A Diselenide Turn-On Fluorescent Probe for the Detection of Thioredoxin Reductase

We report the first diselenide-based probe for the selective detection of thioredoxin reductase (TrxR), an enzyme commonly overexpressed in melanomas. The probe design involves conjugation of a seminaphthorhodafluor dye with a diselenide moiety. TrxR reduces the diselenide bond, triggering a fluorescence turn-on response of the probe. Kinetic studies reveal favorable binding of the probe with TrxR with a Michaelis–Menten constant (K_m) of 15.89 μm . Computational docking simulations predict a greater binding affinity to the TrxR active site in comparison to its disulfide analogue. In vitro imaging studies further confirmed the diselenide probe exhibited improved signaling of TrxR activity compared to the disulfide analogue.     

Synthesis, characterization, and single crystal X-ray diffraction studies of cis-Ph2C2H2(η5-C5H4)2Ca(THF)2

cis-[(1,2-diphenyl-1,2-dicyclopentadienyl)ethanediyl]bis(tetrahydrofuran)calcium is prepared by reductively coupling phenylfulvene with activated calcium to produce cis and trans isomers which can be separately crystallized. The cis isomer crystallizes in the monoclinic space group P2₁/c. The cell parameters are: a = 9.7006(1), b = 18.9839(1), c = 14.2018(2) Å, = 91.263(1)°, V = 2614.70(5) ų, D _calc = 1.252 mg/m³, and Z = 4. Spectroscopic and crystallographic data for the cis-isomer are presented and discussed.     

Single particle size and fluorescence spectra from emissions of burning materials in a tube furnace to simulate burn pits

A single-particle fluorescence spectrometer (SPFS) and an aerodynamic particle sizer were used to measure the fluorescence spectra and particle size distribution from the particulate emissions of 12 different burning materials in a tube furnace to simulate open-air burning of garbage. Although the particulate emissions are likely dominated by particles <1 μm diameter, only the spectra of supermicron particles were measured here. The overall fluorescence spectral profiles exhibit either one or two broad bands peaked around 300–450 nm within the 280–650 nm spectral range, when the particles are illuminated with a 263-nm laser. Different burning materials have different profiles, some of them (cigarette, hair, uniform, paper, and plastics) show small changes during the burning process, and while others (beef, bread, carrot, Styrofoam, and wood) show big variations, which initially exhibit a single UV peak (around 310–340 nm) and a long shoulder in visible, and then gradually evolve into a bimodal spectrum with another visible peak (around 430–450 nm) having increasing intensity during the burning process. These spectral profiles could mainly derive from polycyclic aromatic hydrocarbons with the combinations of tyrosine-like, tryptophan-like, and other humic-like substances. About 68 % of these single-particle fluorescence spectra can be grouped into 10 clustered spectral templates that are derived from the spectra of millions of atmospheric aerosol particles observed in three locations; while the others, particularly these bimodal spectra, do not fall into any of the 10 templates. Therefore, the spectra from particulate emissions of burning materials can be easily discriminated from that of common atmospheric aerosol particles. The SFFS technology could be a good tool for monitoring burning pit emissions and possibly for distinguishing them from atmospheric aerosol particles.     

Gas barrier properties of poly(ε‐caprolactone)/clay nanocomposites: Influence of the morphology and polymer/clay interactions

Poly(ε‐caprolactone)/montmorillonite nanocomposites were prepared maintaining a constant inorganic content with three means: melt blending of poly(ε‐caprolactone) with natural or organomodified clays, in situ polymerization of ε‐caprolactone in the presence of organomodified clays, and initiation of ε‐caprolactone polymerization from the silicate layer with appropriate organomodified montmorillonites and activator. In this last case, the polymer chains were grafted to the silicate layers and it was possible to tune up the grafting density. The presence of clays did not modify the polymer crystallinity. It was shown that the in situ polymerization process from the clay surface improved the clay dispersion. The gas barrier properties of the different composite systems were discussed both as a function of the clay dispersion and of the matrix/clay interactions. The highest barrier properties were obtained for an exfoliated morphology and the highest grafting density. Similar evolution of the permeability and the diffusion coefficients was observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 205–214, 2005     

Synchronizing vans and cargo bikes in a city distribution network

One of the significant side-effects of growing urbanization is the constantly increasing amount of freight transportation in cities. This is mainly performed by conventional vans and trucks and causes a variety of problems such as road congestion, noise nuisance and pollution. Yet delivering goods to residents is a necessity. Sustainable concepts of city distribution networks are one way of mitigating difficulties of freight services. In this paper we develop a two-echelon city distribution scheme with temporal and spatial synchronization between cargo bikes and vans. The resulting heuristic is based on a greedy randomized adaptive search procedure with path relinking. In our computational experiments we use artificial data as well as real-world data of the city of Vienna. Furthermore we compare three distribution policies. The results show the costs caused by temporal synchronization and can give companies decision-support in planning a sustainable city distribution concept.

     

Stabilizing Pentacene By Cyclopentannulation

A new class of stabilized pentacene derivatives with externally fused five‐membered rings are prepared by means of a key palladium‐catalyzed cyclopentannulation step. The target compounds are synthesized by chemical manipulation of a partially saturated 6,13‐dibromopentacene precursor that can be fully aromatized in a final step through a DDQ‐mediated dehydrogenation reaction (DDQ=2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone). The new 1,2,8,9‐tetraaryldicyclopenta[fg,qr]pentacene derivatives have narrow energy gaps of circa 1.2 eV and behave as strong electron acceptors with lowest unoccupied molecular orbital energies between ?3.81 and ?3.90 eV. Photodegradation studies reveal the new compounds are more photostable than 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene).     

Pressure-driven flow of wormlike micellar solutions in rectilinear microchannels

In this paper the inhomogeneous response of the (two species) VCM model (Vasquez et al., A network scission model for wormlike micellar solutions. I. Model formulation and homogeneous flow predictions, J. Non-Newtonian Fluid Mech. 144 (2007) 122–139) is examined in steady rectilinear pressure-driven flow through a planar channel. This microstructural network model incorporates elastically active network connections that break and reform mimicking the behavior of concentrated wormlike micellar solutions. The constitutive model, which includes non-local effects arising from Brownian motion and from the coupling between the stress and the microstructure (finite length worms), consists of a set of coupled nonlinear partial differential equations describing the two micellar species (a long species ‘A’ and a shorter species ‘B’) which relax due to reptative and Rouse-like mechanisms as well as rupture of the long micellar chains. In pressure-driven flow, the velocity profile predicted by the VCM model deviates from the regular parabolic profile expected for a Newtonian fluid and exhibits a complex spatial structure. An apparent slip layer develops near the wall as a consequence of the microstructural boundary conditions and the shear-induced diffusion and rupture of the micellar species. Above a critical pressure drop, the flow exhibits shear banding with a high shear rate band located near the channel walls. This pressure-driven shear banding transition or ‘spurt’ has been observed experimentally in macroscopic and microscopic channel flow experiments. The detailed structure of the shear banding profiles and the resulting flow curves predicted by the model depend on the magnitude of the dimensionless diffusion parameter. For small channel dimensions, the solutions exhibit ‘non-local’ effects that are consistent with very recent experiments in microfluidic geometries (Masselon et al., Influence of boundary conditions and confinement on non local effects in flows of wormlike micellar systems, Phys. Rev. E 81 (2010) 021502).