Light induced multiphase chemistry of gas-phase ozone on aqueous pyruvic and oxalic acids.

In this study for the first time it has been shown that pyruvic acid can affect the atmospheric multiphase reactions of ozone with oxalic acid due to its properties as a photosensitizer. To this end, the photochemical batch multiphase reactions of a mixture of pyruvic acid/oxalic acid (PA/OA) and gas-phase ozone under simulated sunlight were studied as a function of time using high pressure liquid chromatography equipped with a UV detector (HPLC-UV) and electrospray ionization mass spectrometry (ESI-MS) to investigate product formation. Following the simultaneous ozone and light irradiation the first peak for pyruvic and oxalic acids (retention time = 3.68 min) decreased to 67% of the initial intensity after a 12 h reaction while a broad and not well defined peak appeared at longer retention times. After prolonged exposure times this broad peak shifted to shorter retention times: from 14 min at 2 h reaction to 8 min at 12 h. The HPLC-UV analysis of the reaction mixture simultaneously exposed to ozone and irradiated by simulated sunlight for 6-12 h revealed the presence of high weight molecular mass products and formation at longer times of highly non-polar products. The results obtained from ESI-MS have clearly demonstrated that the distribution of high molecular weight products is consistent with an oligomer system. No evidence of oligomer formation was found after the sample (PA/OA) was exposed only to either ozone or irradiated with UV/Vis light using the same instrumental conditions.

Blockade of T-lymphocyte KCa3.1 and Kv1.3 channels as novel immunosuppression strategy to prevent kidney allograft rejection.

Currently, there is an unmet clinical need for novel immunosuppressive agents for long-term prevention of kidney transplant rejection as alternatives to the nephrotoxic calcineurin inhibitor cyclosporine (CsA). Recent studies have shown that K(+) channels have a crucial role in T-lymphocyte activity. We investigated whether combined blockade of the T-cell K(+) channels K(Ca)3.1 and K(v)1.3, both of which regulate calcium signaling during lymphocyte activation, is effective in prevention of rejection of kidney allografts from Fisher rats to Lewis rats. All recipients were initially treated with CsA (5 mg/kg d) for 7 days. In rats with intact allograft function, treatment was continued for 10 days with either CsA (5 mg/kg d), or a combination of TRAM-34 (K(Ca)3.1 inhibitor; 120 mg/kg d) plus Stichodactyla helianthus toxin (ShK, K(v)1.3 inhibitor; 80 microg/kg 3 times daily), or vehicle alone. Kidney sections were stained with periodic acid-Schiff or hematoxylin-eosin and histochemically for markers of macrophages (CD68), T-lymphocytes (CD43), or cytotoxic T-cells (CD8). Our results showed that treatment with TRAM-34 and ShK reduced total interstitial mononuclear cell infiltration (-42%) and the number of CD43+ T-cells (-32%), cytotoxic CD8+ T-cells (-32%), and CD68+ macrophages (-26%) in allografts when compared to vehicle treatment alone. Efficacy of TRAM-34/ShK treatment was comparable with that of CsA. In addition, no visible organ damage or other discernible adverse effects were observed with this treatment. Thus, selective blockade of T-lymphocyte K(Ca)3.1 and K(v)1.3 channels may represent a novel alternative therapy for prevention of kidney allograft rejection.

Size distribution of black (BC) and total carbon (TC) in Vienna and Ljubljana.

During two campaigns in winter 2004, size segregated impactor samples (0.1-10 microm) and filter samples were taken in two Central European cities (Vienna, Austria and Ljubljana, Slovenia). The impactor samples were analyzed for major inorganic ions and short-chain organic acids, total carbon (TC) and black carbon (BC). Maximum concentrations of total mass were 71.6 microg m(-3) in Vienna and 73.1 microg m(-3) in Ljubljana. Minimum concentrations in Vienna were only half those in Ljubljana. The BC content of the aerosol was similar (ca. 8%), but the BC/TC ratio was higher in Vienna than in Ljubljana (0.39 vs. 0.29), reflecting the different contribution of diesel traffic emissions. The mass median diameters of the submicron size distributions of all major fractions (total mass, TC, BC and SO(4)(2-)) were smaller in Vienna (0.43 microm, 0.41 microm, 0.38 microm and 0.48 microm, respectively) than in Ljubljana (0.55 microm, 0.44 microm, 0.42 microm and 0.60 microm, respectively). Impactor/filter ratios for total mass were 0.79 in Vienna and 0.82 in Ljubljana, while the ratios for BC were 0.56 in Vienna and 0.49 in Ljubljana. An estimation of the mixing state of accumulation mode BC indicated that 33% and 37% of BC, respectively, are mixed externally to the aerosol in the accumulation size range in Vienna and Ljubljana.

[Endothelial ion channels -- novel targets for antihypertensive therapy]. / Endotheliale Ionenkanäle -- neue Targets der Hypertonietherapie?

Endothelial cation channel are important regulators of vascular tone by modulating intracellular Ca(2+)-signaling and thus adequate synthesis of vasodilating factors. The overall importance of these ion channels suggests that they may represent novel pharmacotherapeutic targets in addition to the well-known voltage-gated calcium channels in vascular smooth muscle. In this short overview we summarize the current knowledge about endothelial ion channels and their roles for endothelium-dependent vasodilatation. Furthermore, we perspectively discuss the usefulness of specific openers of endothelial Ca(2+)-activated K(+)-channels and TRPV-channels as novel antihypertensive drugs.

Passing of fluorescein derivatives into the hyphae of Phanerochaete chrysosporium.

Fluorescein derivatives added into the growth medium were decolorized during submerged cultivation of Phanerochaete chrysosporium. The highest decrease of absorbance A450 was observed in the growth phase regardless of the presence of inducers Tween 80 or poly(ethylene glycol) (PEG). Fluorescein linked to PEG was prepared and, after addition to cultures, shown to stimulate the production of lignin peroxidase. Passing of fluorescing substances into hyphae (observed by confocal microscopy) showed that they were concentrated on some structures inside hyphae.

Stimulation of ligninolytic enzyme production in Phanerochaete chrysosporium by polyoxyalkanes.

AIMS: Poly(ethylene glycol) (PEG) and some substances similar to PEG in chemical structure were tested as stimulators of ligninolytic enzyme production in shaken culture of Phanerochaete chrysosporium. METHODS AND RESULTS: The substances that caused high enzymatic activity were linear polymers [poly(ethylene glycol), poly(propylene glycol), poly(butylene glycol) and poly(vinyl alcohol)] and cyclic polymers (crown ether). They can have terminal groups other than -OH [PEG (di)methyl ether, PEG sulphate, PEG derivative with the amino group and xanthate]. The maximum lignin peroxidase activities were compared with the surface pressure caused by the stimulator. Addition of polymers composed of charged monomer units did not increase the enzymatic activity and the fungi did not grow at all on addition of polymers having a fixed positive charge. CONCLUSIONS: Lignin peroxidase activity was increased after the addition of polymers with uncharged monomer units. It was higher and its maximum was reached in a shorter time on addition of polymers with higher molecular weights. SIGNIFICANCE AND IMPACT OF STUDY: Beside Tweens there are several polymers that stimulate ligninolytic enzyme production in shaken culture of P. chrysosporium. Their characteristics are: similarity to PEG in chemical structure, having uncharged monomer units and high molecular weight.