Recent advances of Pluronic-based copolymers functionalization in biomedical applications.

The design of polymeric biocompatible nanomaterials for biological and medical applications has received special attention in recent years. Among different polymers, the triblock type copolymers (EO)x(PO)y(EO)x or Pluronics® stand out due its favorable characteristics such as biocompatibility, low tissue adhesion, thermosensitivity, and structural capacity to produce different types of macro and nanostructures, e.g. micelles, vesicles, nanocapsules, nanospheres, and hydrogels. However, Pluronic itself is not the "magic bullet" and its functionalization via chemical synthesis following biologically oriented design rules is usually required aiming to improve its properties. Therefore, this paper presents some of the main publications on new methodologies for synthetic modifications and applications of Pluronic-based nanoconstructs in the biomedical field in the last 15 years. In general, the polymer modifications aim to improve physical-chemical properties related to the micellization process or physical entrapment of drug cargo, responsive stimuli, active targeting, thermosensitivity, gelling ability, and hydrogel formation. Among these applications, it can be highlighted the treatment of malignant neoplasms, infectious diseases, wound healing, cellular regeneration, and tissue engineering. Functionalized Pluronic has also been used for various purposes, including medical diagnosis, medical imaging, and even miniaturization, such as the creation of lab-on-a-chip devices. In this context, this review discusses the main scientific contributions to the designing, optimization, and improvement of covalently functionalized Pluronics aiming at new strategies focused on the multiple areas of the biomedical field.

Design and Optimization of Stimuli-responsive Emulsion-filled Gel for Topical Delivery of Copaiba Oil-resin.

This study presents a phytotherapeutic emulsion-filled gel design composed of Pluronic® F127, Carbopol® C934P, and high level of copaiba oil-resin (PHY-ECO). Mathematical modeling and response surface methodology (RSM) were employed to access the optimal ratio between the oil and the polymer gel-matrix constituents. The chemometric approach showed robust mechanical and thermoresponsive properties for emulsion gel. The model predicts viscosity parameters at 35.0°C (skin temperature) from PHY-ECOs. Optimized PHY-ECOs were described by 18-20% (w/w) F127, 0.25% (w/w) C934P, and 15% (w/w) copaiba oil-resin, and showed interfacial layers properties that led to high physicochemical stability. Besides, it had thermal stimuli-responsive that led large viscosity range before and after skin administration, observed by oscillatory rheology. These behaviors give the optimized smart PHY-ECO high design potential to be used as a pharmaceutical platform for CO delivery, focusing on the anti-inflammatory therapy and skin wound care.

Kinetic spectrophotometric method for real-time monitoring of ultraviolet photoreactions: A mini-photoreactor.

It is proposed a new approach to evaluate the performance of ultraviolet photoreactions by integrating UV-LED and a UV-Vis cuvette as a mini-reactor for kinetic monitoring in a spectrophotometer not influenced by external light. This system uses only 3.0 mL of solutions in a rectangular quartz cuvette with a mini-bar magnetic stirrer in a cell holder and a UV-LED of 5 W with λmax at 370 nm was positioned on the top of the cuvette and maintained at 25.0 oC. The effectiveness of this photoreactor was demonstrated by measuring the real-time degradation of two model compounds, salicylic acid and methylene blue, in homogeneous and heterogenous systems. Photolysis of MB with H2O2 results in increasing of rate constants as [H2O2] increased. Heterogeneous photocatalysis of MB and SA was fastest achieved in ZnO dosage of 0,20 g.L-1. This mini-photoreactor allows monitoring the real-time kinetic performance collecting almost a thousand points in each experiment, leading to accurate rate constants. Moreover, this system presented positive environmental aspects such as: lower reactants and catalyst amounts, lower cost and waste amounts, use of the UV-LED radiation and labor time saving. This is a novel approach to determine the photoreaction effectiveness and it can be applied to systematic studies especially for the kinetic parameter determinations.

Antibacterial photodynamic therapy for dental caries: evaluation of the photosensitizers used and light source properties.

Photodynamic therapy studies have shown promising results for inactivation of microorganisms related to dental caries. A large number of studies have used a variety of protocols, but few studies have analyzed photosensitizers and light source properties to obtain the best PDT dose response for dental caries. This study aims to discuss the photosensitizers and light source properties employed in PDT studies of dental caries. Three questions were formulated to discuss these aspects. The first involves the photosensitizer properties and their performance against Gram positive and Gram negative bacteria. The second discusses the use of light sources in accordance with the dye maximum absorbance to obtain optimal results. The third looks at the relevance of photosensitizer concentration, the possible formation of self-aggregates, and light source effectiveness. This review demonstrated that some groups of photosensitizers may be more effective against either Gram positive or negative bacteria, that the light source must be appropriate for dye maximum absorbance, and that some photosensitizers may have their absorbance modified with their concentration. For the best results of PDT against the main cariogenic bacteria (Streptococcus mutans), a variety of aspects should be taken into account, and among the analyzed photosensitizer, erythrosin seems to be the most appropriate since it acts against this Gram positive bacteria, has a hydrophilic tendency and even at low concentrations may have photodynamic effects. Considering erythrosin, the most appropriate light source should have a maximum emission intensity at a wavelength close to 530 nm, which may be achieved with low cost LEDs.

pKa determinations of xanthene derivates in aqueous solutions by multivariate analysis applied to UV-Vis spectrophotometric data.

Xanthenes form to an important class of dyes which are widely used. Most of them present three acid-base groups: two phenolic sites and one carboxylic site. Therefore, the pKa determination and the attribution of each group to the corresponding pKa value is a very important feature. Attempts to obtain reliable pKa through the potentiometry titration and the electronic absorption spectrophotometry using the first and second orders derivative failed. Due to the close pKa values allied to strong UV-Vis spectral overlap, multivariate analysis, a powerful chemometric method, is applied in this work. The determination was performed for eosin Y, erythrosin B, and bengal rose B, and also for other synthesized derivatives such as 2-(3,6-dihydroxy-9-acridinyl) benzoic acid, 2,4,5,7-tetranitrofluorescein, eosin methyl ester, and erythrosin methyl ester in water. These last two compounds (esters) permitted to attribute the pKa of the phenolic group, which is not easily recognizable for some investigated dyes. Besides the pKa determination, the chemometry allowed for estimating the electronic spectrum of some prevalent protolytic species and the substituents effects evaluation.