Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single-(ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles are presented, using counter-ion structure and DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Performance of polymeric reinforcements in vehicle structures submitted to frontal impact

Preformed structural reinforcements have shown good performance in crash tests, where the great advantage is their weight. These reinforcements are designed with the aim of increasing the rigidity of regions with large deformations, thus stabilising sections of the vehicle that work as load path during impact. The objective of this work is to show the application of structural reinforcements made of polymeric material PA66 in the field of vehicle safety, through finite element simulations. Simulations of frontal impact at 50 km/h and in ODB (offset deformable barrier) at 57 km/h configurations (standards such as ECE R-94 and ECE R-12) were performed in the software LS-DYNA R (R) and MADYMO (R). The simulations showed that the use of polymeric reinforcements leads to a 70% reduction in A-pillar intrusion, a 65% reduction in the displacement of the steering column and a 59% reduction in the deformation in the region of the occupant legs and feet. The level of occupant injuries was analysed by MADYMO (R) software, and a reduction of 23.5% in the chest compression and 80% in the tibia compression were verified. According to the standard, such conditions lead to an improvement in the occupant safety in a vehicle collision event.

Femtosecond Laser in Polymeric Materials: Microfabrication of Doped Structures and Micromachining

The use of laser light to modify the material's surface or bulk as well as to induce changes in the volume through a chemical reaction has received great attention in the last few years, due to the possibility of tailoring the material's properties aiming at technological applications. Here, we report on recent progress of microstructuring and microfabrication in polymeric materials by using femtosecond lasers. In the first part, we describe how polymeric materials' micromachining, either on the surface or bulk, can be employed to change their optical and chemical properties promising for fabricating waveguides, resonators, and self-cleaning surfaces. In the second part, we discuss how two-photon absorption polymerization can be used to fabricate active microstructures by doping the basic resin with molecules presenting biological and optical properties of interest. Such microstructures can be used to fabricate devices with applications in optics, such as microLED, waveguides, and also in medicine, such as scaffolds for tissue growth.

Polymeric Nanoparticles as Oral Delivery Systems for Encapsulation and Release of Polyphenolic Compounds: Impact on Quercetin Antioxidant Activity & Bioaccessibility

A delivery system containing polymeric (Eudragit) nanoparticles has been developed for encapsulation and controlled release of bioactive flavonoids (quercetin). Nanoparticles were fabricated using a solvent displacement method. Particle size, morphology, and charge were measured by light scattering, electron microscopy and zeta-potential. Encapsulation efficiency (EE) and release profiles were determined using electrochemical methods. Molecular interactions within the particle matrix were characterized by X-ray diffraction, differential scanning calorimetry, and infrared spectroscopy. Antioxidant properties of free and encapsulated quercetin were analyzed by TBARS and fluorescence spectroscopy. Bioaccessibility of quercetin was evaluated using an in vitro digestion model. Relatively small (d a parts per thousand aEuro parts per thousand 370 nm) anionic polymeric nanoparticles were formed containing quercetin in a non-crystalline form (EE a parts per thousand aEuro parts per thousand 67 %). The main interaction between quercetin and Eudragit was hydrogen bonding. Encapsulated quercetin remained stable during 6 months storage and maintained its antioxidant activity. Quercetin bioaccessibility within simulated small intestinal conditions was improved by encapsulation. The knowledge obtained from this study will facilitate the rational design and fabrication of polymeric nanoparticles as oral delivery systems for encapsulation, protection, and release of bioactive compounds.

Microbial characterization and removal of anionic surfactant in an expanded granular sludge bed reactor

This study evaluated linear alkylbenzene sulfonate removal in an expanded granular sludge bed reactor with hydraulic retention times of 26 h and 32 h. Sludge bed and separator phase biomass were phylogenetically characterized (sequencing 16S rRNA) and quantified (most probable number) to determine the total anaerobic bacteria and methanogenic Archaea. The reactor was fed with a mineral medium supplemented with 14 mg l(-1) LAS, ethanol and methanol. The stage I-32 h consisted of biomass adaptation (without LAS influent) until reactor stability was achieved (COD removal >97%). In stage II-32 h, LAS removal was 74% due to factors such as dilution, degradation and adsorption. Higher HRT values increased the LAS removal (stage III: 26 h - 48% and stage IV: 32 h - 64%), probably due to increased contact time between the biomass and LAS. The clone libraries were different between samples from the sludge bed (Synergitetes and Proteobacteria) and the separator phase (Firmicutes and Proteobacteria) biomass. (C) 2011 Elsevier Ltd. All rights reserved.

Crystal structure and spectroscopic properties of polymeric adducts of the tetra-mu-haloaspirinate-dicopper(II)

Eight new copper(II) complexes with halo-aspirinate anions have been synthesized: [Cu-2(Fasp)(4)(MeCN)(2)] center dot 2MeCN (1), [Cu-2(Clasp)(4)(MeCN)(2)]center dot 2MeCN (2), [Cu-2(Brasp)(4) (MeCn)(2)] center dot 2MeCn (3), {[Cu-2(Fasp)(4)(Pyrz)] center dot 2MeCN}(n) (4) {[Cu-2(Clasp)(4)(Pyrz)] center dot 2MeCN}(n) (5), [Cu-2(Brasp)(4)(Pyrz)](n) (6), [Cu-2(Clasp)(4)(4,4'-Bipy)](n) (7), and [Cu-2(Brasp)(4)(4,4'-Bipy)](n) (8) (Fasp: fluor-aspirinate; Clasp: chloro-aspirinate; Brasp: bromo-aspirinate; MeCN: acetonitrile; Pyrz: pyrazine; 4,4'-Bipy: 4,4'-bipyridine). The crystal structure of two 2 and 4 have been determined by X-ray diffraction methods. All compounds have been studied employing elemental analysis, IR, and UV-Visible spectroscopic techniques. The results have been compared with previous data reported for complexes with similar structures.

Photophysical properties and interactions of xanthene dyes in aqueous micelles

Photosensitizers (PS) photodynamic activities are regulated by their location in the biological target, which modulates their photophysical and photochemical features. In this work the PS partition for the Xanthene Dyes Fluorescein (FSC), Eosin Y(EOS), Erythrosin B (ERY) and Rose Bengal B (RBB) in biomimetic models (SDS, CTAB and Pluronic P-123 micelles) and the effects on their photophysical characteristics are evaluated. The hydrophobic and electrostatic forces that govern the PS-micelle interaction are analyzed. At physiological pH (7.25), the ability of the dianionic protolytic form of the dyes to be positioned into the micelle palisade and its micelle interaction depends not only on the hydrophobicity of the dye but also on the micellar surface charge. The Binding Constants obey exactly the same order of the Partition Coefficients for the dyes in P-123 and CTAB micelles. The Stern-Volmer treatment pointed out that dyes are located inside the micelle, especially ERY and RBB. The magnitude of the dye-micelle interaction increased from SDS, P-123 and finally CTAB micelles due to the charges between dye and micelle, and among the xanthenes, their hydrophobic characteristics. Within the micelle pseudo phase, ERY and RBB are still very efficient photosensitizers exhibiting high quantum yield of singlet oxygen, which turns them very attractive especially with P-123 polymeric system as drug delivery systems in photodynamic therapy. (C) 2012 Elsevier B.V. All rights reserved.

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

In this communication, we investigate the effect of different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP-K40) on the growth process of zinc molybdate (beta-ZnMoO4) microcrystals synthesized under hydrothermal conditions at 140 degrees C for 8 h. These microcrystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) measurements. XRD patterns proved that these crystals are monophasic and present a wolframite-type monoclinic structure. FE-SEM images revealed that the surfactants modified the crystal shapes, suggesting the occurrence of distinct crystal growth processes. The CTAB cationic surfactant promotes the hindrance of small nuclei that leads to the formation of rectangle-like crystals, SDS anionic surfactant induces a growth of irregular hexagons with several porous due to considerable size effect of counter-ions on the crystal facets, PVP-K40 non-ionic surfactant allows a reduction in size and thickness of plate-like crystals, while without surfactants have the formation of irregular plate-like crystals. Finally, the PL properties of beta-ZnMoO4 microcrystals were explained by means of different shape/size, surface defects and order-disorder into lattice. (C) 2011 Elsevier B.V. All rights reserved.

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 degrees C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 C for 2 h. The degree of structural order disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Derivative spectrophotometric method for determination of acyclovir in polymeric nanoparticles

A derivative spectrophotometric method was validated for quantification of acyclovir in poly (n-butylcyanoacrylate) (PBCA) nanoparticles. Specificity, linearity, precision, accuracy, recovery, detection (LOD) and quantification (LOQ) limits were established for method validation. First-derivative at 295.2 nm eliminated interferences from nanoparticle ingredients and presented linearity for acyclovir concentrations ranging from 1.25 to 40.0 µg/mL (r = 0.9999). Precision and accuracy data demonstrated good reproducibility. Recovery ranged from 99.3 to 101.2. LOD was 0.08 µg/mL and LOQ, 0.25 µg/mL. Thus, the proposed method proved to be easy, low cost, and accurate, and therefore, an useful alternative to quantify acyclovir in nanoparticles.

Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Study of an anisotropic polymeric cellular material under compression loading

This paper emphasizes the influence of micro mechanisms of failure of a cellular material on its phenomenological response. Most of the applications of cellular materials comprise a compression loading. Thus, the study focuses on the influence of the anisotropy in the mechanical behavior of cellular material under cyclic compression loadings. For this study, a Digital Image Correlation (DIC) technique (named Correli) was applied, as well as SEM (Scanning Electron Microscopy) images were analyzed. The experimental results are discussed in detail for a closed-cell rigid poly (vinyl chloride) (PVC) foam, showing stress-strain curves in different directions and why the material can be assumed as transversely isotropic. Besides, the present paper shows elastic and plastic Poisson's ratios measured in different planes, explaining why the plastic Poisson's ratios approach to zero. Yield fronts created by the compression loadings in different directions and the influence of spring-back phenomenon on hardening curves are commented, also.

Polymeric micelles and molecular modeling applied to the development of radiopharmaceuticals

Micelles composed of amphiphilic copolymers linked to a radioactive element are used in nuclear medicine predominantly as a diagnostic application. A relevant advantage of polymeric micelles in aqueous solution is their resulting particle size, which can vary from 10 to 100 nm in diameter. In this review, polymeric micelles labeled with radioisotopes including technetium (99mTc) and indium (111In), and their clinical applications for several diagnostic techniques, such as single photon emission computed tomography (SPECT), gamma-scintigraphy, and nuclear magnetic resonance (NMR), were discussed. Also, micelle use primarily for the diagnosis of lymphatic ducts and sentinel lymph nodes received special attention. Notably, the employment of these diagnostic techniques can be considered a significant tool for functionally exploring body systems as well as investigating molecular pathways involved in the disease process. The use of molecular modeling methodologies and computer-aided drug design strategies can also yield valuable information for the rational design and development of novel radiopharmaceuticals.

Speckle patterns during the spreading of lung surfactant.

Pulmonary surfactant is a very important product in the medical treatment of the syndrome of insufficiency respiratory in neonates. The synthesis of this surfactant in labs need to optimize the rate of spreading in the alveolar interstitial liquid obtaining a monolayer of the phospholipids membrane base capable to maintains several of the dynamical properties of the respiratory system during breathing. The recover of theses mechanical properties has to be archived using the minimal quantities of product and with the optimal proteins composition (SP-B in special). In this paper we show our results of obtaining and process speckle pattern images of the spreading of phospholipids membrane composed the matrix of this product (DPPC) when physiologic interstitial liquid are presented.

Investigation of the interaction of alkali ions with surfactant head groups for the formation of lyotropic biaxial nematic phase via optical birefringence measurements.

Lyotropic liquid crystals exhibiting nematic phases were obtained from the mixtures potassium laurate/alkali sulfate salts (M2SO4)/1-undecanol (UndeOH)/water and sodium dodecyl sulfate (SDS)/M2SO4/1-dodecanol (DDeOH)/water, where M2SO4 represents the alkali sulfate salts being Li2SO4, Na2SO4, K2SO4, Rb2SO4 or Cs2SO4. The birefringences measurements were performed via laser conoscopy. Our results indicated that cosmotropic and chaotropic behaviors of both ions and head groups are very important to obtain lyotropic biaxial nematic phase. To obtain the biaxial nematic phase, surfactant head group and ion present in lyotropic mixture have relatively opposite behavior, e.g. one more cosmotropic (more chaotropic) other less cosmotropic (less chaotropic) or vice versa.