Gelation in Photoinduced ATRP with Tuned Dispersity of the Primary Chains.

We investigated gelation in photoinduced atom transfer radical polymerization (ATRP) as a function of Cu catalyst loading and thus primary chain dispersity. Using parallel polymerizations of methyl acrylate with and without the addition of a divinyl crosslinker (1,6-hexanediol diacrylate), the approximate values of molecular weights and dispersities of the primary chains at incipient gelation were obtained. In accordance with the Flory-Stockmayer theory, experimental gelation occurred at gradually lower conversions when the dispersity of the primary chains increased while maintaining a constant monomer/initiator/crosslinker ratio. Theoretical gel points were then calculated using the measured experimental values of dispersity and initiation efficiency. An empirical modification to the Flory-Stockmayer equation for ATRP was implemented, resulting in more accurate predictions of the gel point. Increasing the dispersity of the primary chains was found not to affect the distance between the theoretical and experimental gel points and hence the extent of intramolecular cyclization. Furthermore, the mechanical properties of the networks, such as equilibrium swelling ratio and shear storage modulus showed little variation with catalyst loading and depended primarily on the crosslinking density.

Fluorescent Patterns by Selective Grafting of a Telechelic Polymer.

The preparation of patterned ultrathin films (sub-10 nm) composed of end-anchored fluorescently labeled poly(methyl methacrylate) (PMMA) is presented. Telechelic PMMA was synthesized utilizing activator regenerated by electron transfer atom transfer radical polymerization and consecutively end-functionalized with alkynylated fluorescein by Cu-catalyzed azide-alkyne cycloaddition (CuAAC) "click" chemistry. The polymers were grafted via the α-carboxyl groups to silica or glass substrates pretreated with (3-aminopropyl)triethoxysilane (APTES). Patterned surfaces were prepared by inkjet printing of APTES onto glass substrates and selectively grafted with fluorescently end-labeled PMMA to obtain emissive arrays on the surface.

Facile Aqueous Route to Nitrogen-Doped Mesoporous Carbons.

An aqueous-based approach for the scalable synthesis of nitrogen-doped porous carbons with high specific surface area (SSA) and high nitrogen content is presented. Low molecular weight polyacrylonitrile (PAN) is solubilized in water in the presence of ZnCl2 that also acts as a volatile porogen during PAN pyrolysis to form mesoporous structures with significantly increased SSA. By templating with commercial SiO2 nanoparticles, nanocellulose fillers or filter paper, nanocarbons with SSA = 1776, 1366, and 1501 m2/g, respectively and 10 wt % N content were prepared. The materials formed by this benign process showed excellent catalytic activity in oxygen reduction reaction via the four-electron mechanism.

In-Situ Platinum Deposition on Nitrogen-Doped Carbon Films as a Source of Catalytic Activity in a Hydrogen Evolution Reaction.

Copolymer-templated nitrogen-doped carbon (CTNC) films deposited on glassy carbon were used as electrodes to study electrochemically driven hydrogen evolution reaction (HER) in 0.5 M H2SO4. The activity of these materials was extremely enhanced when a platinum counter electrode was used instead of a graphite rod and reached the level of commercial Pt/C electrodes. Postreaction scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) measurements of electrode surfaces revealed that incorporation of even extremely low amounts of Pt resulted in this considerable gain of HER activity. High resolution XPS analysis and density functional theory (DFT) calculations confirmed that pyridinic nitrogen atoms act as active sites for Pt coordination and deposition. The Pt can be incorporated in both molecular (Pt(2+)) and metallic (Pt(0)) form. This study shows that great caution must be taken when designing "metal-free" HER catalysts based on N-doped carbons.

Polyelectrolyte multilayers with perfluorinated phthalocyanine selectively entrapped inside the perfluorinated nanocompartments.

A novel perfluorinated magnesium phthalocyanine (MgPcF64) was synthesized and employed to probe nanodomains in hydrophobically modified, amphiphilic cationic polyelectrolytes bearing alkyl and/or fluoroalkyl side chains. MgPcF64 was found to be solubilized exclusively in the aqueous solutions of the fluorocarbon modified polycations, occupying the perfluorinated nanocompartments provided, while analogous polyelectrolytes with alkyl side chains forming hydrocarbon nanocompartments could not host the MgPcF64 dye. Multilayer films were fabricated by means of the layer-by-layer (LbL) deposition method using sodium poly(styrene sulfonate) as a polyanion. Linear multilayer growth was confirmed by UV-Vis spectroscopy and spectroscopic ellipsometry. Atomic force microscopy studies indicated that the micellar conformation of the polycations is preserved in the multilayer films. Fluorescence spectroscopy measurements confirmed that MgPcF64 stays embedded inside the fluorocarbon domains after the deposition process. This facile way of selectively incorporating water-insoluble, photoactive molecules into the structure of polyelectrolyte multilayers may be utilized for nanoengineering of ultrathin film-based optoelectronic devices.

[Regeneration of corneal epithelium using keratin modified chitosan membranes]. / Regeneracja nablonka rogówki przy zastosowaniu membran chitozanowych modyfikowanych keratyna.

The cornea is a transparent front layer of the eye. It functions like a window that controls and focuses the light entering into the eye. The cornea contributes to 65-75% of the eye's total focusing power and it acts as a physical barrier against pathogenic microorganisms, dirt and other noxious physical factors. The corneal tissue is arranged in five basic layers. The outermost layer (epithelium) is made up of highly regenerative cells that allow for quick healing of superficial injuries. Eye infections, diseases, or mechanical injury can harm corneal epithelium and cause blindness. Under certain circumstances, to prevent that, it is recommended to perform complete corneal transplantation. However, due to lack of sufficient number of donors, researchers are searching for alternative solutions.. Regeneration of epidermal tissue can restore and ensure normal functioning of cornea. For that purpose proper grafts are needed. The goal of current research was to develop the material for scaffold preparation providing optimal conditions for the epithelium cornea cell culturing and to determine its chemical, physical, and biological properties. The scaffolds, which could be applied in ophthalmology should fulfill a lot of requirements, among them such as biocompatibility, biodegradability, restorability, non-toxicity. They should also have adequate mechanical strength, flexibility and porosity. The aim of this work was to synthesize and to determine the properties of polymeric material for ophthalmic surgery applications. A hydrogel scaffold in the form of membrane was obtained from chitosan - natural, biocompatible, biologically inert, stable in the natural environmental and antibacterial polysaccharide derived from chitin. Biodegradable chitosan films containing keratin were crosslinked with genipin - a naturally occurring and nontoxic agent. In this study we present physicochemical characterization of the scaffolds. Porosity, contact angle and swelling ratio (at different pH) were determined. The optical microscope technique was used to visualize the microstructure of the scaffolds. Atomic force microscopy (AFM) measurements revealed the topography of the surfaces of membranes. The biological tests have shown that epithelial cells seeded on the membranes proliferated efficiently.

Potentiated antitumor effects of a combination therapy with a farnesyltransferase inhibitor L-744,832 and butyrate in vitro.

Farnesyltransferase inhibitors, butyrate and butyric acid derivatives have previously been reported to exert anti-tumor activity in experimental models in vitro and in vivo and have recently gained acceptance as potential anticancer agents. In our study, we examined antitumor effects of a combination of a farnesyltransferase inhibitor L-744,832 and butyrate in vitro against MDA-MB-231 and MIA PaCa-2 human cancer cells. This combination therapy showed synergistic antitumor activity against MDA-MB-231 cells, which was at least in part due to induction of p27KIP1 expression. Both drugs increased intracellular levels of p53 as well but there was no significant difference between the groups treated with single drugs and the group treated with their combination. In MIA PaCa-2 cells, the combination therapy exerted additive antitumor activity. Our results illustrate possible application of the farnesyltransferase inhibitor L-744,832 and butyrate as a combination therapy of cancer.

Cerivastatin demonstrates enhanced antitumor activity against human breast cancer cell lines when used in combination with doxorubicin or cisplatin.

Competitive inhibitors of 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) reductase are commonly used in the clinic to treat hypercholesterolemia and have been reported to exert antitumor effects. Cerivastatin is a novel, synthetic and the most pharmacologically potent inhibitor of HMG-CoA reductase. We decided to examine the cytostatic/cytotoxic activity of cerivastatin against human breast cancer cell lines and to test whether the effects of cerivastatin could be potentiated by doxorubicin and cisplatin. Cytostatic/cytotoxic effects of cerivastatin used alone or in the combination with chemotherapeutics were measured with MTT assay. The cell cycle distribution and apoptosis induction were evaluated with flow cytometer. The expression of p21 and p27 cyclin-dependent kinase inhibitors was measured with Western blotting. Isobologram analysis was performed to study the drug interactions. We observed that cerivastatin exerts cytostatic/cytotoxic effects against four human tumor cell lines (T-47D, T4-2, MDA-MB-231, MCF-7). We also demonstrated that cerivastatin exerts growth inhibitory effect through induction of p21 cyclin-dependent kinase inhibitor and inhibition of cell cycle progression. In the two tumor cell lines studied, one sensitive (MDA-MB-231) and one moderately resistant (T4-2) to the cytostatic/cytotoxic effects of cerivastatin we examined the effects of combined treatment with cerivastatin and either doxorubicin or cisplatin. Cerivastatin potentiated cytostatic/cytotoxic effects of cisplatin against T4-2 cells and those of doxorubicin against both cell lines. In T4-2 cells the interaction between doxorubicin and cerivastatin and between cisplatin and cerivastatin was found to be synergistic. Altogether, these studies indicate that cerivastatin is another HMG-CoA reductase inhibitor with potent antitumor effects.

Antitumor effects of photodynamic therapy are potentiated by 2-methoxyestradiol. A superoxide dismutase inhibitor.

Photodynamic therapy (PDT), a promising therapeutic modality for the management of solid tumors, is a two-phase treatment consisting of a photosensitizer and visible light. Increasing evidence indicates that tumor cells in regions exposed to sublethal doses of PDT can respond by rescue responses that lead to insufficient cell death. We decided to examine the role of superoxide dismutases (SODs) in the effectiveness of PDT and to investigate whether 2-methoxyestradiol (2-MeOE(2)), an inhibitor of SODs, is capable of potentiating the antitumor effects of this treatment regimen. In the initial experiment we observed that PDT induced the expression of MnSOD but not Cu,Zn-SOD in cancer cells. Pretreatment of cancer cells with a cell-permeable SOD mimetic, Mn(II)-tetrakis(4-benzoic acid)porphyrin chloride, and transient transfection with the MnSOD gene resulted in a decreased effectiveness of PDT. Inhibition of SOD activity in tumor cells by preincubation with 2-MeOE(2) produced synergistic antitumor effects when combined with PDT in 3 murine and 5 human tumor cell lines. The combination treatment was also effective in vivo producing retardation of the tumor growth and prolongation of the survival of tumor-bearing mice. We conclude that inhibition of MnSOD activity by 2-MeOE(2) is an effective treatment modality capable of potentiating the antitumor effectiveness of PDT.