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.     

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).     

Fracture surface characteristics of unfilled thermosets

Many of the features that cause the great complexity of the fracture surfaces of thermosets are suggested to have a simple explanation. These features include the “basic longitudinal texture,” “steps,” “welts,” “arrays of skewed cracks,” and the “stacked lamellar texture.” The explanation for their occurrence is based on the hypothesis of an instability of the propagating crack front that produces a “fingering” ahead of the crack.     

2-adic complexity of SLCE sequence

Aiming at the 2-adic complexity of Sidelnikov-Lempel-Cohn-Eastman sequences,autocorrelation function value of this kind of sequence was obtained by using the cyclotomic number.Based on the relationship between 2-adic complexity and autocorrelation function,properties of 2-adic complexity value were analyzed.According to the greatest common divisor between the autocorrelation function value and the period of SLCE sequence,the condition that the 2-adic complexity of a SLCE sequence reaches its maximum value was given.The results show that 2-adic complexity of SLCE sequence on many finite field can reach the maximum value.     

Temperature influence on the behavior of polysulfone‐b‐poly(alkylene oxide)‐b‐poly(dimethylsiloxane) triblock copolymers in a selective solvent

Triblock copolymers containing polysulfone, poly(alkylene oxide), and poly(dimethylsiloxane) segments were obtained by addition of preformed α,ω‐bis(hydrogensilyl) poly(dimethylsiloxane) oligomers to alyl end‐capped poly(alkylene oxide)‐b‐polysulfone. Viscometric and UV absorption measurements were carried out in dilute 1,2‐dichlorethane solutions, in the temperature range of 20–75°C. The specific interactions exhibited by the block copolymers in a selective solvent are influenced by the copolymer composition and temperature. The results point to a conformational transition phenomenon, located around 55°C, which is attributed to the transition from a segregated to a pseudo‐Gaussian conformation through a compressed‐segregated conformation. POLYM. ENG. SCI., 57:114–118, 2017. © 2016 Society of Plastics Engineers     

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.