Stable Pyrrole‐Linked Bioconjugates through Tetrazine‐Triggered Azanorbornadiene Fragmentation

An azanorbornadiene bromovinyl sulfone reagent for cysteine‐selective bioconjugation has been developed. Subsequent reaction with dipyridyl tetrazine leads to bond cleavage and formation of a pyrrole‐linked conjugate. The latter involves ligation of the tetrazine to the azanorbornadiene‐tagged protein through inverse electron demand Diels–Alder cycloaddition with subsequent double retro‐Diels–Alder reactions to form a stable pyrrole linkage. The sequence of site‐selective bioconjugation followed by bioorthogonal bond cleavage was efficiently employed for the labelling of three different proteins. This method benefits from easy preparation of these reagents, selectivity for cysteine, and stability after reaction with a commercial tetrazine, which has potential for the routine preparation of protein conjugates for chemical biology studies.     

c(RGDfK)- and ZnTriMPyP-Bound Polymeric Nanocarriers for Tumor-Targeted Photodynamic Therapy

Active targeting strategies are currently being extensively investigated in order to enhance the selectivity of photodynamic therapy. The aim of the present research was to evaluate whether the external decoration of nanopolymeric carriers with targeting peptides could add more value to a photosensitizer formulation and increase antitumor therapeutic efficacy and selectivity. To this end, we assessed PLGA-PLA-PEG nanoparticles (NPs) covalently attached to a hydrophilic photosensitizer 5-[4-azidophenyl]-10,15,20-tri-(N-methyl-4-pyridinium)porphyrinato zinc (II) trichloride (ZnTriMPyP) and also to c(RGDfK) peptides, in order to target α_vβ₃ integrin-expressing cells. In vitro phototoxicity investigations showed that the ZnTriMPyP-PLGA-PLA-PEG-c(RGDfK) nanosystem is effective at submicromolar concentrations, is devoid of dark toxicity, successfully targets α_vβ₃ integrin-expressing cells and is 10-fold more potent than related nanosystems where the PS is occluded instead of covalently bound.     

Noether symmetry for Gauss–Bonnet dilatonic gravity

Noether symmetry for Gauss–Bonnet Dilatonic interaction exists for a constant dilatonic scalar potential and a linear functional dependence of the coupling parameter on the scalar field. The symmetry with the same form of the potential and coupling parameter exists all in the vacuum, radiation and matter dominated era. The late time acceleration is driven by the effective cosmological constant rather than the Gauss–Bonnet term, while the later compensates for the large value of the effective cosmological constant giving a plausible answer to the well-known coincidence problem.     

On the Rate of Explosion for Infinite Energy Solutions of the Spatially Homogeneous Boltzmann Equation

Let μ ₀ be a probability measure on ℝ³ representing an initial velocity distribution for the spatially homogeneous Boltzmann equation for pseudo Maxwellian molecules. As long as the initial energy is finite, the solution μ _t will tend to a Maxwellian limit. We show here that if , then instead, all of the mass “explodes to infinity” at a rate governed by the tail behavior of μ ₀. Specifically, for L0, define

Water and polymer dynamics in chemically cross-linked hydrogels of poly(vinyl alcohol): a molecular dynamics simulation study

A topologically extended model of a chemically cross-linked hydrogel of poly(vinyl alcohol) (PVA) at high hydration degree has been developed for a molecular dynamics simulation with atomic detail at 323 K. The analysis of the 5 ns trajectory discloses structural and dynamic aspects of polymer solvation and elucidates the water hydrogen bonding and diffusion in the network. The features of local polymer dynamics indicate that PVA mobility is not affected by structural constraints of chemical junctions at the investigated cross-linking density, with a prevailing dumping effect due to water interaction. Simulation results are validated by a favorable comparison with findings of an incoherent quasi-elastic neutron scattering study of the same hydrogel system.     

Determination of UV filters and antimicrobial agents in environmental water samples

Although there is increasing concern about residues from personal care products entering the aquatic environment and their potential to accumulate to levels that pose a health threat to humans and wildlife, we still know little about the extent and magnitude of their presence in the aquatic environment. In this study we describe a procedure for isolation, and subsequent determination, of compounds commonly added to personal care products. The compounds of interest include UV filters with the commercial name Eusolex (homosalate, 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate) and two common anti-microbial agents, clorophene and triclosan. Water samples were filtered, acidified, and extracted by use of solid-phase extraction. Extracted compounds were then derivatised before analysis by gas chromatography–mass spectroscopy. By use of our method we obtained limits of detection of 13–266 ng L⁻¹ for UV filters, and 10–186 ng L⁻¹ for triclosan and clorophene. Recoveries were 82–98% for deionised water and 50–98% for natural water (seawater, pool water, lake water, and river water). Samples collected in Slovenia included seventeen recreational waters (seawater, pool water, lake water, and river water; August 2004) and four wastewaters (January 2005). The most abundant UV filter was benzophenone-3 (11–400 ng L⁻¹). Of the two anti-microbial agents studied, trace amounts, only, of triclosan were present in the river Kolpa (68 ng L⁻¹) and in an hospital effluent (122 ng L⁻¹).     

The Second Appell Function for one Large Variable

We consider the Mellin convolution integral representation of the second Appell function given in [8]. Then, we apply the asymptotic method designed in [12] for this kind of integrals to derive new asymptotic expansions of the Appell function F ₂ for one large variable in terms of hypergeometric functions. For certain values of the parameters, some of these expansions involve logarithmic terms in the asymptotic variables. The accuracy of the approximations is illustrated with numerical experiments.