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Poly(N-isopropylacrylamide) (PNIPA) and Poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPA-co-AA)) microgels loaded with 5-aminolevulinic acid (ALA) were prepared by the spray-drying method. The amount of drug loaded was 290 µg ALA/mg microgel for PNIPA and 244 µg ALA/mg microgel for P(NIPA-co-AA) microgels. Maximum in vitro drug release took place within 15-30 min for PNIPA and 1-1.5 h for P(NIPA-co-AA) microgels as a function of pH, at 37°C. Transdermal delivery from microgels showed permeation fluxes 10 times higher than the passive diffusion flux. The cytotoxicity of microgels synthesized in HeLa cells after the application of photodynamic therapy (PDT) was superior compared with the administration of ALA in solution alone. Finally, the use of these microgels as a delivery vehicle for ALA constitutes a system capable of enhancing its topical administration and PDT effectiveness.

In this work the synthesis of smart nanoparticles capable of respond to external stimulus (pH and temperature variations) is reported. To avoid post-polymerization modification, functionalized monomers able to respond to pH and temperature changes were and then polymerized. The synthesized monomers have the capability for coupling with folic acid which is the target molecule. For this reason their polymers can be used as targeted drug delivery systems. Smart polymeric nanoparticles were prepared by direct and inverse microemulsion polymerization of the synthesized monomers. The nanoparticles were charged with drugs and their release kinetic was studied.

This paper reports an FT-IR study of blends of poly(mono-n-alkyl itaconates) with poly(N,N-dimethylacrylamide) (PDMA) and poly(ethyloxazoline) (PEOX). Strong hydrogen bonding has been found, and both polybases have shown similar acceptor strengths. Derivative techniques show asymmetric profiles for the free carbonyl band of the polybases, resulting in shifted band locations. The extent of the interassociation has been estimated by spectral curve fitting of the polybase carbonyl band. The results show that the interaction degree in blends with PEOX does not depend on the length of the poly(monoalkyl itaconate) side group, while an inter-associating ability loss is observed in blends with PDMA as the side-group size of the polyacid increases. This different behavior is attributed to the greater interspacing between vicinal carbonyl groups in PEOX. This band shows conformational sensitivity and reflects the conformational changes that occur as the steric hindrances present in the medium (due to the bulky side groups of the polyacids) increase.

Abstract: For two variable chemical oscillators, a simple strategy is to combine autocatalysis with a term including a binomial Michaelian denominator (constant+concentration). This strategy is applied in this paper to the context of polymerization reactions. In order to achieve autocatalysis a kinetic scheme of the form is applied, where the dimeric form D is included. The Michaelian term can be obtained in different ways, for example: (i) a third compound Z flows through the system and eliminates the monomer, (ii) compound Z can be radical initiators, and (iii) compound Z, which eliminates monomer, can be a special conformation (adsorbent) of the polymer. Three mechanisms are developed using these Michaelian terms. After decreasing the number of variables to two, by assuming a non-significant variation of the others, and normalizing the kinetic equations with respect to a certain steady state, phase plane techniques are applied to prove the existence of a limit cycle in the three models. Both monomer concentration and propagator concentration in the three models (cases 2.1 and 2.2) or the concentration of the adsorbent polymers are taken as oscillating variables. [Copyright &y& Elsevier]

Abstract: A simple polymerization scheme has been studied introducing small modifications leading to a stable focus type steady state (with damped oscillations) or unstable focus type (which combined with a no return enclosure for phase trajectories will show cycle limit sustained oscillations). Two variables have been employed in this analysis: X∝ monomer, . Limit cycle oscillations requires the addition of autocatalysis with respect to the monomer, J+X→2X, and so does an “enzymatic” block assuming that . The combination of both collateral additions makes the steady state an unstable focus and allows a simple Poincaré–Bendixson proof for the existence of the limit cycle. [ABSTRACT FROM AUTHOR]

The article focuses on a study which examined the influence of copolymerization variables on the flocculation performance (FP) of highly concentrated cationic flocculants based on 80/20 weight percent [2-(acryloyloxy)ethyl]trimethylammoniumchloride/acrylamide in an inverse microemulsion. Using the measurement of the capillarity suction time (CST), the FP of the cationic polymers was analyzed. The action mechanisms of the generally accepted flocculation theory were noted.

A simple radical polymerization is proposed in this paper, with step-by-step chain growth (Ri + M → Ri+1), and termination by transfer to a third body (Ri + S → polymer) such as the solvent. It is assumed that, for a certain critical degree of polymerization n, the propagator Rn reacts with substrate H to produce a deactivator (V) of the first propagator (H + Rn → Rn + V; V + R1 → P1) R1. Assuming that monomer, M, and precursor concentrations are constant, and assuming that the deactivator reaches fast a steady state, the resulting kinetic equations are formally linear, but they admit, perturbations rj(t) of the steady-state concentrations of the propagators R1, R2, ..., Rn, which are periodic functions of time. Even more, they can be purely sinusoidal functions (which have been called “harmonic,” in analogy to the solutions of the well-known classical harmonic oscillator) with phase shift between perturbations rj(t) = Rj- (Rj)0 and rj+1(t) = Rj+1 - (Rj+1)0. Based on these periodic solutions and aiming to a model as simple as possible, a theoretical analysis is made, resulting in that the minimum value for n would be n = 3. Of course, these harmonic oscillations “driven by trimer” are equally found in the group of all the remaining propagators with polymerization degree higher than 3 (variable Y = ∑∞j=4 Rj). © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 507–511, 2009 [ABSTRACT FROM AUTHOR]

The influence of initiator concentration, specific flow rate of initiator addition (Qsp), initial copolymerization temperature (Ti), aqueous phase pH and total comonomer concentration (TCC) on flocculating performance of latex particles of acrylamide and [2- (acryloyloxy)ethyl]trimethylammonium chloride copolymers with a cationic charge density of 40%, obtained by inverse microemulsion copolymerization by using a surfactant blend of Arlacel 83 and Softanol 90 as emulsifier and Rolling M-245, a mixture of n-decane and n-tetradecane in about 40/60 weight ratio, as oil phase, has been studied for high TCC, ranging from 28 to 34.5% (w/w). Comonomer inverse microemulsion copolymerizations were carried out in the semicontinuous mode by adding continuously an aqueous solution of sodium metabisulfite as initiator into stirred inverse comonomer microemulsions. Initiator concentration has a strong influence on viscosity, viscometnc structunng degree (VSI) and average weight molar mass (Mw) of copolymers in the range from 5 to 25 g/L. Both viscosity and Mw decrease with increasing initiator concentration. Best flocculating performance is obtained from 10 to 20 g/L, values at which VSI shows a minimum. Under the experimental conditions used, Qsp (153 to 310 mL/h/kg of comonomer), T (25 to 35°C) and aqueous phase pH (2.5 to 4.5) have almost no influence on both viscosity and VSI and, hence, on flocculating performance. On the contrary, TCC has a slight influence on copolymer viscosity but a strong one on VSI which increases dramatically with TCC, being the worst flocculating performance obtained at the highest TCC studied (34.5% (w/w)). Flocculating performance results are explained in terms of copolymer structuring degree and collapsed state of copolymer chains inside latex particles as well as in terms of the composition drift with conversion. [ABSTRACT FROM AUTHOR]

The specific interactions in blends of poly(mono-n-alkyl itaconate)s with two tertiary polyamides, the (PDMA) and the poly(ethyloxazoline)(PEOX), were studied. Hydrogen bonding between carboxylic acid groups of poly(mono-alkyl itaconate)s and carbonyl groups of PDMA and PEOX was found. The interassociation extent was measured by spectral fitting of the Amide I band and reveals a loss of interassociating ability in blends with PDMA am the length of the size group of the poly(mono-n-alkyl itaconate) increases, while in blends with PEOX the interassociation degree remains constant for a given composition. This different behavior is attributed to the larger interspacing between vicinal carbonyl groups in PEOX. Spectral changes upon heating showed an increase of thermal stability of the polyacid in the blends, larger in blends with PDMA than PEOX. These changes are explained in terms of the hydrogen bonding and the rigidity of the system. Finally, the ratio of absortion coefficients for the Amide I band was obtained. [ABSTRACT FROM AUTHOR]