A sex-dependent algorithm including kappa free light chain for multiple sclerosis diagnosis.

Multiple sclerosis (MS) diagnosis includes the presence of restricted oligoclonal bands (OCB) in cerebrospinal fluid (CSF), but it has several limitations, as it is an observer-dependent time-consuming technique and offers a dichotomous result. Thus kappa free light chains (KFLC) have emerged as a quantitative alternative. However, the cut-off values for KFLC have not been well established yet and it is not clear if differences between sexes exist.

Biochemical biomarkers for multiple sclerosis.

Introduction: Multiple sclerosis (MS) is the most frequent demyelinating disease of the central nervous system. Although there is currently no definite cure for MS, new therapies have recently been developed based on a continuous search for new biomarkers.

Development: MS diagnosis relies on the integration of clinical, imaging and laboratory findings as there is still no singlepathognomonicclinical feature or diagnostic laboratory biomarker.

Tungiasis in a southern tamandua (Tamandua tetradactyla) from Formosa province, Argentina.

Tunga penetrans causes tungiasis, a parasitic disease of humans and domestic animals. In this work we report the presence of tungiasis in the southern tamandua (Tamandua tetradactyla) from Formosa, Argentina. An individual of southern tamandua was found dead on the roadside and it presented lesions consisted with neosomes located on its four limbs.

Coordination Chemistry of Cu Complexes of Small N-Alkylated Tetra-azacyclophanes with SOD Activity.

A new tetraaza-pyridinophane macrocycle (L1) N-alkylated with two isopropyl and one methyl groups symmetrically disposed has been prepared and its behavior compared with those of the unsubstituted pyridinophane (L3) and the related compound with three methyl groups (L2). The protonation studies show that, first, a proton binds to the central methylated amine group of L1, while, second protonation leads to a reorganization of the protons that are at this stage attached to the lateral isopropylated amines. The X-ray structure of [HL1] agrees with the UV-vis and NMR studies as well as with the results of DFT calculations.

A Potential New Threat to Wild Life: Presence of UV Filters in Bird Eggs from a Preserved Area.

The present study uses bird eggs of seven wild species as a biomonitoring tool for sunscreens occurrence. Seven UV filters (UV-Fs), including 3 hydroxy-metabolites of oxybenzone (benzophenone 3, BP3) were characterized in unhatched eggs from Doñana Natural Space (Spain). High frequency of detection was observed for all UV-Fs, ranging from 95% to 100%.

Pyrethroid insecticides in wild bird eggs from a World Heritage Listed Park: A case study in Doñana National Park (Spain).

Recent studies demonstrated that the common pyrethroid insecticides are present in aquatic biota tissues. In this study, 123 samples of unhatched eggs of 16 wild bird species collected from 2010 to 2012 in Doñana National and Natural Park were analysed to determine 13 pyrethroids. This study represents the first time that pyrethroids are detected in tissues of terrestrial biota, 93% of these samples being positive to those pollutants.

Temporal trends in classical and alternative flame retardants in bird eggs from Doñana Natural Space and surrounding areas (south-western Spain) between 1999 and 2013.

Several halogenated flame retardants were detected in black kite, white stork and greater flamingo unborn eggs from Doñana Natural Space (Spain) collected in 1999, 2003, 2011 and 2013. The main components of Penta-BDE commercial mixture (BDE-47, -99 and -100) showed a decrease in the studied time interval, concurring with the ban of this mixture in the European Union (EU) in 2006. On the other hand, BDE-209, the main component of Deca-BDE mixture showed a clear trend in black kites but further monitoring is needed since its production ceased at the end of 2013.

Bioaccumulation and biomagnification of emerging and classical flame retardants in bird eggs of 14 species from Doñana Natural Space and surrounding areas (South-western Spain).

The occurrence of classical (polybrominated diphenyl ethers, PBDEs) and emerging FRs (dechloranes, hexabromobenzene (HBB), pentabromoethyl benzene (PBEB) and decabromodiphenyl ethane (DBDPE)) in unborn eggs of 14 different species from Doñana Natural Space and surrounding areas was studied. PBDEs, Dec-602, Dec-603 and DP were detected in all the species, whereas HBB, PBEB, DBDPE and Dec-604 were not detected in any sample. ΣPBDE and ΣDechlorane levels ranged from 1.

Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu(2+)metal ions within polytopic receptors.

Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out.

Structural reorganisation in polytopic receptors revealed by kinetic studies.

One of the first kinetic studies of metal ion reorganisation between the different sites of a tritopic polyaza ligand reveals well defined pathways for the movement of the metal ion.

Hydrogen and copper ion induced molecular reorganizations in two new scorpiand-like ligands appended with pyridine rings.

The synthesis of two new ligands constituted of a tris(2-aminoethyl)amine moiety linked to the 2,6 positions of a pyridine spacer through methylene groups in which the hanging arm is further functionalized with a 2-pycolyl (L1) or 3-pycolyl (L2) group is presented. The protonation of L1 and L2 and formation of Cu(2+) complexes have been studied using potentiometric, NMR, X-ray, and kinetic experiments. The results provide new information about the relevance of molecular movements in the chemistry of this kind of so-called scorpiand ligand.

Geometric isomerism in pentacoordinate Cu2+ complexes: equilibrium, kinetic, and density functional theory studies reveal the existence of equilibrium between square pyramidal and trigonal bipyramidal forms for a tren-derived ligand.

A ligand (L1) (bis(aminoethyl)[2-(4-quinolylmethyl)aminoethyl]amine) containing a 4-quinolylmethyl group attached to one of the terminal amino groups of tris(2-aminoethyl)amine (tren) has been prepared, and its protonation constants and stability constants for the formation of Cu(2+) complexes have been determined. Kinetic studies on the formation of Cu(2+) complexes in slightly acidic solutions and on the acid-promoted complex decomposition strongly suggest that the Cu(2+)-L1 complex exists in solution as a mixture of two species, one of them showing a trigonal bipyramidal (tbp) coordination environment with an absorption maximum at 890 nm in the electronic spectrum, and the other one being square pyramidal (sp) with a maximum at 660 nm. In acidic solution only a species with tbp geometry is formed, whereas in neutral and basic solutions a mixture of species with tbp and sp geometries is formed.

Participatory dam systems modelling: a case study of the transboundary Guadiana River in the Iberian Peninsula.

Modelling tools have been widely used to investigate best management practices. But in contrast to the plethora of modelling studies, the practical implementation of outcomes is comparatively small. There is an urgent need to implement results and to show the practical validation of the concept developed, especially against the context of water stress mitigation.

Hydrogen and copper ion-induced molecular reorganizations in scorpionand-like ligands. A potentiometric, mechanistic, and solid-state study.

Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two of its arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been further functionalized with a fluorophoric naphthalene group.

Crucial role of anions on the deprotonation of the cationic dihydrogen complex trans-[FeH(eta2-H2)(dppe)2]+.

The kinetics of reaction of the dihydrogen complex trans-[FeH(eta2-H2)(dppe)2]+ with an excess of NEt3 to form cis-[FeH2(dppe)2] shows a first-order dependence with respect to both the metal complex and the base. The corresponding second-order rate constant only shows minor changes when the solvent is changed from THF to acetone. However, the presence of salts containing the BF4-, PF6-, and BPh4- anions causes larger kinetic changes, the reaction being accelerated by BF4- and PF6- and decelerated in the presence of BPh4-.

Ag(I) complexes with alkylidene-bis(2-aminopyrimidines) as building units for discrete metallomacrocyclic frames. A structural and solution study.

Alkylidene-bis(2-aminopyrimidines) (pyr2Cx, x = 2-5) are useful ligands to interact with Ag(I) yielding discrete metallocycles. Crystal structures of the [(pyr2C2)Ag(NO3)]2 and [(H-pyr2C4)Ag(NO3)2]2 have been isolated where each macrocyclic moiety interacts with their surroundings through weak interactions, yielding 3D discrete structures, On the other hand, the solution study shows that the equilibrium constants for the formation of Ag(pyr2Cx)+ complexes are higher than the literature values for Ag(I) complexes with single pyrimidines, although the differences could be explained by invoking the solid-state structures of the Ag(I)-pyr2Cx complexes.

Levels of persistent organochlorine residues in eggs of greater flamingos from the Guadalquivir marshes (Doñana), Spain.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) residue levels were determined in 53 unhatched eggs from greater roseus flamingos (Phoenicopterus ruber). Eggs were collected in 1996 from the National Park of Doñana (Guadalquivir marshes, Southwest Spain), immediately after one breeding colony abandoned the nesting site due to predator attacks. The main metabolite of p,p'-DDT, p,p'-DDE, was the OCP residue found at higher concentrations, with a geometric mean of 721 ng/g wet weight.

Stability and kinetics of the acid-promoted decomposition of Cu(II) complexes with hexaazacyclophanes: kinetic studies as a probe to detect changes in the coordination mode of the macrocycles.

The synthesis, protonation and Cu(II) coordination features of the novel azacyclophane type receptors 2,6,10,13,17,21-hexaza[22]-(2,6)-pyridinophane (L2), 2,6,9,12,15,19-hexaza[20]-(2,6)-pyridinophane (L5) and 2,6,9,12,15,19-hexaza[20]metacyclophane (L6) are presented. The protonation and Cu(II) constants are analysed and compared with the previously reported open-chain polyamines 4,8,11,15-tetrazaoctadecane-1,18-diamine (L1) and 4,7,10,13-tetraazahexadecane-1,16-diamine (L4) and of the cyclophane 2,6,10,13,17,21-hexaaza[22]paracyclophane (L3). All the systems form mono- and dinuclear complexes whose stability and pH range of existence depend on the type of hydrocarbon chains and molecular topology.

The effect of the "inert" counteranions in the deprotonation of the dihydrogen complex trans-[FeH(eta 2-H2)(dppe)2]+: kinetic and theoretical studies.

Kinetic studies indicate that trans-[FeH(H2)(dppe)2]+ reacts with an excess of NEt3 to form cis-[FeH2(dppe)2] in a single kinetic step. The second-order rate constant is strongly affected by the presence of added salts, an acceleration being observed with BF4- and PF6- salts and a deceleration with BPh4-. Theoretical calculations indicate that the role of the accelerating anions consists of the formation of ion pairs that provide a more effective reaction pathway for deprotonation.

Hydrogen-ion driven molecular motions in Cu2+-complexes of a ditopic phenanthrolinophane ligand.

One of the first kinetic evaluations of a metal ion interchange between the two coordination sites of a ditopic macrocycle is presented.

Synthesis, equilibrium studies and structural characterisation of the Zn(II) complexes with trimethylene-N6,N6'-bisadenine.

The new compound trimethylene-N(6),N(6')-bisadenine (L), in which two adenine molecules are linked together by a trimethylene bridge that connects the N(6) atoms, has been prepared. Reaction of L with HgCl(2) and ZnCl(2) in concentrated HCl solution leads to crystalline solids. The X-ray characterisation of the Hg(II) complex (H(2)L)[HgCl(4)].

Mechanisms of Reactions of Dihydrogen Complexes: Formation of trans-[RuH(H(2))(dppe)(2)](+) and Substitution of Coordinated Dihydrogen.

The reactions between cis-[RuH(2)(DPPE)(2)] and a number of acids in THF solution (DPPE = Ph(2)PCH(2)CH(2)PPh(2)) show biphasic kinetics, with initial formation of trans-[RuH(H(2))(DPPE)(2)](+) followed by slower substitution of coordinated dihydrogen by the anion of the acid. The formation of the dihydrogen complex is a second-order process that occurs with an inverse kinetic isotope effect and rate constants k(HX) strongly dependent on the nature of the acid. There is a linear correlation between the values of log k(HX) for cis-[RuH(2)(DPPE)(2)] and the related cis-[FeH(2)(PP(3))] [PP(3) = P(CH(2)CH(2)PPh(2))(3)] that leads to two parameters, S and R, that can be used as a measure of the selectivity and intrinsic reactivity of the dihydride toward acids.

Lead shot ingestion in two raptor species from Doñana, Spain.

Diurnal raptors inhabiting wetland areas where waterfowl shooting is conducted have many opportunities to ingest lead (Pb) shot pellets when feeding on their prey. Exposure to Pb shot was studied in the Spanish imperial eagle (Aquila adalberti), an endangered species with a world population of about 150 breeding pairs, and in the red kite (Milvus milvus) from Doñana (southwest Spain). Lead exposure was evaluated by the presence of Pb shot in the pellets of both species.