Eisen und Stab

Ohne Zusammenfassung     

Enzymatic‐ and light‐degradable hybrid nanogels: Crosslinking of polyacrylamide with acrylate‐functionalized Dextrans containing photocleavable linkers

Enzymatically cleavable and light‐degradable hybrid nanogels were prepared by free radical inverse miniemulsion copolymerization of acrylamide (AAm) with a newly synthesized functional dextran crosslinker containing acrylate moieties attached to the backbone via a photolabile linker, that is, dextran‐photolabile linker‐acrylate (Dex‐PL‐A). The Dex‐PL‐A/AAm feed ratio was systematically varied to investigate the influence of the particle composition on the gel properties. The resulting hydrogel nanoparticles were examined with regard to their degradation behavior upon the appliance of the two orthogonal stimuli by turbidity measurements in combination with dynamic light scattering. Although continuous photolytic cleavage of the photolabile linkers between polyacrylamide chains and dextran molecules was found to proceed fast and quantitatively yielding completely disintegrated networks, stepwise irradiation resulted in partial degradation of crosslinking points. Thus, nanogels of a desired specific degree of swelling (DGS) can be obtained by adjusting the irradiation time accordingly. Partial enzymatic cleavage of the dextran backbones of the Dex‐PL‐A crosslinking molecules resulted in an increase in the DGS of the nanogels up to a constant value. Subsequent irradiation of those swollen hydrogel particles was used to fully degrade the network structure in a second step. Hence, a two‐step degradation profile was realized by the combination of the two orthogonal stimuli. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The relative efficiency of option hedging strategies using the third-order stochastic dominance

Computational Management Science - The selection of an appropriate portfolio hedging strategy is a concern for both investment theory and practice. Options are believed to be flexible and useful...     

The Gender Productivity Gap in Croatian Science: Women Are Catching up with Males and Becoming Even Better

How much different genders contribute to citations and whether we see different gender patterns between STEM and non-STEM researchers are questions that have long been studied in academia. Here we analyze the research output in terms of citations collected from the Web of Science of males and females from the largest Croatian university, University of Zagreb. Applying the Mann–Whitney statistical test, for most faculties, we demonstrate no gender difference in research output except for seven faculties, where males are significantly better than females on six faculties. We find that female STEM full professors are significantly more cited than male colleagues, while male non-STEM assistant professors are significantly more cited than their female colleagues. There are ten faculties where females have the larger average citations than their male colleagues and eleven faculties where the most cited researcher is woman. For the most cited researchers, our Zipf plot analyses demonstrate that both genders follow power laws, where the exponent calculated for male researchers is moderately larger than the exponent for females. The exponent for STEM citations is slightly larger than the exponent obtained for non-STEM citations, implying that compared to non-STEM, STEM research output leads to fatter tails and so larger citations inequality than non-STEM.     

Tunable biohybrid hydrogels from coacervation of hyaluronic acid and PEO-based block copolymers

Accurately tuning the macroscopic properties of biopolymer-based hydrogels remains challenging due to the ill-defined molecular architecture of the natural building blocks. Here, we report a biohybrid coacervate hydrogel, combining the biocompatibility and biodegradability of naturally occurring hyaluronic acid (HA) with the tunability of a synthetic polyethylene oxide (PEO) -based ABA-triblock copolymer. Coacervation of the cationic ammonium or guanidinium-functionalized copolymer A-blocks with the anionic HA leads to hydrogel formation. Both mechanical properties and water content of the self-healing hydrogels can be controlled independently by altering the copolymer structure. By controlling the strength of the interaction between the polymer network and small-molecule cargo, both release rate and maximum release are controlled. Finally, we show that coacervation of HA and the triblock copolymer leads to increased biostability upon exposure to hyaluronidase. We envision that noncovalent crosslinking of HA hydrogels through coacervation is an attractive strategy for the facile synthesis of tunable hydrogels for biomedical applications.     

Quantitative Voronovskaya-Type Results for Polynomially Bounded Functions

We prove quantitative Voronovskaya-type results and Grüss–Voronovskaya inequalities for polynomially bounded functions. The results are given in terms of suitable K-functionals and applied to linking Szász–Mirakyan and Baskakov operators.     

Polymeric Photoresist Nanoparticles: Light‐Induced Degradation of Hydrophobic Polymers in Aqueous Dispersion

Nanoparticles consisting of a photoreactive polymer able to radically switch its hydrophobicity are successfully prepared by miniemulsion polymerization. Irradiation with UV light causes degradation of the particles whereat complete dissolution is achieved by changing the initial hydrophobic photoresist polymer into hydrophilic poly(methacrylic acid). Incorporation of the fluorescence‐sensitive Nile red serves as a solvatochromic probe to study the particle degradation. Diffusion of either Nile red out from or water into the former hard spherical nanoparticles is studied and not only renders the described material an ideal system for applications, where in situ dissolution of nanoparticles may be needed, but also bears the additional advantage of performing controlled burst release.