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Occurrence of 7-methyl-7-hexadecenoic acid, the corresponding alcohol, 7-methyl-6-hexadecenoic acid, and 5-methyl-4hexadecenoic acid in sperm whale oils.

Two sperm whale oils from the northern hemisphere and two from the southern hemisphere were fractionated. Triglyceride and wax esters were examined for fatty acids and alcohols with monoethylenic unsaturation bearing a methyl branch on an ethylenic carbon. The 7-methyl-7-hexadecenoic acid (0.37-1.37%) was accompanied by the corresponding alcohol (0.28-0.72%), but these materials were not accompanied by shorter chain homologues. The 7-methyl-6-hexadecenoic acid was relatively less important (0.23-0.68%), but was accompanied by 5-methyl-4-hexadecenoic acid (0.10-0.39%), and a partially identified C13 compound. Chromatographic properties on silver nitrate impregnated silicic acid TLC and on three GLC liquid phases are reported.

Animals↗

[Materials for reconstruction of the middle ear].

To rehabilitate most cases of conductive hearing loss closure of ear drum perforations and rebuilding of the ossicular chain can be performed. Due to the great number of biocompatible bone substitute materials available it is occasionally difficult for the surgeon to choose the most favorable substitute. Autogenous structures (ossicles, cortical bone, cartilage) and allogenous tissues (ossicles, cortical bone, cartilage, dentin) are possible bone replacement materials. Xenogenic tissue is currently not used in middle ear surgery. Ionomer cement is a hybrid material for replacement of bone but does not fit direct classification of the various classes of alloplastic materials in current use: that is, metals (gold, steel wire, platinum, titanium), plastics (polyethylene, polytetrafluorethylene) and ceramics (ceramic oxide, carbon, calcium-phosphate ceramic, vitreous ceramic). For restoration of the sound conductive apparatus preference is given to autogenous ossicles because cortical bone is resorbed and cartilage weakens over time. Most surgeons do not use allogenous tissue, because of the possible transmission of such infectious disease as immunodeficiency syndrome or Creutzfeldt-Jakob disease. Only dentin deserves special attention as a possible bone substitute in the middle ear because its form can be preserved during sterilization. Based on the observations available to date, it becomes apparent that titanium implants hold greater promise than gold. Form-stable synthetic materials are not generally recommended due to foreign body reactions which have been confirmed by many investigators. Ceramic materials (e.g. ceramic oxide, carbon, calcium-phosphate ceramic, glass ceramic) are well tolerated in the middle ear and have also proved to be useful over time. Hybrid bone substitute ionomer cement is easily workable and well integrated, showing a good functional outcome. For many years good results in otosclerosis surgery have been achieved with a prosthesis made of platinum-wire and Teflon. Short-term follow-up periods hold great promise with pistons made of gold. Autogenous ossicles, ionomer cement and recently titanium protheses--as far as usable--are employed by the author for reconstructing the middle ear. For the time being platinum-Teflon prostheses and gold are used in otosclerosis surgery.

Animals↗

Biphasic kinetics of metal ion reactivation of trypsin-thiol complexes.

This report describes biphasic kinetic data obtained when trypsin was inhibited by a thiol-containing inhibitor present in Ehrlich ascites tumour cells and then subjected to addition of Hg2+, Cu2+ or Ag+. This resulted in an initial re-activation of the trypsin, followed by inhibition of the enzyme with the addition of higher concentrations of these ions. The significance of these observations is 2-fold: (i) help to elucidate the mechanism of metal ion activation of latent enzymes, and (ii) also indicate that, in certain circumstances, the concentration of added metal ion determines whether the metal acts as an activator or an inhibitor of enzyme activity.

Copper↗

Complexation of polysaccharide and monosaccharide with thiolate boronic acid capped on silver nanoparticle.

Synthesized thiolate boronic acid was found to complex with both a polysaccharide (dextran) and a monosaccharide (glucose) with similar affinities but displayed more affinity with dextran than with glucose when capped as a ligand on silver nanoparticle. Coupling on multiple sites of dextran, the silver particles were aggregated. The aggregated particles displayed a decrease of absorbance at 397 nm and an increase at 640 nm. Luminescence intensity displayed an upward deviation increase with the concentration of dextran. The luminescence spectral change was ascribed to surface-enhanced fluorescence by the enhanced field from the aggregated metallic particles.

Boronic Acids↗

Toxicity of silver to two freshwater algae, Chlamydomonas reinhardtii and Pseudokirchneriella sub-capitata, grown under continuous culture conditions: influence of thiosulphate.

In a test of the biotic ligand model (BLM), the uptake and toxicity of silver, in the absence or presence of the inorganic ligand, thiosulphate, were assessed for two freshwater green algae, Chlamydomonas reinhardtii and Pseudokirchneriella sub-capitata, using turbidostat continuous cultures. In the initial experiments, run in the absence of thiosulphate, the influent Ag concentration was varied from 0 to 75 nM in steps; for each influent concentration, silver uptake was calculated and the algal growth rate was determined. Silver uptake rates at low Ag concentrations were similar for both algae (e.g., 14-19 nmolm(-2)h(-1), for influent Ag(+) concentrations of approximately 9 nM) but at higher exposures uptake by P. sub-capitata exceeded that of C. reinhardtii. Despite this higher uptake rate, in the absence of thiosulphate P. sub-capitata was not more sensitive to free silver; 50% growth inhibition was reached at influent free Ag(+) concentrations of 15+/-7 and 22+/-13 nM for C. reinhardtii and P. sub-capitata, respectively. In the second series of experiments, the free Ag(+) concentration was held constant ( approximately 9 nM in the influent; 2-3 nM in the effluent) while the concentration of the silver thiosulphate complex, AgS(2)O(3)(-), was increased from 9 to 90 nM in steps. Under such conditions, the BLM would predict that silver uptake and toxicity should remain constant. On the contrary, both silver uptake and silver toxicity increased, indicating that the anionic silver thiosulphate complex enters the algal cells via a membrane-bound sulphate transporter and contributes to uptake and toxicity. However, for both algae there were indications that silver assimilated in this manner was somewhat less toxic to the algal cell than silver that entered via cation transport only. Physiological indicators of stress revealed possible different intracellular targets for these two freshwater algae, proteins and enzymes for C. reinhardtii and the photosynthetic apparatus for P. sub-capitata.

Animals↗

Silver activates mast cells through reactive oxygen species production and a thiol-sensitive store-independent Ca2+ influx.

In genetically susceptible human and/or experimental animals, heavy metals such as mercury, gold, and silver have been shown to highly induce adverse immunological reactions such as allergy and autoimmunity, in which mast cell degranulation is implicated as playing a role. We previously reported that silver activates mast cells and induces Ca2+ influx without stimulating intracellular signaling events required for activation of store-operated Ca2+ channels (SOCs). The purpose of the present study was to elucidate the possible involvement of reactive oxygen species (ROS) in the biological effects of silver. Analysis using oxidant-sensitive fluorescent probes such as dichlorodihydrofluorescein and scopoletin, as well as MCLA-amplified chemiluminescence, showed that silver induced intracellular production and/or extracellular release of ROS. Silver induced mast cell degranulation in a Ca2+ -dependent manner. Unlike IgE antigen, silver-induced Ca2+ influx was not affected by depletion of internal Ca2+ stores. Instead, the metal-induced Ca2+ influx was abolished and reversed by the cell-impermeant thiol-reducing agent dithiothreitol, indicating the regulation by oxidation of vicinal thiols on the cell surface. Consistent with this view, Ca2+ influx was blocked by the glutathione peroxidase mimetic ebselen (2-phenyl-1,2-benzisoselenazol-3(2H)-one) and the superoxide dismutase mimetic manganese(III) tetrakis 4-(benzoic acid)porphyrin, but not by exogenously added catalase or superoxide dismutase. These findings indicate that silver evokes the release of ROS and oxidation of thiols critical for the activation of a Ca2+ channel other than SOC. Such a novel ROS-dependent pathway might play a role in mast cell degranulation in metal-induced allergic and autoimmune reactions.

Animals↗

Influence of synthetic parameters on the size, structure, and stability of dodecanethiol-stabilized silver nanoparticles.

Metal nanoparticles (NP) are very attractive because of their size- and shape-dependent properties. A widely used preparation of ligand-stabilized metal NP is the two-phase liquid-liquid method using dodecanethiol (DT) as ligand. This work presents various procedures to synthesize dodecanethiol-capped silver NPs, all of them based on a two-phase liquid-liquid method. Small alterations in the synthetic parameters lead to dramatic modifications in the nanoparticles' average size, size distribution width, stability, and structure, as well as in their ability to self-assemble.

Chemical Phenomena↗

Synthesis of Ag-Fe3O4 heterodimeric nanoparticles.

We report a general synthetic method for construction of size-controlled Ag-Fe3O4 heterodimeric nanoparticles using the Fe3O4 nanoparticles as the seeds. The Ag-Fe3O4 heterodimeric nanoparticle can be controlled by tuning the size of the Fe3O4 seed and reaction conditions for synthesis of the Ag nanoparticles grown on it. The as-synthesized nanoparticles can be readily converted into aqueous-soluble form with newly introduced functional groups on the surface of Ag-Fe3O4 heterodimeric nanoparticles.

Dimerization↗

Induction of apoptosis in yeast and mammalian cells by exposure to 1,10-phenanthroline metal complexes.

1,10-Phenanthroline (phen) and metal-phen complexes display fungicidal and fungiststic activity, disrupt mitochondrial function and induce oxidative stress. We have examined the effect of these drugs on the structure of yeast and mammalian cell organelles and the integrity of cellular DNA. Exposure of Candida albicans to [Mn(phen)2(mal)].2H2O or [Ag2(phen)3(mal)].2H2O (mal H2 = malonic acid) resulted in DNA degradation whereas exposure to phen or [Cu(phen)2(mal)].2H2O did not. All drugs induced extensive changes to the internal structure of yeast cells including retraction of the cytoplasm, nuclear fragmentation and disruption of the mitochondrion. In the case of cultured mammalian cells [Cu(phen)2(mal)].2H2O induced apoptosis as evidenced by the ladder pattern of DNA fragments following gel electrophoresis and also the blebbing of the cell membrane. The other drugs produced non-specific DNA degradation in mammalian cells. In conclusion, phen and metal-phen complexes have the potential to induce apoptosis in fungal and mammalian cells. Given their distinct mode of action compared to conventional anti-fungal drugs, phen and metal-phen complexes may represent a novel group of anti-fungal agents for use either in combination with existing drugs or in cases where resistance to conventional drugs has emerged.

Antifungal Agents↗