initiated aqueous solution polymerization of fully and partially neutralized acrylic acid was carried out at room temperature under full exposure to air. The effect of neutralization degree on the polymerization rate and product properties was studied. Increasing neutralization of the reaction mixture with sodium hydroxide resulted in greater conversion of acrylic acid to sodium acrylate. The rate of polymerization, determined from a gravimetric off-line water removal technique, was shown to decrease significantly with decreasing degree of neutralization. Molecular weight also decreased with decreasing degree of neutralization. The glass transition temperature and hydrophilicity of the polymer product decreased with increasing degree of neutralization. In-line infrared monitoring was also used to monitor the reaction progress and was shown to be an effective tool for this purpose.     

Composite of SiO2 and Hydrogel Having Microphase Separated Structure: Physical Properties Dependence on pH

Abstract

Organic-inorganic composite gel was prepared by using PEG-modified urethane acrylate (PMUA) gel and tetraethoxysilane (TEOS). PMUA gel was prepared by the phase-inversion emulsion polymerization of PMUA emulsion. The gelation of PMUA emulsion using this method enables PMUA gel to swell with H₂O, TEOS, and ethanol. Hydrolysis and condensation reaction rates of the sol-gel process are strongly influenced by the pH controlled by catalysts such as HCl and NH₄OH. Additionally, the morphology on the cross section of composite and the amount of silica ingredient incorporated into the composite gel were dependent on solvent, the molar ratio of H₂O to TEOS, as well as the pH value.

As the silica content increased, due to hydrogen bonds interacting between PMUA gel and SiO₂, particles, the tensile strength of composites considerably increased, whereas the elongation at break decreased. The incorporation of silica ingredient in PMUA gel/silica composites was verified with FTIR/ATR and SEM. The amount of the silica component in the composite was indirectly investigated by using TGA thermal analysis.     

Preparation of Poly(N‐isopropylacrylamide) Microgels using Different Initiators Under Various pH Values

Ammonium persulfate (APS), 2,2′‐azobis(amidinopropane) dihydrochloride (V50) and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) were utilized to prepare temperature‐sensitive poly(N‐isopropylacrylamide) (PNIPAM) microgels by precipitation polymerization under various reaction pH conditions. Their particle sizes and swelling ratios depended on the reaction pH due to the pH dependence on the ionization degree of the decomposed fragments originating from the initiators and their hydrophilicity‐hydrophobicity. The more hydrophobic initiator, under the reaction pH conditions used, could be partitioned to a greater extent into the microgel particles due to the hydrophobicity of PNIPAM chains at the reaction temperature, which led to a more cross‐linked structure inside the microgels resulting in their smaller swelling ratio. pH dependence of surface charge density of the microgels with amidino groups or carboxylic acid groups on their surfaces was evidenced by the variation of their zeta potentials as a function of pH.     

The Copolymerization of Alkenes with Maleic Anhydride

The investigations presented deal with the experimental results of the copolymerization of maleic anhydride (MAn) with alkenes. The course of the reaction is explained by the overall rate of the copolymerization (v _Br), which correlates with the solution viscosity of the copolymer, and the dependence of the v _Br maximum on the mole ratio of the monomers at constant total monomer concentration. The use of solvents with increasing donor power leads to increased complexing of the free MAn molecules and of the MAn radical chain ends. The results demonstrate that, for low 1-alkenes, the addition of the MAn chain radical is the rate-determining step of the copolymerization. As the substituents on the olefinic double bond become larger or the double bond shifts to the 1,2-position, the addition of MAn to the hydrocarbon radical becomes more and more the rate-determining step. On the other hand, an increase of the CT complexation of the MAn polymer radical by use of donor solvents decreases the alkene addition rate.     

Insights into the photophysics,protonation and Cu2+ ion coordination behaviour of anthracene-9,10-dione-based chemosensors

Carboxylic acid–diamine-based Cu²⁺ chromogenic sensors (3 and 4) exhibited colour switching from red to blue with good sensitivity and selectivity towards Cu²⁺ among other physiologically important alkali, alkaline earth and heavy metal ions. This colour-switching phenomenon arises due to selective deprotonation of aryl amine NH by Cu²⁺. Significantly, chemosensor 3 (λ_max 492 nm) shows multiple modes of complexation towards Cu²⁺. It is very much evident from the appearance of blue colour (λ_max 615 nm) at pH >7.0 and yellow colour (λ_max 465 nm) at pH < 4.0. In addition, chemosensor 3 exhibits a unique logic gate system that involves ‘INHIBIT’ and ‘TRANSFER’ logic gates.     

pH-Responsive Phase Transition of Supramolecular Hydrogel Consisting of Glycosylated Amino Acetate and Carboxylic Acid Derivative

By addition of a carboxylated amino acetate (2) to a low-molecular-weight hydrogel (1) which has a unique thermally induced volume-phase transition character, a macroscopic pH-responsive feature is newly conferred on the supramolecular hydrogel. The direct observation of temperature-dependent behavior of the mixed hydrogel clearly showed that the thermally induced swelling-shrinkage type of the volume phase transition at pH 4 is shifted to the gel–sol transition at pH 7 by 10?mol% addition of 2 to the hydrogel 1. On the basis of the measurements by TEM, SEM, XRD and FT-IR, it is conceivable that incorporation of the anionic carboxylate of 2 slightly disturbs the packing of the hydrogen bond belt of the mixed hydrogel. Such a slight disturbance greatly leads to the sol–gel transition by elevating temperature, instead of the volume-phase transition. Introduction of dynamic characteristics to supramolecular systems in a macroscopic level may extend the potential of these materials in various fields.     

Continuous Detection of pH‐responsive Drug Delivery System in Cells in situ by Confocal Laser Scanning Microscopy

Mesoporous silica nanoparticles (MSN) were coated by pH‐responsive polymer chitosan‐poly (methacrylic acid) (CS‐PMAA). This nano drug delivery system showed good application prospects and the polymer‐coated microspheres were promising site‐specific anticancer drug delivery carriers in biomedical field. A continuous detection of pH‐responsive drug delivery system in cells in situ, utilizing MSN/CS‐PMAA composite microspheres, was proposed. Two kinds of different cell lines, tumor cell line (Hela) and normal somatic cells (293T), were used to investigate the behaviours of the drug loaded system in the cells. Conclusions could be drawn from the fluorescent images obtained by confocal laser scanning microscopy (CLSM), modified drug‐loaded microspheres (MSN/CS‐PMAA) were ingested into cells more easily, the uptake of DOX@FITC‐MSN/CS‐PMAA by HeLa/293T cells were performed at pH 7.4/pH 6.8, DOX was released during the ingestion process, fluorescence intensity decreased with time because of efflux transport and photo‐bleaching. Fluoresence detection by flow cytometry was performed as comparison. The continuous fluorescent observation in situ could be widely used in the pH‐responsive releasing process of drug delivery system in the cells.     

Application of Different Zeolites for Improvement of the Characteristics of a pH‐FET Biosensor Based on Immobilized Urease

Different modifications of the zeolites Na⁺‐Beta and LTA were applied for improving the working characteristics of a urea biosensor. The bioselective membrane of the biosensor was based on urease and different zeolites co‐immobilized with bovine serum albumin on the surface of a pH‐FET. It was shown that the biosensors modified with the zeolites H⁺‐Beta30 and H⁺‐Beta50 are characterized by increased sensitivity to urea. The influence of the zeolite concentration on the sensitivity of the biosensors was studied. The optimal concentration of the zeolites H⁺‐Beta30 and H⁺‐Beta50 in the bioselective membrane was 15 %. Different variants of co‐immobilization of urease and zeolite H⁺‐Beta30 were studied and the optimal method was selected. Thus, a general conclusion is that the urea biosensor sensitivity can be improved using zeolite H⁺‐Beta30 for urease immobilization in the bioselective membrane.