Northernmost occurrence of the offshore rockfish, <i>Pontinus kuhlii</i> (Scorpaeniformes: Scorpaenidae), in the Mediterranean sea

An adult male specimen of the offshore rockfish, Pontinus kuhlii (Bowdich, 1825), was caught off the coast of Alghero (NW Sardinia, Italy) in August 2004. That capture represents the second documented record of this Atlantic migrant in Italian waters, after more than a century from the first report. Furthermore, the new specimen is the largest specimen of this species ever recorded in the Mediterranean Basin and the most northern capture for this geographic area. Morphologic and meristic characters of the collected fish are described and the existence of a Mediterranean population is hypothesized

Synthesis, Stability Constant Determination, and Structural Study of Some Complexes of a Zinc Triad Containing Pyridyl-amine-quinoline and Pyridyl-thio-quinoline

The potentially fluorescent and terdentate ligands containing nitrogen or sulfur as coordinating atom were synthesized and used in the formation of perchlorate or chloride complexes of the metals of the Zn triad. The reaction of the ligands with metal perchlorate salts yields the corresponding bis-chelate derivatives, whereas the same ligands react with metal chloride salts to give monochelate complexes. All of these complexes undergo NMR-scale fast fluxional rearrangement in solution. Some structural X-ray diffractometric studies were also performed and the ensuing data confirm the surmised structures and the solution rearrangement in the case of monochelate substrates and of one Hg derivative, respectively. The equilibrium constants of formation in the case of monochelate derivatives were also determined in water by means of spectrophotometric titration of the studied ligand with the metal ions. The values of the equilibrium constants were confirmed by supplementary determination taking into account the exchange between two different metals and/or dissociation equilibria. The fluorescence activity of ligands and complexes was eventually studied and notably one fluorescent silent ligand gives rise to fluorescent zinc derivatives

Exploring the Role of Killer Cell Immunoglobulin-Like Receptors and Their HLA Class I Ligands in Autoimmune Hepatitis

Background Natural killer cells are involved in the complex mechanisms underlying autoimmune diseases but few studies have investigated their role in autoimmune hepatitis. Killer immunoglobulin-like receptors are key regulators of natural killer cell-mediated immune responses. Methods and Findings KIR gene frequencies, KIR haplotypes, KIR ligands and combinations of KIRs and their HLA Class I ligands were investigated in 114 patients diagnosed with type 1 autoimmune hepatitis and compared with a group of 221 healthy controls. HLA Class I and Class II antigen frequencies were compared to those of 551 healthy unrelated families representative of the Sardinian population. In our cohort, type 1 autoimmune hepatitis was strongly associated with the HLA-B18, Cw5, DR3 haplotype. The KIR2DS1 activating KIR gene and the high affinity HLA-C2 ligands were significantly higher in patients compared to controls. Patients also had a reduced frequency of HLA-Bw4 ligands for KIR3DL1 and HLA-C1 ligands for KIR2DL3. Age at onset was significantly associated with the KIR2DS1 activating gene but not with HLA-C1 or HLA-C2 ligand groups. Conclusions The activating KIR gene KIR2DS1 resulted to have an important predictive potential for early onset of type 1 autoimmune hepatitis. Additionally, the low frequency of the KIR-ligand combinations KIR3DL1/HLA-Bw4 and KIR2DL3/HLA-C1 coupled to the high frequency of the HLA-C2 high affinity ligands for KIR2DS1 could contribute to unwanted NK cell autoreactivity in AIH-1

Insertion of Substituted Alkynes into the Pd-C Bond of Methyl and Vinyl Palladium(II) Complexes Bearing Pyridylthioethers as Ancillary Ligands. The Influence of Ligand Substituents at Pyridine and Sulphur on the Rate of Insertion

The palladium(II) chloro methyl complexes bearing the bidentate 6-R-C5H3N-2-CH2SR' (RN-SR'; R = H, Me, Cl; R' = Me, t-Bu, Ph) and the potentially terdentate 2,6-(CH2SR')(2)-C5H3N (S-N-S(R'); R'= Me, t-Bu, Ph) pyridylthioethers as ancillary ligands were synthesized, characterized, and reacted with substituted alkynes ZC equivalent to CZ (Z = COOMe, Z' = COOt-Bu, Z" = COOEt). The reactions were followed under second-order conditions by H-1 NMR technique, and the reaction rates were determined. The corresponding vinyl derivatives were synthesized, and in the case of the complexes [PdCl(ZC=CZMe)(MeN-SPh)] and [PdCl(ZC= CZMe)(C1N-St-Bu)] (Z = COOMe) reaction rates for alkyne insertion yielding the corresponding butadienyl complexes were also determined. The rate of insertion of the second alkyne on the vinyl complex is more than 3 orders of magnitude lower than the first insertion rate in both the studied complexes, thereby allowing easy separation between vinyl and butadienyl derivatives and an easy preparation of mixed butadienyl esters. Furthermore, the reaction rates are strongly dependent on the steric and electronic features of the ancillary ligands. In particular, the distortion of the complex main coordination plane, induced by the substituent in position 6 of the pyridine ring, was found to significantly influence the substrate reactivity. The structures of the mono-inserted vinyl [PdCl(ZC CZMe)(MeN-St-Bu)] (1) and the bis-inserted butadienyl [PdCl((ZC=CZ)(2)Me)(MeN-St-Bu)] (2) complexes were determined by X-ray diffraction, and the persistence of a structural distortion of the complex skeleton was observed. Moreover, the distortion may be related to facile ancillary ligand displacement, a feature that can be exploited for the synthesis of substrates that would not be easily obtained otherwise

Sorption and separation of palladium, platinum and gold chlorocomplexes by means of a dipicolinic acid polystyrene-based chelating resin

A chelating ion-exchange resin containing dipicolinic acid as functional group and based on microporous chloromethylated cross-linked polystyrene-divinylbenzene (2 %) copolymer has been prepared. Its sorption and desorption characteristics for Pd(II), Pt(II), Pt(IV) and Au(III) have been studied in aqueous chloride solutions under a number of experimental conditions, both in batch and in column, at room temperature and constant ionic strength (μ = 1 mol/l, KCl/ HCl). In column operations at pH 6, Pd(II) can be separated from Pt(H) or Pt(IV) owing to the different rate of formation of the immobilized chelated species. From a mixture of Pd(II, Pt(IV) and Au(III) at pH 6, Pt(IV) flows unaffected, whereas Au(III) and Pd(II) are both retained and successively separated by selective elution. From the same mixture at pH ≤ 0 only Au(III) is sorbed by anionic exchange. © 1991

Combined Salivary Proteome Profiling and Machine Learning Analysis Provides Insight into Molecular Signature for Autoimmune Liver Diseases Classification

Autoimmune hepatitis (AIH) and primary biliary cholangitis (PBC) are autoimmune liver diseases that target the liver and have a wide spectrum of presentation. A global overview of quantitative variations on the salivary proteome in presence of these two pathologies is investigated in this study. The acid-insoluble salivary fraction of AIH and PBC patients, and healthy controls (HCs), was analyzed using a gel-based bottom-up proteomic approach combined with a robust machine learning statistical analysis of the dataset. The abundance of Arginase, Junction plakoglobin, Desmoplakin, Hexokinase-3 and Desmocollin-1 decreased, while that of BPI fold-containing family A member 2 increased in AIHp compared to HCs; the abundance of Gelsolin, CD14, Tumor-associated calcium signal transducer 2, Clusterin, Heterogeneous nuclear ribonucleoproteins A2/B1, Cofilin-1 and BPI fold-containing family B member 2 increased in PBCp compared to HCs. The abundance of Hornerin decreased in both AIHp and PBCp with respect to HCs and provided an area under the ROC curve of 0.939. Machine learning analysis confirmed the feasibility of the salivary proteome to discriminate groups of subjects based on AIH or PBC occurrence as previously suggested by our group. The topology-based functional enrichment analysis performed on these potential salivary biomarkers highlights an enrichment of terms mostly related to the immune system, but also with a strong involvement in liver fibrosis process and with antimicrobial activity