Comparative triad of routes to an alkyne-BF2 azadipyrromethene near-infrared fluorochrome

A series of three inter-related synthetic routes to a water soluble alkyne substituted BF₂-azadipyrromethene fluorochrome is described. Each route allows for the introduction of the required reactive alkynyl group and water solubilizing propane-sulfonic acid through either more advanced pyrrole intermediates or through their earlier synthetic precursors. The advantages and disadvantages of each route lie in the number of synthetic steps required versus the formation of undesired azadipyrromethene by-products. Upon its synthesis, the alkyne-bearing fluorochrome was shown to efficiently participate in CuACC reactions with a series of azido substrates in water at room temperature and 37?°C. NIR-photophysical properties of the fluorochrome and its conjugates were similar, showing strong potential for in vitro and in vivo imaging applications.     

Chromatin Regulates Genome Targeting with Cisplatin

Cisplatin derivatives can form various types of DNA lesions (DNA-Pt) and trigger pleiotropic DNA damage responses. Here, we report a strategy to visualize DNA-Pt with high resolution, taking advantage of a novel azide-containing derivative of cisplatin we named APPA, a cellular pre-extraction protocol and the labeling of DNA-Pt by means of click chemistry in cells. Our investigation revealed that pretreating cells with the histone deacetylase (HDAC) inhibitor SAHA led to detectable clusters of DNA-Pt that colocalized with the ubiquitin ligase RAD18 and the replication protein PCNA. Consistent with activation of translesion synthesis (TLS) under these conditions, SAHA and cisplatin cotreatment promoted focal accumulation of the low-fidelity polymerase Polη that also colocalized with PCNA. Remarkably, these cotreatments synergistically triggered mono-ubiquitination of PCNA and apoptosis in a RAD18-dependent manner. Our data provide evidence for a role of chromatin in regulating genome targeting with cisplatin derivatives and associated cellular responses.     

Interplay between solid state microstructure and photophysics for poly(9,9‐dioctylfluorene) within oriented polyethylene hosts

We present a study of isotropic and uniaxially oriented binary blend films comprising ≤1 wt % of the conjugated polymer poly(9,9‐dioctylfluorene) (PFO) dispersed in both ultra‐high molecular weight (UHMW) and linear‐low‐density (LLD) polyethylene (PE). Polarized absorption, fluorescence and Raman spectroscopy, scanning electron microscopy, and X‐ray diffraction are used to characterize the samples before and after tensile deformation. Results show that blend films can be prepared with PFO chains adopting a combination of several distinct molecular conformations, namely glassy, crystalline, and the so‐called β‐phase, which directly influences the resulting optical properties. Both PFO concentration and drawing temperature strongly affect the alignment of PFO chains during the tensile drawing of the blend films. In both PE hosts, crystallization of PFO takes place during drawing; the resulting ordered chains show optimal optical anisotropy. Our results clarify the PFO microstructure in oriented blends with PE and the processing conditions required for achieving the maximal optical anisotropy. © 2014 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 22–38     

Efficient synthesis of carbon nanotubes with improved surface area by low-temperature solvothermal route from dichlorobenzene

The synthesis of well-aggregated carbon nanotubes in the form of bundles was achieved by the catalytic reduction of 1,2-dichlorobenzene by a solvothermal approach. The use of 1,2-dichlorobenzene as a carbon source yielded a comparably good percentage of carbon nanotubes in the range of 60–70 %, at a low reaction temperature of 200°C. The products obtained were analysed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. The X-ray diffraction studies implied the presence of pure, crystalline, and well-ordered carbon nanotubes. The scanning electron and transmission electron microscopic images revealed the surface morphology, dimensions and the bundled form of the tubes. These micrographs showed the presence of multi-walled carbon nanotubes with an outer diameter of 30–55 nm, inner diameter of 15–30 nm, and lengths of several hundreds of nanometers. Brunauer-Emmett-Teller-based N₂ gas adsorption studies were performed to determine the surface area and pore volume of the carbon nanotubes. These carbon nanotubes exhibit a better surface area of 385.30 m² g^?1. In addition, the effects of heating temperature, heating time, amount of catalyst and amount of carbon source on the product yield were investigated.     

Hydro-amination/-amidation of 1,3-diynes with indoles/azoles/amides under modified Ullmann conditions: stereo- and regio-selective synthesis of N-alkenynes via N-H bond activation

An efficient strategy for the stereo- and regio-selective synthesis of N-alkenynes has been described. The salient feature of the reaction involves hydro-amination/amidation of 1,3-diynes with indoles/azoles/amides via transition-metal catalyzed activation of N-H bond. The resulting N-alkenynes derived from N-heterocycles and cyclic amides were obtained as a mixture of Z/E isomers with Z-stereoselectivity ranging from 60% to 95%. In contrast, acyclic amides afforded N-alkenynes with exclusive E-stereoselectivity, albeit in reduced yield ranging from ∼10% to 41%.     

Dynamic templating of colloidal patterns in three dimensions with nonuniform electric fields

Order-disorder transitions in colloidal systems are an attractive option for making switchable materials. Electric-field-driven order-disorder transitions are especially attractive for this purpose because the tuning parameter is easily and externally controllable. However, precise positional control of 3D structure is immensely challenging. Using patterned electrodes, we demonstrate that ac electric fields-dominantly dielectrophoresis (DEP) coupled with an electrohydrodynamic mechanism consisting of induced-charge electro-osmosis (ICEO)-can be used to template colloidal order dynamically in three dimensions. We find that the electric field geometry dictates the location, size, and shape of colloidal patterns and can produce patterns with surprising complexity.     

Polymer-bound 4-methylcoumarin/1-heptanoyl-5-fluorouracil photodimers: NMR elucidation of dimer structure

Heterodimers based on the polymer-bound chromophore 4-methylcoumarin and the prodrug 1-heptanoyl-5-fluorouracil, synthesized by photochemical [2 + 2]-cycloaddition are promising photoresponsive drug depots. Drug release experiments are one possibility to deliver proof of a successful reversible drug immobilization, whereas NMR spectroscopy is a potent tool for further structural characterization of these polymer-bound heterodimers. In case of the random copolymer poly(methyl methacrylate-co-7-(2'-methacryloyloxyethoxy)-4-methylcoumarin) three dimers have been identified of which the syn head-to-tail was the predominant one. In contrast, only the syn head-to-head dimer was formed in reasonable yield when the 4-methylcoumarin monofunctionalized pMMA was used as the base polymer. 1D and 2D NMR spectroscopic techniques combined with some theoretical calculations helped in successfully closing one major gap concerning polymer bound 4-methylcoumarin/1-heptanoyl-5-fluorouracil heterodimers that are of potential use in photoresponsive drug delivery devices.     

Polymer/bacteria composite nanofiber non-wovens by electrospinning of living bacteria protected by hydrogel microparticles

Physically crosslinked PVA-hydrogel microparticles are utilized for encapsulation of E. coli and M. luteus. The bacteria survive dry storage or treatment with bacteria-hostile organic solvents significantly better than unprotected bacteria as proven by culture-test experiments. The bacteria-protecting PVA microparticles are available for standard polymer-solution-processing techniques, as exemplarily shown by co-electrospinning of living bacteria encapsulated in dry PVA-hydrogel microparticles together with PVB-, PLLA-, and PCL-form organic solvents.     

Use of proton transfer reaction time-of-flight mass spectrometry for the analytical detection of illicit and controlled prescription drugs at room temperature via direct headspace sampling

The first reported use of proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) for the detection of a range of illicit and prescribed drugs is presented here. We describe the capabilities of PTR-TOF-MS to detect the following commonly used narcotics—ecstasy (N-methyl-3,4-methylenedioxyamphetamine), morphine, codeine, cocaine and heroin—by the direct sampling of the headspace above small solid quantities (approximately 50 mg) of the drugs placed in glass vials at room temperature, i.e. with no heating of the sample and no pre-concentration. We demonstrate in this paper the ability to identify the drugs, both illicit and prescribed, using PTR-TOF-MS through the accurate m/z assignment of the protonated parent molecule to the second decimal place. We have also included in this study measurements with an impure sample of heroin, containing typical substances found in “street” heroin, to illustrate the use of the technology for more “real-world” samples. Therefore, in a real-world complex chemical environment, a high level of confidence can be placed on the detection of drugs. Although the protonated parent is observed for all drugs, the reactant channel leading to this species is not the only one observed and neither is it necessarily the most dominant. Details on the observed fragmentation behaviour are discussed and compared to electrospray ionisation MSⁿ studies available in the literature.