Vapochromic polyketone films based on aggregation‐induced enhanced emission

Aliphatic polyketone (PK) films physically mixed with moderate amounts (0.6 wt%) of 4,4′‐bis(2‐benzoxazolyl)stilbene (BBS) fluorophores were demonstrated to be sensitive to volatile organic compounds. Notably, BBS/PK blends were prepared by means of a continuous 1‐step extrusion process in a pilot‐scale twin screw extruder and compression molded followed by rapid quenching in liquid nitrogen to get thin films (thickness of 150 μm) containing molecularly dispersed blue emissive BBS fluorophores. The 0.6 wt% BBS/PK films demonstrated significant vapochromism when exposed to volatile organic compounds characterized by favorable interactions with the polymer matrix such as chloroform. Solvent absorption caused PK matrix plasticization, thus increasing BBS mobility and triggering the self‐associations of molecules into bluish green‐emissive excimers/aggregates thanks to the emersion of the typical band at 500 nm. This phenomenon preferentially involves the BBS/PK film layers close to the air‐contact surface without affecting the bulk characteristics of the PK matrix. The easy modulation of the luminescent properties of PK films by varying the supramolecular organization of BBS dispersed molecules by chemical perturbations, and the use of melt‐processing procedures suggests the use for the first time of aliphatic PK in the development of smart materials for sensing applications.     

Synthesis, characterization, DNA interaction and potential applications of gold nanoparticles functionalized with Acridine Orange fluorophores

Two new water-soluble gold nanoparticles (AO-TEG-Au and AO-PEG-Au NPs) are prepared and characterized. They are stabilized by thioalkylated oligoethylene glycols and functionalized with fluorescent Acridine Orange (AO) derivatives. Despite the different core sizes (11.8 and 3.9 nm respectively) and shell composition, they are both well dispersed and are stable in water, even if some self-aggregation is observed in the case of AO-TEG-Au NPs. However, AO-PEG-Au NPs show much lower emission efficiency with respect to AO-TEG-Au NPs. Spectrophotometric and spectrofluorometric experiments indicate that both types of nanoparticle are able to bind to calf thymus DNA, either by external binding or partial intercalation. Preliminary FACS flow cytometry tests seem to indicate that the AO-TEG-Au nanoparticle is able to cross the cell membrane where it is absorbed by Chinese hamster ovary (CHO) cells at the picomolar concentration level.     

Quality control of benserazide-levodopa and carbidopa-levodopa tablets by capillary zone electrophoresis

In modern practice, the treatment of Parkinson's disease and syndrome is carried out using pharmaceutical formulations containing a combination of levodopa and a decarboxylation inhibitor (carbidopa or benserazide). Two pharmaceutical formulations were quantified by capillary zone electrophoresis using two procedures which differed only in the kind of background electrolyte used. One procedure used a 25 mM phosphate buffer, pH 2.5, while the second one used a 25 mM borate buffer, pH 8.5. The electrophoretic analysis was carried out using an uncoated fused- silica capillary, a separation voltage of 20 kV with currents typically less than 60 microA, and spectrophotometric detection at 205 nm. Calibration curves were performed for levodopa (concentration range 1-100 microg/mL), for carbidopa and benserazide (1-50 microg/mL), and the plots of the peak area versus concentration were found to be linear with a correlation coefficient better than 0.9990. Satisfactory results were obtained when commercial tablets were analyzed in terms of accuracy (98-102%), repeatability (0.6-2.0%), and intermediate precision (1.1-2.6%).     

Julolidine-labelled fluorinated block copolymers for the development of two-layer films with highly sensitive vapochromic response

Fluorinated block copolymers composed of a polystyrene (S_x) first block and a polyacrylate second block carrying hydrophobic/lipophobic perfluorohexyl side chains (AF) were prepared by atom transfer radical polymerization (ATRP). Fluorescence emission properties were imparted to the copolymers by incorporation in the second block of a julolidine-based fluorescent molecular rotor (JCBF). The synthesized block copolymers were used as the fluorescent low-surface energy thin top-layer onto a polystyrene bottom-layer to produce novel two-layer film vapochromic sensors. Contact angle and X-ray photoelectron spectroscopy (XPS) measurements revealed that the two-layer film surfaces were hydrophobic and lipophobic at the same time and highly enriched in fluorine content as a result of the effective segregation of the perfluorinated tails to the polymer-air interface. The fluorescence intensity of the two-layer films decreased significantly when they were exposed to vapours of organic solvents, including tetrahydrofurane, chloroform, and trifluorotoluene. However, an AF content-dependent sensing behaviour was also observed, with the two-layer films containing the copolymer with the shorter fluorinated block giving a more rapid and almost quantitative decrease in fluorescence variation. Fluorescence emission of the films was also proved to vary with temperature. Both the vapochromic and thermochromic responses were reversible after successive solicitation cycles. The fluorescence variation of the two-layer films was much more marked than that of the corresponding PS/JCBF blend, thus providing a system potentially applicable as highly sensitive volatile organic compound (VOC) sensor, thanks to the active role of the fluorinated block in promoting the migration of the fluorophore to the outermost surface layers.     

Preparation and Optical Properties of New Metal/Macromolecule Architectures

Polymer nanocomposite films with unusual and anisotropic optical properties were obtained by the controlled in-situ generation of noble metal nanoparticles (NPs). Poly(vinyl alcohol) (PVA) and poly(ethylene-co-vinylalcohol) (EVAl) nanocomposites containing gold and silver NPs were efficiently produced by a photo-reduction or thermal process both operating directly in the solid state and resulted efficiently stabilized by the presence of polymer hydroxyl groups, which prevent particles agglomeration. Uniaxial drawing of the NPs/polymer composites promoted anisotropic packing of the embedded particles along the stretching direction of the film, resulting in a shift of the surface plasmon resonance well above 40 nm and thus producing a well-defined polarization-dependent colour change. Such nanostructured materials when are obtained in the form of thin films can be applied to several fields, from sensor to photonics (i.e., macromolecular strain sensor, linear absorbing polarizer).     

Computational Design,Synthesis, and Mechanochromic Properties of New Thiophene‐Based π‐Conjugated Chromophores

The possibility of exploiting supramolecular architectures for the preparation of innovative mechanochromic devices has been extended by designing novel thienyl‐substituted 1,4‐bis(ethynyl)benzene dyes, which are characterized by a conjugated, rigid, rodlike core structure. This new family of chromophores was synthesized according to a simple two‐step sequential cross‐coupling reaction, and the optical properties were investigated in solution and in a polymeric matrix. To tune the mechanochromic performances in smart polymer materials, a virtual screening was set up that was able to select a derivative with optimal spectral features. The effective combination of experimental and computational investigations allowed us to spot those homologues with already potential anisotropic and aggregachromic features and characterized by the best spectral properties and luminescent response. The best candidate was synthesized and dispersed into a polyethylene matrix, indeed achieving an “in silico designed” mechanochromic material. Besides the specific applications of this novel material, the integration of computational and experimental techniques reported here defines an efficient protocol that can be applied to make a selection among similar dye candidates, which constitute the essential responsive part of such supramolecular devices.     

HILIC LC‐MS for the determination of 2′‐C‐methyl‐cytidine‐triphosphate in rat liver

A very accurate and selective LC‐MS/MS method was developed and validated for the quantification of 2′‐C‐modified nucleoside triphosphate in liver tissue samples. An efficient pretreatment procedure of liver tissue samples was developed, using a fully automated SPE procedure with 96‐well SPE plate (weak anion exchange sorbent, 30 mg). Nucleotide hydrophilic interaction chromatography has been performed on an aminopropyl column (100 mm×2.0 mm, 3 μm) using a gradient mixture of ACN and ACN/water (5:95 v/v) with 20 mM ammonium acetate at pH 9.45 as mobile phase at 300 μL/min flow rate. The 2′‐C‐modified nucleoside triphosphate was detected in the negative ESI mode in multiple reaction monitoring (MRM) mode. Calibration curve was linear over the 0.05–50 μM concentration range. Satisfying results, confirming the high reliability of the established LC‐MS/MS method, were obtained for intraday precision (CV = 2.5–9.1%) and accuracy (92.6–94.8%) and interday precision (CV = 9.6–11.5%) and accuracy (94.4–102.4%) as well as for recovery (82.0–112.6%) and selectivity. The method has been successfully applied for pharmacokinetic studies of 2′‐C‐methyl‐cytidine‐triphosphate in liver tissue samples.     

Synthesis of tris-hydroxymethyl-based nitrone derivatives with highly reactive nitronyl carbon

A novel series of α-phenyl-N-tert-butyl nitrone derivatives, bearing a hydrophobic chain on the aromatic ring and three hydroxyl functions on the tert-butyl group, was synthesized through a short and convenient synthetic route based on a one-pot reduction/condensation of tris(hydroxymethyl)nitromethane with a benzaldehyde derivative. Because of the presence of hydroxyl functions on the tert-butyl group, an intramolecular Forrester-Hepburn reaction leading to the formation of an oxazolidine-N-oxyl compound was observed by electron paramagnetic resonance (EPR). The mechanism of cyclization was further studied by computational methods showing that intramolecular hydrogen bonding and high positive charge on the nitronyl carbon could facilitate the nucleophilic addition of a hydroxyl group onto the nitronyl carbon. At high nitrone concentrations, a second paramagnetic species, very likely formed by intermolecular nucleophilic addition of two nitrone molecules, was also observed but to a lesser extent. In addition, theoretical data confirmed that the intramolecular reaction is much more favored than the intermolecular one. These nitrones were also found to efficiently trap carbon-centered radicals, but complex spectra were observed due to the presence of oxazolidine-N-oxyl derivatives.     

New anion conducting membranes based on functionalized styrene–butadiene–styrene triblock copolymer for fuel cells applications

In this work, the functionalization of polystyrene‐b‐poly(butadiene)‐b‐polystyrene triblock copolymer (SBS) with vinylbenzyl chloride and benzoyl peroxide (BPO) or α,α′‐azo‐bis‐isobutyronitrile (AIBN) as free radical initiators was reported. The functionalization degree (FD), calculated by ¹H NMR spectroscopy and confirmed by elemental analysis, was highly tunable (from 4 to 10 mol %) and positively correlated to the starting percentage of radical initiator. More specifically, at the same initiator molar percentage grafting efficiency is higher using BPO rather than AIBN. Quaternization reaction of the grafted benzyl chloride groups with the bifunctional tertiary amine 1,4‐diazabicyclo[2.2.2]octane (Dabco) led to a chemically and thermally stable homogeneous anion‐exchange membrane. Electrochemical parameters were evaluated for Dabco‐quaternized grafted copolymers having different FDs, and compared with a commercial Tokuyama benchmark membrane. Experimental data showed a positive correlation between FD and both water swelling and ionic conductivity. Best trade‐off between ionic conductivity and water swelling was found for membrane having FD 9.1 mol %, which conductivity is comparable with the Tokuyama benchmark one and water uptake is only slightly higher. The results are discussed based on the molecular parameters with particular reference to ionic content and distribution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011