Metabolic Profiling of VOCs Emitted by Bacteria Isolated from Pressure Ulcers and Treated with Different Concentrations of Bio-AgNPs

Considering the advent of antibiotic resistance, the study of bacterial metabolic behavior stimulated by novel antimicrobial agents becomes a relevant tool to elucidate involved adaptive pathways. Profiling of volatile metabolites was performed to monitor alterations of bacterial metabolism induced by biosynthesized silver nanoparticles (bio-AgNPs). Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae and Proteus mirabilis were isolated from pressure ulcers, and their cultures were prepared in the presence/absence of bio-AgNPs at 12.5, 25 and 50 µg mL⁻¹. Headspace solid phase microextraction associated to gas chromatography–mass spectrometry was the employed analytical platform. At the lower concentration level, the agent promoted positive modulation of products of fermentation routes and bioactive volatiles, indicating an attempt of bacteria to adapt to an ongoing suppression of cellular respiration. Augmented response of aldehydes and other possible products of lipid oxidative cleavage was noticed for increasing levels of bio-AgNPs. The greatest concentration of agent caused a reduction of 44 to 80% in the variety of compounds found in the control samples. Pathway analysis indicated overall inhibition of amino acids and fatty acids routes. The present assessment may provide a deeper understanding of molecular mechanisms of bio-AgNPs and how the metabolic response of bacteria is untangled.     

Retention of gallium ions from acidic solutions by pyridine strong‐base anion exchangers

Using the batch method, the retention of Ga(III) from HCl solutions by two gel‐type pyridine strong‐base anion exchangers containing 1‐methyl‐ or 1‐butyl‐4‐vinylpyridinium chloride structural units, called S₁ and S₂ resins, respectively, was studied. The influence of the HCl and Ga(III) concentrations as well as of the contact time between the resin and the liquid phase was investigated. The parameters, which characterize the retention process, were estimated using Langmuir and Freundlich isotherms. Both resins exhibited a higher affinity for gallium ions from a 6M HCl solution. According to Langmuir isotherms, maximum retention capacities of 44.44 and 60 mg Ga(III)/g dry resin for the S₁ and S₂ resins, respectively, were obtained. Freundlich isotherms provide additional proof for a higher affinity of the S₂ resin for Ga(III) from HCl solutions. It is clear that the substituent length increase on N⁺ atoms led to an increasing affinity of the pyridine strong base anion exchangers toward Ga(III). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3440–3444, 2002     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

Polyimides containing 4,4′‐bipyridinium units

New polyimides containing 4,4′‐bipyridinium units were synthesized by the reaction of bis(dichloromaleimide)arylene derivatives with 4,4′‐bipyridine in meta‐cresol. IR and ¹H‐NMR spectroscopy and elemental analysis as well confirmed their structures. The polymers were characterized by viscometric measurements, softening points, and thermogravimetric data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2091–2100, 2004     

The stacked lamellar texture on the fracture surfaces of fibre composites

A fracture surface texture, which has been variously termed as lacerations, hackles or serrations, is often observed on the matrix surface of fibre composites, most often in resin-rich regions. This texture, referred to here as a stacked lamellar texture to emphasize its plate-like nature, was studied in an E-glass/epoxy composite. Scanning electron fractographs of these materials suggest that the stacked lamellar texture arises from crack fingers due to a meniscus instability mechanism interacting with a reorienting stress field.     

Synthesis of poly(urethane-urea) varnish bearing azobenzene chromophoric pendants

A new diol with azoaromatic pendant was prepared by N-phenyl-4-amido-3,4-dichloromaleimide with 2-mercaptoethanol in the presence of NaOH, and used to obtain photosensible poly(urethane-urea) varnish. A poly(urethane-urea) varnish bearing azobenzene chromophores, based on a poly(ethylene adipate)diol (average molecular weight—2000), 4,4′-dibenzyldiisocyanate, diethylene glycol, trimethylolpropane, and afore-mentioned diol, were prepared and characterized. The polymers were characterized by FTIR spectroscopy, thermal analysis (DMA, DSC, and TGA), and the photochromic behavior by UV irradiation of thin films was discussed.     

Contactless Spin Switch Sensing by Chemo-Electric Gating of Graphene

Direct electrical probing of molecular materials is often impaired by their insulating nature. Here, graphene is interfaced with single crystals of a molecular spin crossover complex, [Fe(bapbpy)(NCS)₂], to electrically detect phase transitions in the molecular crystal through the variation of graphene resistance. Contactless sensing is achieved by separating the crystal from graphene with an insulating polymer spacer. Next to mechanical effects, which influence the conductivity of the graphene sheet but can be minimized by using a thicker spacer, a Dirac point shift in graphene is observed experimentally upon spin crossover. As confirmed by computational modeling, this Dirac point shift is due to the phase-dependent electrostatic potential generated by the crystal inside the graphene sheet. This effect, named as chemo-electric gating, suggests that molecular materials may serve as substrates for designing graphene-based electronic devices. Chemo-electric gating, thus, opens up new possibilities to electrically probe chemical and physical processes in molecular materials in a contactless fashion, from a large distance, which can enhance their use in technological applications, for example, as sensors.     

Polyimides with 3,3’-Bipyrrolidine-2,2’,5,5’-Tetrone Units

Summary New linear polymers with 3,3’-bipyrrolidine-2,2’,5,5’-tetrone units were prepared by the ring-coupling reaction of α,α’-bis(chlorosuccinimide)s under the action of dust zinc and iodine. Bis(α-chlorosuccinimide)s were synthesized by the dehydrocyclization of the bismaleamic acids in the presence of thionyl chloride. The IR, ¹H-NMR and ¹³C-NMR spectroscopy and elemental analysis confirmed the structure of monomers and polymers. The thermal behaviour of the polymers was monitored using dynamic thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Chemical modification of chloromethylated polysulfones via click reactions

A new approach to the modification of azidomethyl polyethersulfones using click reactions with acetylenic derivatives in the presence of CuBr as catalyst is presented. An azidomethyl polyethersulfone was prepared by the reaction of chloromethylated polysulfone with sodium azide in dimethylformamide. By the Cu(I)‐catalysed Huisgen 1,3‐dipolar cycloaddition reaction of the azidomethyl polyethersulfone to acetylenic derivatives, new polyethersulfones containing 1,2,3‐triazole rings were obtained. The structures of the polymers were confirmed using attenuated total reflectance Fourier transform infrared and NMR spectroscopy. The polymers were characterized using dynamic mechanical analysis, thermogravimetric analysis, stress‐strain and water contact angle measurements and solubility tests. The polymers bearing 1,2,3‐triazole rings having OH or COOH as substituents exhibited static contact angles smaller than that of the parent polyethersulfone. Copyright © 2010 Society of Chemical Industry