RESUMEN
The reconstitution of the integral membrane protein photosynthetic reaction center (RC) in polymersomes, i.e. artificial closed vesicles, was achieved by the micelle-to-vesicle transition technique, a very mild protocol based on size exclusion chromatography often used to drive the incorporation of proteins contemporarily to liposome formation. An optimized protocol was used to successfully reconstitute the protein in a fully active state in polymersomes formed by the tri-block copolymers PMOXA22-PDMS61-PMOXA22. The RC is very sensitive to its solubilizing environment and was used to probe the positioning of the protein in the vesicles. According to charge-recombination experiments and to the enzymatic activity assay, the RC is found to accommodate in the PMOXA22 region of the polymersome, facing the water bulk solution, rather than in the PDMS61 transmembrane-like region. Furthermore, polymersomes were found to preserve protein integrity efficiently as the biomimetic lipid bilayers but show a much longer temporal stability than lipid based vesicles.
Asunto(s)
Membranas Artificiales , Proteínas del Complejo del Centro de Reacción Fotosintética/metabolismo , Polímeros/química , Interacciones Hidrofóbicas e Hidrofílicas , Cinética , Transporte de Proteínas , Rhodobacter sphaeroides/enzimologíaRESUMEN
Four thiolated oligoarylene molecules (i) 4-methoxy-terphenyl-4â³-methanethiol (MTM), (ii) 4-methoxy-terphenyl-3â³,5â³-dimethanethiol (MTD), (iii) 4-nitro-terphenyl-4â³-methanethiol (NTM), and (iv) 4-nitro-terphenyl-3â³,5â³-dimethanethiol (NTD) were synthesized and self-assembled as monolayers (SAMs) on polycrystalline Au electrodes of organic field-effect transistors (OFETs). SAMs were characterized by contact angle and AC/DC electrochemical measurements, whereas atomic force microscopy was used for imaging the pentacene films grown on the coated electrodes. The electrical properties of functionalized OFETs, the electrochemical SAMs features and the morphology of pentacene films were correlated to the molecular organization of the thiolated oligoarylenes on Au, as calculated by means of the density functional theory. This multi-methodological approach allows us to associate the systematic replacement of the SAM anchoring head group (viz. methanethiol and dimethanethiol) and/or terminal tail group (viz. nitro-, -NO2, and methoxy, -OCH3) with the change of the electrical features. The dimethanethiol head group endows SAMs with higher resistive features along with higher surface tensions compared with methanethiol. Furthermore, the different number of thiolated heads affects the kinetics of Au passivation as well as the pentacene morphology. On the other hand, the nitro group confers further distinctive properties, such as the positive shift of both threshold and critical voltages of OFETs with respect to the methoxy one. The latter experimental evidence arise from its electron-withdrawing capability, which has been verified by both DFT calculations and DC electrochemical measurements.
RESUMEN
This data article is related to our recently published research paper "Exploiting a new glycerol-based copolymer as a route to wound healing: synthesis, characterization and biocompatibility assessment", De Giglio et al. (Colloids and Surfaces B: Biointerfaces 136 (2015) 600-611) [1]. The latter described a new copolymer derived from glycerol and tartaric acid (PGT). Herein, an investigation about the PGT-ciprofloxacin (CIP) interactions by means of Fourier Transform Infrared Spectroscopy (FT-IR) acquired in Attenuated Total Reflectance (ATR) mode and Differential Scanning Calorimetry (DSC) was reported. Moreover, CIP release experiments on CIP-PGT patches were performed by High Performance Liquid Chromatography (HPLC) at different pH values.
RESUMEN
The use of biocompatible materials based on naturally derived monomers plays a key role in pharmaceutical and cosmetic industries. In this paper we describe the synthesis of a new low molecular weight copolymer, based on glycerol and l-tartaric acid, useful to develop biocompatible dermal patches with drug delivery properties. The copolymer's chemical composition was assessed by FT-IR (Fourier transform infrared spectroscopy), (1)H NMR ((1)H Nuclear Magnetic Resonance) and XPS (X-ray photoelectron spectroscopy), while its molecular weight distribution was estimated by SEC (size exclusion chromatography). Copolymer thermal properties were studied by TGA (thermogravimetric analysis). Biological evaluations by MTT assay and SEM (scanning electron microscopy) observations performed with murine fibroblasts and human keratinocytes (HaCaT) revealed a good compatibility of the proposed copolymer. Ciprofloxacin was selected as model drug and its release was evaluated by HPLC (high performance liquid chromatography), showing that the new copolymer supplied promising results as drug delivery system for wound healing applications. Furthermore, investigations on Skin-Mesenchymal stem cells (S-MSCs) behaviour and gene expression showed that the copolymer and its combination with ciprofloxacin did not affect their stemness. In this regard, the fabrication of dermal patches with new, low cost materials for local treatment of skin infections represents an attractive strategy in order to bypass the worrying side effects of systemic antibiotic therapy. Overall, the performed physico-chemical characterization, drug release test and biological evaluations showed that this new copolymer could be a promising tool for the in situ delivery of bioactive molecules during skin lesions treatment.
Asunto(s)
Materiales Biocompatibles , Glicerol/química , Polímeros/química , Cicatrización de Heridas , Animales , Línea Celular , Humanos , Ratones , Microscopía Electrónica de Rastreo , Espectroscopía de Protones por Resonancia MagnéticaRESUMEN
Poly(2,3,5,6-tetrafluoro-1,4-phenylenevinylene) (PTFPV) was prepared for the first time by the Stille cross-coupling reaction and the resulting material was characterized through MALDI-TOF mass spectrometry, employing a novel sample preparation protocol suitable for insoluble compounds; preliminary optical and electrooptical measurements were performed.
RESUMEN
A novel strategy for the synthesis of well-defined oligo(phenylenevinylene)s was developed. The procedure is entirely based upon two coupling processes, both involving vinyltrimethylsilanes. Bis(styryl)benzenes 2a-g bearing two octyloxy groups in the central aromatic ring and various substituents on the external aromatic rings were prepared in good yield by a regio- and stereoselective coupling reaction of 1 with different arenediazonium tetrafluoroborates. Oligomers with a more extended conjugated system, 4a-c, and with m-phenylene subunits 13a,b, were also readily obtained by conversion of the unsaturated trimethylsilyl derivatives 3a,c,d to the corresponding boron derivatives and a subsequent coupling reaction with compounds 2a and 2c.
RESUMEN
The third-order nonlinear optical properties of a series of copoly(2, 3, 5, 6-tetrafluoro-1, 4-phenylenevinylene-2, 5-dioctyloxy-1, 4-phenylenevinylene) that contain variable ratios of two differently substituted monomers have been studied in chloroform solutions at l=1064 nm by the picosecond Z-scan technique. Nonlinear refractive index n(2) of the samples investigated has been found to be negative, and a strong dependence of its magnitude on the copolymer's composition has been observed. The highest third-order nonlinear optical susceptibility, |x((3))|=(6 +/- 2)x 10(-10) esu, was measured for a copolymer obtained by reaction of equimolar quantitites of the parent monomers.