Influence of diamino acid derivatives of protoporphyrin IX on mouse immunological system: preliminary results

Immunological response related to photodynamic therapy (PDT) is one of the basic elements that influence on the efficiency of this cancer treatment method. Diamino acid derivatives of protoporphyrin IX are promising photosensitizing agents that are intended to be the components of new anti-tumor drug. The influence of three derivatives - PP(Ser)(2)Arg(2), PP(Ala)(2)Arg(2), PP(Phe)(2)Arg(2) and a mixture of these compounds called Sensyphyrine on mouse immunological system was investigated where animals were exposed and unexposed to the laser irradiation. Porphyrins solutions were injected intravenously, mice were irradiated with the red diode laser at lambda=632 nm. Cells and blood samples were taken at time intervals after irradiation. The levels of interleukin-6, interleukin-1beta and the production of reactive forms of nitrogen by macrophages were determined. The results show that all of the diamino acid derivatives of protoporphyrin IX indicate an immunological response when the light is applied. Each of the porphyrin revealed different impact on mice immunological system. The most potent stimulant properties disclosed PP(Phe)(2)Arg(2) derivative for which the highest values of IL-1beta, IL-6 and NO(2)(-) were noticed. The weakest immunological activation revealed PP(Ser)(2)Arg(2) derivative.     

Molecular geometry as a source of chemical information. 5. Substituent effect on proton transfer in para-substituted phenol complexes with fluoride--a B3LYP/6-311+G study

The simplified model system [p-X-PhO...H...F](-), where -X are -NO, -NO(2), -CHO, -H, -CH(3), -OCH(3), and -OH, with various O...F distance was used to simulate the wide range of the H-bond strength. Structural changes due to variation of the substituent as well as the H-bond strength are well monitored by the changes in the aromaticity index HOMA and by two empirical measures of the H-bond strength-the (1)H NMR chemical shift of proton involved and the C-O bond length. Changes in H-bonding strengths and the position of proton transfer while shortening the O...F distance are well described by the Hammett equation.     

Preparation of ready-to-use, stockable and reconstituted collagen

Collagen is a widely used material in biomedical applications. Although processes that prepare collagen and collagen-based materials that show suitable properties after extraction exist, a ready-to-use, easily stockable, with tailored collagen concentration has not yet been developed. Using rat tail tendons, acid soluble collagen solutions were prepared by two different methods. To improve cell viability of pure collagen films, solutions with physiological pH were also prepared by mixing with NaOH solution. Specimens in the form of thin sheets were then fabricated by solvent evaporation. Next, IR spectroscopy, tensile testing techniques as well as human fibroblast cell morphology and cytotoxicity were used to validate the significant variations in the processes. The results demonstrated that, during the synthesis of collagen stock solution, lyophilization and mechanical blending had little effect on the final properties and therefore offers a method for obtaining solutions with a more homogeneous and modifiable collagen concentration and longer storage time. Neutralizing the stock solution with aqueous NaOH prior to solvent evaporation provided films that had lower mechanical properties but significantly improved biological performance.     

Investigation of the role of cadmium sulfide in the surface passivation of lead sulfide quantum dots

Surface passivation of PbS nanocrystals (NC), resulting in strong photoluminescence, can be achieved by the introduction of CdS precursors. The role of CdS in the surface passivation of PbS NCs is uncertain, as the crystalline structure of CdS and PbS are different, which should impede effective epitaxial overgrowth. Absorption spectroscopy is used to show that the CdS precursors strongly interact with the PbS NC surface. Electron microscopy reveals that the introduction of CdS precursors results in an increased particle size, consistent with overcoating. However, we also find the process to be highly non-uniform. Nevertheless, evidence for epitaxial growth is found, suggesting that effective surface passivation may be possible.     

Application of ICP-MS,INAA and RNAA to the determination of some “difficult” elements in infant formulas

In this work a determination of selected elements in the infant formulas commercially available on the Polish market was done. 14 different materials (milk-based formulas and grain porridges) were analyzed. Both, inductively coupled plasma mass spectrometry (ICP-MS) and instrumental neutron activation analysis (INAA) were applied for the determination of As, Cr, Fe and Se, which are recognized as the problematic elements for ICP-MS. For As and Se, the radiochemical NAA was also used. The daily intake of Se and Fe in the age 0–6 months for non-breast fed infants was estimated and compared with present safety limits.

     

Influence of Culture Medium Composition and Light Conditions on the Accumulation of Bioactive Compounds in Shoot Cultures of <Emphasis Type="Italic">Scutellaria lateriflora</Emphasis> L. (American Skullcap) Grown In Vitro

Methanolic extracts from in vitro grown Scutellaria lateriflora shoots cultured on five Murashige and Skoog (MS) medium variants supplemented with different combinations of 6-benzylaminopurine (BAP) and α-naphthaleneacetic acid (NAA) under different light conditions (monochromatic light, white light and no light) were analysed by HPLC for three groups of metabolites: flavonoids (26 compounds), phenolic acids and their precursors (19+2) and phenylethanoid glycosides (2). The analyses revealed the presence of baicalein, baicalin, wogonin, wogonoside, 3,4-dihydroxyphenylacetic acid and verbascoside. There was clear evidence of the influence of plant growth regulators and light conditions on the accumulation of the analysed groups of secondary metabolites. The amounts of the compounds changed within a wide range—for the total flavonoid content, 30.2-fold (max. 1204.3 mg·100 g^?1 dry weight (DW)); for 3,4-dihydroxyphenylacetic acid, 5.5-fold (max. 33.56 mg·100 g^?1 DW); and for verbascoside, 1.5-fold (169.15 max. mg·100 g^?1 DW). The best medium for the production of most of the compounds was the Murashige and Skoog variant with 1 mg l^?1 BAP and 1 mg l^?1 NAA. For verbascoside, the best ‘productive’ medium was the MS variant supplemented with 0.5 mg l^?1 BAP and 2 mg l^?1 NAA. The accumulation of the metabolites was stimulated to the greatest extent by blue light, under which the extracts were found to contain the highest total amount of flavonoids and the highest amounts of flavonoid glucuronides, baicalin and wogonoside, as well as of verbascoside. Their amounts were, respectively, 1.54-, 1.49-, 2.05- and 1.86-fold higher than under the control white light.     

RNAA in metrology: A highly accurate (definitive) method

The idea of highly accurate (definitive) methods by radiochemical neutron activation analysis (RNAA) is presented and illustrated with several examples of methods worked out in this Laboratory over the past several years. Definitive methods by RNAA are constructed by combining reactor neutron activation with very selective and quantitative post-irradiation separation of the indicator radionuclide by column chromatography followed by γ-ray spectrometric measurement. All conditions for the determination of the individual element are optimized and uncertainties associated with every step of the analytical procedure are minimized. Even after the method has been thoroughly elaborated and validated through the analysis of appropriate certified reference materials (CRMs), the results obtained in each series of measurements are acknowledged as obtained by definitive method only when a series of previously formulated criteria is simultaneously fulfilled. The examples of definitive methods for the determination of cadmium, cobalt and molybdenum, respectively, in biological materials are presented. Each of these methods has detection limit of the order of ng g⁻¹ or better, and yields accurate and precise results. The expanded standard uncertainty is of the order of 2.6% for the case of single-element determination (Co) and 3.4-5.2% for the less favourable case (Mo) where there is necessity for simultaneous determination of uranium to correct for interference due to fission reaction. Definitive methods by RNAA may constitute an option or alternative with respect to ID-MS as methods of “guaranteed accuracy” being also a perspective solution in the case of monoisotopic elements, for which ID-MS cannot be used.     

Application of a metal ion-imprinted polymer based on salen-Cu complex to flow injection preconcentration and FAAS determination of copper

A new Cu(II)-imprinted polymer (Cu-IIP) for preconcentration of copper by liquid-solid extraction via flow injection technique has been proposed. Cu-IIP was obtained by copolymerization of salen-Cu(II) complex with styrene and divinylbenzene using suspension polymerization technique. Granules fraction of 60-80 microm in diameter was used as a microcolumn packing. Cu(II) sorption was proved to be the most effective from solutions of pH 7, whereas similar elution effectiveness was observed when applying as eluents hydrochloric or nitric acid in the concentration range of 0.5-10% (v/v). The system exhibited good long-term stability and acid resistance. Batch sorbent capacity was found to be 0.11 mmol g(-1) of a dry polymer. Enrichment factor (EF) for 30 s loading time was 16. Preconcentration of Cu(II) and potentially interfering metal ions is strongly pH dependent. Examination of Cu(II) sorption in the presence of Pb(II), Cd(II), Zn(II) and Ag(I) showed significant influence of cadmium and zinc ions only and that was for the interferent concentrations above 0.5 mg L(-1) (Cu-IIP mass of ca. 35 mg). The interference effect was reduced with the sorbent mass increase. Fe(III) and Mn(II) ions, present in treated tap water in relatively high concentrations, did not interfere. Effective pH adjusting of the loaded solution in on-line mode, when applying diluted Clark-Lubs buffering solution, allowed accurate copper determination in tap water (compared to graphite furnace atomic absorption spectrometry, GFAAS) using standard addition or combination calibration method.     

LIGHT-DRIVEN H2 PRODUCTION WITH PROFLAVIN AND HYDROGENASE: COMPARISON OF CYTOCHROME C3 AND METHYL VIOLOGEN AS e- MEDIATORS

We have studied the hydrogenase-catalyzed production of H, when either its natural electron mediator cytochrome c₃ (c₃) or the artificial mediator methyl viologen (MV) was reduced by illumination of proflavin (PF) in the presence of ethylenediaminetetraacetate (EDTA). The reduction rates of MV and c₃ were comparable at equivalent concentrations of PF, taking into account the four redox sites of c₃. However, when the concentration of c₃ exceeded that of PF, the reduction rate decreased. We explain this by light quenching. In the H₂-producing system, MV was more efficient than c₃ as electron mediator when the initial reaction rates were compared. However, under certain conditions with MV, the rate of H₂ production decreased rapidly with time of illumination, whereas with c₃ it consistently remained stable. Possible reasons for this difference are discussed.
Severe inactivation of hydrogenase was observed in the absence of the primary electron donor EDTA. It is concluded that this inactivation is caused by the excited state of PF     

Surface Properties of Poly(vinyl alcohol) with Iron(III)chloride Before and After UV-Irradiation

Summary: Surface properties of poly(vinyl alcohol) (PVA) with low content of FeCl₃ (1, 5 wt.%) were studied by measurements of contact angles and atomic force microscopy. The results of contact angles and the surface free energy calculations revealed that the hydrophilicity of the surface of PVA films depended on the content of iron (III) chloride in these polymeric films. Introduced salt also affected photochemical reactions in poly(vinyl alcohol). Photooxidation of PVA was more effective in the presence of FeCl₃ because of formation of reactive chlorine atoms, which were capable of initiating new reactions. Also the morphology and roughness parameters of PVA film changed when iron (III) chloride was added.