Thylakoid-associated polyamines adjust the UV-B sensitivity of the photosynthetic apparatus by means of light-harvesting complex II changes

The sensitivity of the photosynthetic apparatus to ultraviolet-B (UV-B) irradiation was studied in cultures of unicellular green alga Scenedesmus obliquus incubated in low light (low photosynthetically active radiation intensity [LL]) and high light (high photosynthetically active radiation intensity [HL]) conditions, treated or not with exogenous polyamines. Biochemical and physicochemical measurements showed that UV-B radiation induces a decrease in the thylakoid-associated putrescine (Put) and an increase in spermine (Spm), so that the reduction of Put/Spm ratio leads to the increase of light-harvesting complex II (LHCII) size per active reaction center and, consequently, the amplification of UV-B effects on the photosynthetic apparatus. The separation of oligomeric and monomeric forms of LHCII from isolated thylakoids showed that UV-B induces an increase in the oligomeric forms of LHCII, which was more intense in LL than in HL. By manipulating the LHCII size with exogenous polyamines, the sensitivity degree of the photosynthetic apparatus to UV-B changed significantly. Specifically, the addition of Put decreased highly the sensitivity of LL culture to UV-B because of the inhibitory effect of Put on the LHCII size increasing, whereas the addition of Spm enhanced the UV-B injury induced in HL culture because of the increasing of LHCII size. The ability of the photosynthetic apparatus to recover the UV-B induced changes was also investigated.     

Total arsenic content of nine species of Antarctic macro algae as determined by electrothermal atomic absorption spectrometry

Total arsenic in nine species Antarctic macro algae has been measured, by electrothermal atomic absorption spectrometry using a Pd/Mg(NO₃)₂ matrix modifier, to determine their capacity to accumulate the element. Macro algae were collected in February during the 2000 austral summer season at Jubany Station (Argentinean scientific station) around Potter Cove, King George Island. An optimized two-step microwave (MW) program was used to digest the samples. Dried samples were treated with HNO₃, H₂O₂, and HF, left overnight, then subjected to the first MW cycle. After cooling HNO₃ and HClO₄ were added and samples were subjected to the second MW cycle of digestion treatment. The effect of power and time on As recovery was examined. The analytical features of the method were: detection limit, 0.24 g g^–1 (dry mass); precision (RSD), 4.2–5.7%; recovery 91–105%. A wide range of As-retention capacity (41.0–447 g g^–1 dry mass) was observed among the different species. The highest levels of As were found in Phaeurus antarcticus (447 g g^–1 dry mass). This organism satisfies several prerequisites to be considered for consideration as a biomonitor in future studies.     

Reduction of the concentration difference of proteins in biological liquids using a library of combinatorial ligands

The discovery of polypeptides and proteins with relevance to a particular biological state is complicated by their vast number and concentration range in most biological mixtures. Depletion methodologies are frequently used to remove the most abundant species; however, this removal not only fails significantly to enrich trace proteins, it may also nonspecifically deplete them due to their interactions with the removed high-abundance proteins. Here we report a simple-to-use methodology that reduces the protein concentration range of a complex mixture like whole serum through the simultaneous dilution of high-abundance proteins and the concentration of low-abundance proteins. This methodology utilizes solid-phase ligand libraries of immense diversity, generated by "split, couple, recombine" combinatorial chemistry, that are used for affinity-based binding to the proteins of a given mixture. With a controlled sample-to-ligand ratio it is possible to modulate the relative concentration of proteins such that many peptides or proteins that are undetectable by classical analytical methods become easily accessible. The reduction in the dynamic range of unfractionated serum is specifically described along with treatment of other proteomes such as extracts from Escherichia coli, chicken egg white and cell culture supernatant. Mono- and bi-dimensional electrophoresis (1-DE and 2-DE respectively) and surface-enhanced laser desorption/ionization-mass spectrometry (SELDI-TOF-MS) technology demonstrate the reduction in protein concentration range. Combining this approach with additional fractionation methods further increased the number of detectable species.     

Spectroscopic and theoretical studies of derivatives of 1,6- and 1,7-naphthyridines

The solvatochromism in 8-hydroxy-1,6-naphthyridin-5(6H)-one-7-carboxylic acid methyl ester (1), 5-hydroxy-1,7-naphthyridin-8(7H)-one-6-carboxylic acid methyl ester (2), and 4-hydroxy-2-methyl-1(2H)-isoquinolone-3-carboxylic acid methyl ester (3), has been studied in solvents of different polarity and hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) ability. The relative stabilities of isomers for these naphthyridine derivatives and their interaction with the solvent are reported. Two intramolecular hydrogen-bonded structures contribute to the ground state of compound 1. Temperature effects on the absorption bands were recorded to analyse the possible equilibrium between covalent and zwitterionic forms. The formation of zwitterionic species was observed only in HBD solvents, from which is inferred the solvent assistance in the proton transference. AM1 and PM3 semi-empirical calculations were used in support of the proposed interpretations.     

A comparison of 3,4,6a,7,10,10a‐hexahydro‐7,10‐epoxypyrimido[2,1‐a]isoindol‐6(2H)‐one and 2‐(2‐aminoethyl)‐3a,4,7,7a‐tetrahydro‐1H‐4,7‐epoxyisoindole‐1,3(2H)‐dione: structural and reactivity differences of two homologous tricyclic imides

The crystal structures of 3,4,6a,7,10,10a‐hexahydro‐7,10‐epoxypyrimido[2,1‐a]isoindol‐6(2H)‐one, C₁₁H₁₂N₂O₂, and 2‐(2‐aminoethyl)‐3a,4,7,7a‐tetrahydro‐1H‐4,7‐epoxyisoindole‐1,3(2H)‐dione, C₁₀H₁₂N₂O₃, two tricyclic imides, show one and two molecules in the asymmetric unit, respectively. Intermolecular hydrogen‐bonding interactions are observed in both compounds.     

A new calcium 2,5-dihydroxybenzoate: Synthesis,characterization and antioxidant studies and stress mediated cytotoxity in MCF-7 cells

The structure and composition of the calcium 2,5-dihydroxybenzoate (calcium gentisate) were studied by single-crystal and powder X-ray diffraction. Single-crystal X-ray analysis revealed that the compound crystallizes in the orthorhombic space group Pbcn. The Ca(II) cation is coordinated in a monodentate fashion by two symmetry-related gentisate anions and five water molecules. The metal ion and one of the water molecules are located on a 2-fold rotation axis. The adjacent monomeric units are assembled into a 3-D supramolecular framework via O–H…O hydrogen bonds. Comparison of the experimental powder pattern with that simulated from single-crystal X-ray data confirmed the purity and homogeneity of the sample. The FT-IR, UV/VIS, ¹H and ¹³C NMR spectra of the calcium 2,5-dihydroxybenzoic acid were registered and analysed. Moreover the effect of calcium complex and 2,5-dihydroxybenzoic acid on basic oxidative stress parameters, such as thiol group content and lipid peroxidation in the human breast cancer cells MCF-7 was studied. The antiradical and ferric reducing power of these compounds was measured by DPPH, CUPRAC and FRAP methods. The chemical reactivity parameters (e.g. HOMO and LUMO orbitals, ionization potential, electron affinity) for Ca 2,5-dHB and 2,5-dHB were calculated at B3LYP/6-311++G7 level of theory and discussed in relation to their antioxidant properties.     

Selective Formation of Methyl α-Methylsulfanyl Dimethylphosphonothioacetate and Thiopropanoate by Phase Transfer Catalysis

The sulfanylation of methyl dimethylphosphonothioacetate was investigated by a phase transfer catalysis procedure which was shown to be superior to the noncatalytic method. The possibility of electrophilic substitution of the α-sulfanylated phosphonothioacetate to give a quaternary α-carbon atom is shown by the reaction with methyl iodide.

     

Three dimensional imaging using secondary ion mass spectrometry and atomic force microscopy

With the breakthroughs in lateral resolution with regards to secondary ion mass spectroscopy in recent years, new areas of research with much promise have opened up to the scientific community. Even though the much improved lateral resolution of 50 nm can effectively deliver more accurate 3D-images, the traditional 3D reconstructions, consisting of compiling previously acquired successive secondary ion mass spectrometry images into a 3D-stack, do not represent the real localized chemical distribution of the sputtered volume. Based on samples initially analyzed on the Cameca NanoSIMS 50 instrument, this paper portrays the advantages of combining the topographical information from atomic force microscopy and the chemical information from secondary ion mass spectrometry. Taking account of the roughness evolution within the analyzed zone, 3D reconstructions become a lot more accurate and allow an easier interpretation of results. On the basis of an Al/Cu sample, a comparison between traditional 3D imaging and corrected 3D reconstructions is given and the advantages of the newly developed 3D imaging method are explained.