Psychometric properties of the Cognitive Emotion Regulation Questionnaire (CERQ) in Spanish older adults.

The Cognitive Emotion Regulation Questionnaire (CERQ) assesses nine cognitive strategies used to cope with negative events. The aim of this study was to generate validity evidences of this instrument in an older Spanish population. The Spanish version of the CERQ (CERQ-S) and self-report scales, measuring psychological well-being, depression and resilience, were administered to 305 older adults aged 65-90 (70.0 ± 4.7) residents in the Autonomous Community of Madrid, Spain. 150 participants completed the 6-month follow-up in April 2020 (during the COVID-19 pandemic). Confirmatory factor analyses supported 9-strategy structure, with an improved fit 27-item version (CERQ-S-27). Generally adequate composite reliability (CR between 0.63 and 0.84) and temporal stability (ICC between 0.38 and 0.71; p < 0.001) were found. Subscales correlated coherently with measures of depression, well-being and resilience, and T-tests indicated different use between older adults who did or did not have depressive symptoms. Multiple linear regression analysis indicated that subscales predicted depressive symptoms (R2 = 0.17; p < 0.001) and psychological well-being after six months (R2 = 0.21; p < 0.001). Results provided evidences of concurrent, predictive and criterion validity, suggesting that the CERQ-S-27 could be useful for studying use of cognitive emotion regulation strategies among older adults and understanding their influence in ageing and mental health.

Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs.

The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in neoplastic cell lines.

Design, Preparation, and Characterization of Zn and Cu Metallopeptides Based On Tetradentate Aminopyridine Ligands Showing Enhanced DNA Cleavage Activity.

The conjugation of redox-active complexes that can function as chemical nucleases to cationic tetrapeptides is pursued in this work in order to explore the expected synergistic effect between these two elements in DNA oxidative cleavage. Coordination complexes of biologically relevant first row metal ions, such as Zn(II) or Cu(II), containing the tetradentate ligands 1,4-dimethyl-7-(2-pyridylmethyl)-1,4,7-triazacyclononane ((Me2)PyTACN) and (2S,2S')-1,1'-bis(pyrid-2-ylmethyl)-2,2'-bipyrrolidine ((S,S')-BPBP) have been linked to a cationic LKKL tetrapeptide sequence. Solid-phase synthesis of the peptide-tetradentate ligand conjugates has been developed, and the preparation and characterization of the corresponding metallotetrapeptides is described. The DNA cleavage activity of Cu and Zn metallopeptides has been evaluated and compared to their metal binding conjugates as well as to the parent complexes and ligands. Very interestingly, the oxidative Cu metallopeptides 1Cu and 2Cu show an enhanced activity compared to the parent complexes, [Cu(PyTACN)](2+) and [Cu(BPBP)](2+), respectively. Under optimized conditions, 1Cu displays an apparent pseudo first-order rate constant (kobs) of ∼0.16 min(-1) with a supercoiled DNA half-life time (t1/2) of ∼4.3 min. On the other hand, kobs for 2Cu has been found to be ∼0.11 min(-1) with t1/2 ≈ 6.4 min. Hence, these results point out that the DNA cleavage activities promoted by the metallopeptides 1Cu and 2Cu render ∼4-fold and ∼23 rate accelerations in comparison with their parent Cu complexes. Additional binding assays and mechanistic studies demonstrate that the enhanced cleavage activities are explained by the presence of the cationic LKKL tetrapeptide sequence, which induces an improved binding affinity to the DNA, thus bringing the metal ion, which is responsible for cleavage, in close proximity.

Preparation of new half sandwich ruthenium arene complexes with aminophosphines as potential chemotherapeutics.

Aminophosphines 2-(diphenylphosphino)-1-methylimidazole (dpim) and diphenyl-2-pyridylphosphine (PPh(2)py) have been used to prepare two series of Ru(II) arene complexes of formulae [(η(6)-p-cymene)Ru(κ(2)-O,O'-X)(κ(1)-P-dpim)]Y (series a: 1a·Y-3a·Y) and [(η(6)-p-cymene)Ru(κ(2)-O,O'-X)(κ(1)-P-PPh(2)py)]Y (series b: 1b·Y-3b·Y) (where X=acac, acetylacetonate; bzac, benzoyl acetonate; dbzm, dibenzoyl methanoate; Y=BF(4), BPh(4)). The structures of 1a·BF(4), 1a·BPh(4), 3a·BF(4), 1b·BPh(4) and 3b·BPh(4) were determined by X-ray diffraction. The tetrafluoroborate derivatives are more soluble in organic solvents than their tetraphenylborate counterparts. Five BF(4)(-) derivatives (all except the unstable 1b·BF(4)) were selected to evaluate the cytotoxic behavior in vitro against the human cancer cell lines MCF-7 (breast cancer) and CAPAN-1 (pancreatic cancer). 2b·BF(4) and 3b·BF(4) exhibited IC(50) values similar to those of cisplatin. Electrophoresis and AFM studies showed good correspondence between the biological activity levels of 2b·BF(4) and 3b·BF(4) and their ability to modify the DNA structure. Hydrolytic studies indicate that aquation could be involved in the activation mechanism of these complexes and confirm that the hydrolysis rate of 3b·BF(4) is higher than that of 3a·BF(4). Thus, the cytotoxic activity trends are explained in terms of the higher reactivity of derivatives from series b, which in turn is rationalized as being the result of the electronic features of dpim and PPh(2)py established by cyclic voltammetry measurements.

[Assessment of emotional reactivity to food images in bulimia nervosa]. / Evaluación de la reactividad emocional ante imágenes de comida en bulimia nerviosa.

The aim of the study was to assess the influence on reactivity to food images of the following variables: craving-trait, positive or negative mood state, and food restriction. Emotional modulation of the defense startle reflex (RMS) was assessed in 26 women at risk of suffering from bulimia nervosa; they were assigned one of to two groups: high craving-trait and low craving-trait. Before the test, positive or negative mood and restriction vs. non-restriction states were induced in each of the groups. Skin conductance response (SCR) and electromyogram activity from the orbiculari oculi region were recorded after the auditory stimuli; questionnaires such as Food Craving Trait Questionnaire (FCQ-T) and the Self-assessment Manikin (SAM) were used. Results showed that negative affect produced a negative valence of food images, more arousal, and more loss of control, as well as higher SCRs. Subjects with low FCQ-T levels reduced their RMS to food images as a consequence of experiencing positive emotions; when emotions were negative, their RMS increased.

Ligand influence over the formation of dinuclear [2+2] versus trinuclear [3+3] Cu(I) Schiff base macrocyclic complexes.

The preparation and characterization of three new macrocyclic ligands with pendant arms based on the [2+2] condensation of isophthalaldehyde and the corresponding triamine substituted at the central N-atom is reported. None of these new macrocyclic ligands undergo any equilibrium reaction, based on imine hydrolysis to generate [1+1] macrocyclic formation or higher oligomeric compounds, such as [3+3], [4+4], etc., at least within the time scale of days. This indicates the stability of the newly generated imine bond. In sharp contrast, the reaction of the [2+2] macrocyclic Schiff bases with Cu(I) generates the corresponding dinuclear Cu(I) complexes [Cu(2)(L(1))](2+), 1(2+); [Cu(2)(L(2))(CH(3)CN)(2)](2+), 2(2+); and [Cu(2)(L(3))(CH(3)CN)(2)](2+), 3(2+), together with their trinuclear Cu(I) homologues [Cu(3)(L(4))](3+), 4(3+); [Cu(3)(L(5))(CH(3)CN)(3)](3+), 5(3+); and [Cu(3)(L(6))(CH(3)CN)(3)](3+), 6(3+), where the [2+2] ligand has undergone an expansion to the corresponding [3+3] Schiff base that is denoted as L(4), L(5), or L(6). The conditions under which the dinuclear and trinuclear complexes are formed were analyzed in terms of solvent dependence and synthetic pathways. The new complexes are characterized in solution by NMR, UV-vis, and MS spectroscopy and in the solid state by X-ray diffraction analysis and IR spectroscopy. For the particular case of the L(2) ligand, MS spectroscopy is also used to monitor the metal assisted transformation where the dinuclear complex 2(2+) is transformed into the trinuclear complex 5(3+). The Cu(I) complexes described here, in general, react slowly (within the time scale of days) with molecular oxygen, except for the ones containing the phenolic ligands 2(2+) and 5(3+) that react a bit faster.

[Successful aging: criteria and predictors]. / Envejecimiento con éxito: criterios y predictores.

In the Anglo-Saxon scientific literature, successful aging has been consolidated during the last four decades. Nevertheless, several terms have been used as synonymous: healthy, active, productive, optimal, positive aging. Although, all these terms have been described through a broad set of bio-psycho-social factors, usually, research in this field reduces successful aging to daily life functioning and physical health. Also, in spite of the fact that authors consider that determinants might be multi-domain, empirical research usually reduces them to life styles. Logically, the prevalence of this kind of ageing found empirically is not very consistent and research of its determinants or predictors refers to biomedical conditions. In this study, data from 458 participants (170 males and 288 females; mean age: 66.47, range: 55-75) from ELEA ("Longitudinal Study of Active Aging") were examined. The results show (depending on the simple or multidimensional definitions used) a very varied range of proportions of successfully aging older persons as well as a large number of multi-domain predictors of successful ageing, among which are intelligence, personality and motivational psychological characteristics.

DNA-cleavage induced by new macrocyclic Schiff base dinuclear Cu(I) complexes containing pyridyl pendant arms.

A new series of dinuclear Cu(I) complexes with hexaazamacrocyclic Schiff base ligand containing pyridyl pendant arms has been synthesized and characterized. The solid-state structures of [Cu(2)(I)(bsp3py)](CF(3)SO(3))(2) (1(CF(3)SO(3))(2)), [Cu(2)(I)(bsm3py)](SbF(6))(2) (2(SbF(6))(2)), and [Cu(2)(I)(bsp2py)](CF(3)SO(3))(2) (3(CF(3)SO(3))(2)) have been established by single-crystal X-ray diffraction analysis. The geometries of the copper centers in all three cases are almost identical showing a distorted tetrahedral coordination, very close to a trigonal pyramidal arrangement. Interactions of complexes with calf thymus DNA have been investigated by circular dichroism spectroscopy (CD) which suggests that the interaction for each complex is a nonintercalative mode with regard to DNA. The electrophoretic mobility study and the atomic force microscopy (AFM) in the presence of H(2)O(2) reveal a cleavage of pBR322 supercoiled DNA that depends on the nature of the Cu(I) complex used. The most efficient reactivity is observed for complexes 1(CF(3)SO(3))(2) and 2(CF(3)SO(3))(2) whereas complex 3(CF(3)SO(3))(2) displays a lesser reactivity. The different DNA-cleavage activity of complexes 1-3 is due the different electronic factors and complex topology induced by the natures of the different ligands. This work constitutes an example of how small modifications introduced in the macrocyclic backbone of the metal complexes lead to dramatic changes in the nuclease activity.

Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a Cu(II) complex.

The spontaneous oxidation of an amine group to an imine has been observed experimentally in an octa-aza macrocyclic dinucleating ligand LH(4) coordinated to Cu(II). The reaction is bimolecular and spontaneous in which amine groups of one macrocycle are oxidised and the Cu(II) centres of a second macrocyclic complex are reduced. No additional oxidating or external base agents are required. DFT calculations are carried out to compare the reaction with that recently reported for a ligand coordinated to an Fe(III) centre, but which requires an external base as proton acceptor. The computational results show that the copper and iron catalysed amine to imine reactions proceed via different mechanisms.

Anti-cyclic citrullinated peptide and anti-keratin antibodies in patients with idiopathic inflammatory myopathy.

OBJECTIVE: To investigate the prevalence of anti-cyclic citrullinated peptide (anti-CCP) and anti-keratin antibodies (AKAs) in a cohort of patients with idiopathic inflammatory myopathy. METHODS: In a cross-sectional study, we determined the presence of anti-CCP and AKAs by ELISA and IIF, respectively, in a cohort of 90 consecutive patients with idiopathic inflammatory myopathy. Associations between anti-CCP and clinical manifestations or other autoantibodies were determined with the chi-square and Mann-Whitney U-tests. Radiographs of hands were retrospectively evaluated. Serum autoantibody profile was determined in all patients. RESULTS: Twelve patients were positive to anti-CCP (13.3%); in eight cases values were moderate-high. AKAs were not detected in any patient. Comparison between patients positive and negative to anti-CCP did not show clinical or biological differences. Arthritis joint erosions or positive status to anti-synthetase antibodies were not more frequent in patients with anti-CCP antibodies. Prevalence of RF was the only variable significantly associated with the presence of these antibodies (P = 0.043). CONCLUSIONS: High titres of anti-CCP can occasionally be found in patients with inflammatory myopathy. Therefore, a possible diagnosis of RA should be considered with caution in these patients.

Fine-tuning ligand-receptor design for selective molecular recognition of dicarboxylic acids.

The host-guest interaction between the hexaaza macrocyclic ligand 3,7,11,18,22,26-hexaazatricyclo[26.2.2.2]tetratriaconta-1(31),13(34),14,16(33),28(32),29-hexaene (P3) and three rigid dicarboxylic acids (isophthalic acid, H2is; phthtalic acid, H2ph; and terephthalic acid, H2te) has been investigated using potentiometric equilibrium methods and NMR spectroscopy including the measurement of intermolecular nuclear Overhauser effects (NOEs) and self-diffusion coefficients (D). Ternary complexes are formed in aqueous solution as a result of hydrogen bond formation and Coulombic interactions between the host and the guest. In the [(H6P3)(is)]4+ complex, those bonding interactions reach a maximum yielding a log K6R of 4.74. Competitive distribution diagrams and total species distribution diagrams are used to illustrate the main features of these systems. In particular, a selectivity of over 89% at p[H] = 5.0 is obtained for the complexation of the is versus the te substrates. The recognition capacity of P3 over dicarboxylic acids (da) is compared to the related hexaaza macrocycle Me2P3 (7,22-dimethyl-3,7,11,18,22,26-hexaazatricyclo[26.2.2.2]tetratriaconta-1(30),13,15,28,31,33-hexaene) that binds da with a lesser strength, and it is not selective. Theoretical calculations performed at molecular dynamics level have also been carried out and point out that the origin of selectivity is mainly due to the capacity of the P3 ligand receptor to adapt to the geometry of the dicarboxylic acid to form relatively strong hydrogen bonds.

Coronary effects of endothelin-1 and vasopressin during acute hypotension in anesthetized goats.

Coronary effects of endothelin-1 and vasopressin during acute hypotension, and the role of NO and prostanoids in these effects were examined in anesthetized goats. Left circumflex coronary artery flow was measured electromagnetically, and hypotension was induced by constriction of the caudal vena cava in animals non-treated (7 goats) or treated with the inhibitor of NO synthesis N(w)-nitro-L-arginine methyl esther (L-NAME, 5 goats), the cyclooxygenase inhibitor meclofenamate (5 goats) or both drugs (5 goats). Under normotension (22 goats), mean arterial pressure averaged 93 +/- 3 mm Hg and coronary vascular conductance (CVC) 0.37 +/- 0.025 ml/min/mm Hg. Endothelin-1 (0.01-0.3 nmol) and vasopressin (0.03-1 nmol), intracoronarily injected, dose-dependently decreased CVC by up to 56% for endothelin-1 and 40% for vasopressin. During hypotension in every condition tested, mean arterial pressure decreased to approximately 60 mm Hg, and CVC only decreased during hypotension pretreated with L-NAME (23%) or L-NAME + meclofenamate (34%). Under non-treated hypotension, the decreases in CVC by endothelin-1 were augmented approximately 1.5 fold, and those by vasopressin were not modified. This increase in CVR by endothelin-1 was not affected by L-NAME and was reversed by meclofenamate or L-NAME + meclofenamate. The coronary effects of vasopressin were not modified by any of these treatments. Therefore, acute hypotension increases the coronary vasoconstriction in response to endothelin-1 but not to vasopressin. This increased response to endothelin-1 may be related to both inhibition of NO release and release of vasoconstrictor prostanoids.