Direct reactions between CuI and isonicotinic acid (HIN) or the corresponding esters, ethyl isonicotinate (EtIN) or methyl isonicotinate (MeIN), give rise to the formation of the coordination ...polymers CuI(L)n with L=EtIN (1), MeIN (2) and HIN (3). Polymers 1–3 show similar structures based on a CuI double chain in which ethyl‐, methyl isonicotinate or isonicotinic acid are coordinated as terminal ligands. Albeit, their supramolecular architecture differs considerably, affecting the distances and angles of the central CuI double chains and thereby their physical properties. Hence, the photoluminescence shows remarkable differences; 1 and 2 show a strong yellow emission, whereas 3 displays a weak emission; and 1 and 2 are semiconductors with moderate room temperature conductivities, whereas 3 has increased electrical conductivity up to 3×10−3 S cm−1. Additionally, 1 and 2 present an irreversible transition to a highly conducting phase with a conductivity almost 4 orders of magnitude higher and a quasi‐metallic behaviour. Thermogravimetric analysis (TGA) coupled to a mass spectrometer and magnetic measurements point to a partial thermally induced oxidation of the carboxylate groups of the ligands with CuI to Cu0 reduction. DFT calculations have been carried out to rationalise these observations.
In chains: Coordination polymers obtained by direct reactions between CuI and isonicotinic acid or methyl/ethyl isonicotinato esters show a structure based on a CuI double chain with a rather different supramolecular architecture, which affects the distances and angles of the central chain. These structural variations modify both the emission and electrical properties. DFT calculations have been carried out to rationalise these observations.
One-pot reactions between CuI and methyl or methyl 2-amino-isonicotinate give rise to the formation of two coordination polymers (CPs) based on double zig-zag Cu
I
chains. The presence of a NH
group ...in the isonicotinate ligand produces different supramolecular interactions affecting the Cu-Cu distances and symmetry of the Cu
I
chains. These structural variations significantly modulate their physical properties. Thus, both CPs are semiconductors and also show reversible thermo/mechanoluminescence. X-ray diffraction studies carried out under different temperature and pressure conditions in combination with theoretical calculations have been used to rationalize the multi-stimuli-responsive properties. Importantly, a bottom-up procedure based on fast precipitation leads to nanofibers of both CPs. The dimensions of these nanofibres enable the preparation of thermo/mechanochromic film composites with polyvinylidene difluoride. These films are tens of nanometers in thickness while being centimeters in length, representing smaller thicknesses so far reported for thin-film composites. This nanomaterial integration of CPs could represent a source of alternative nanomaterials for opto-electronic device fabrication.
Inhibition of cyclooxygenase-2 (COX-2) has been extensively studied as an approach to reduce proinflammatory markers in acute brain diseases, but the anti-neuroinflammatory role of cyclooxygenase-1 ...(COX-1) inhibition has been rather neglected. We report that
-terphenylamine derivatives are selective COX-1 inhibitors, able to block microglia inflammatory response and elicit a neuroprotective effect. These compounds were synthesized via a three-component reaction of chalcones, β-ketoesters, and primary amines, followed by hydrolysis/decarboxylation of the ester group. Together with their synthetic intermediates and some urea derivatives, they were studied as inhibitors of COX-1 and COX-2. The
-terphenylamine derivatives, which were selective COX-1 inhibitors, were also analyzed for their ability to block microglia inflammatory and oxidative response. Compound
presented an interesting anti-inflammatory and neuroprotective profile by reducing nitrite release, ROS overproduction, and cell death in organotypic hippocampal cultures subjected to LPS. We thus show that COX-1 inhibition is a promising approach to provide enhanced neuroprotection against acute inflammatory processes, which are crucial in the development of a plethora of acute neurodegenerative injuries.
Two coordination polymers (CPs), based on Cu(I)–I double zig-zag chains bearing isonicotinic acid or 3-chloroisonicotinic acid as terminal ligands with molecular recognition capabilities, have been ...synthesized and fully characterized. Both compounds present extended networks with supramolecular interactions directed by the formation of H-bonds between the complementary carboxylic groups, giving supramolecular sheets. The chloro substituent allows establishing additional Cl···Cl supramolecular interactions that reinforce the stability of the supramolecular sheets. These CPs are semiconductor materials; however, the presence of chlorine produces slight changes in the I–Cu–I chains, generating a worse overlap in the Cu–I orbitals, thus determining a decrease in its electrical conductivity value. These experimental results have also been corroborated by theoretical calculations using the study of the morphology of the density of states and 3D orbital isodensities, which determine that conductivity is mostly produced through the Cu–I skeleton and is less efficient in the case of the chloro derivative compound. A fast and efficient bottom-up approach based on the self-assembly of the initial building blocks and the low solutibility of these CPs has proved very useful for the production of nanostructures.
The spatial distribution and temporal trends of trace metals (i.e. Cd, Cu, Hg, Pb and Zn) and a metalloid (i.e. As) along the Spanish Mediterranean coast from 1993 to 2013 are presented with a new ...estimation of their background levels monitored using wild mussels. Over a 20 years period, yearly mussel monitoring was undertaken with a rigorous field sampling protocol using 3 pooled samples strategy (3 x n = 80, with 8 mussels in the 3.0 to 3.9 size categories at each site), obtained in the pre-spawning period (May–June) to minimize biological factors and seasonal variability, which is a fundamental element of the international programme. Spatial distribution was characterized every 5 years and temporal trends were determined in 11 locations. The main aims of the present long term study are to evaluate the environmental status of different coastal locations regarding trace metal levels and follow the evolution of these levels over time after the implementation of regulatory measures. Regarding spatial distribution, the highest values for Cd, Cu, Hg and Pb were found close to known highly anthopogenic cities or shipyard areas. However, As and Zn did not strictly follow this pattern, showing natural increased concentrations in the Levantine Balearic and Strait of Gibraltar-Alboran Sea demarcations respectively. These distributions are associated with the conjunction of two geological formation inputs (Massif Central in France and Iberian Pyritic Belt in Spain) and the oceanographic conditions in the adjacent coastal area. In the case of temporal trends, metal concentrations decreased significantly over time in most stations, confirming the effectiveness of the regulatory measures and prohibitions established under European legislation. Concentrations of Pb were above the established thresholds for human consumption in only 12–14% of the sampling areas. With the information obtained for this study, we estimate background concentrations and propose new Background Assesment Criteria (BAC) for the Spanish Mediterranean coast as a threshold criterion: 1.62 mg/kg d.w. for Cd, 8.75 mg/kg d.w. for Cu, 0.202 mg/kg d.w. for Hg and 2.83 mg/kg d.w. for Pb.
Exceptions should exist for As and Zn, for which there should be different levels in each demarcation, due to the geological, hydrological and oceanographic peculiarities of the Spanish coast. For the Levantine-Balearic demarcation, the proposed background concentrations are 117 mg/kg d.w. for As and 200 mg/kg d.w. for Zn., whereas in the Strait of Gibraltar-Alboran Sea demarcation, they are 27.5 mg/kg d.w. for As, and 471 mg/kg d.w. for Zn. This work demonstrates the vital importance of defining the background levels of metal(loid)s at a regional or subregional level because, for areas not affected by anthropogenic causes which have high values as the result of natural processes, this would avoid the risk of constantly surpassing the levels proposed in directives.
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•Metal(loid) concentrations in mussels have decreased over the years in the Spanish Coast.•Environmental regulatory measures at different scales have proved to be effective.•The geology, hydrology or oceanography of the area influences metal levels.•It is mandatory to define metal(loid) baseline levels at a regional scale.
Home respiratory polygraphy may be a simpler alternative to in-laboratory polysomnography for the management of more symptomatic patients with obstructive sleep apnea, but its effectiveness has not ...been evaluated across a broad clinical spectrum.
To compare the long-term effectiveness (6 mo) of home respiratory polygraphy and polysomnography management protocols in patients with intermediate-to-high sleep apnea suspicion (most patients requiring a sleep study).
A multicentric, noninferiority, randomized controlled trial with two open parallel arms and a cost-effectiveness analysis was performed in 12 tertiary hospitals in Spain. Sequentially screened patients with sleep apnea suspicion were randomized to respiratory polygraphy or polysomnography protocols. Moreover, both arms received standardized therapeutic decision-making, continuous positive airway pressure (CPAP) treatment or a healthy habit assessment, auto-CPAP titration (for CPAP indication), health-related quality-of-life questionnaires, 24-hour blood pressure monitoring, and polysomnography at the end of follow-up. The main outcome was the Epworth Sleepiness Scale measurement. The noninferiority criterion was -2 points on the Epworth scale.
In total, 430 patients were randomized. The respiratory polygraphy protocol was noninferior to the polysomnography protocol based on the Epworth scale. Quality of life, blood pressure, and polysomnography were similar between protocols. Respiratory polygraphy was the most cost-effective protocol, with a lower per-patient cost of 416.7€.
Home respiratory polygraphy management is similarly effective to polysomnography, with a substantially lower cost. Therefore, polysomnography is not necessary for most patients with suspected sleep apnea. This finding could change established clinical practice, with a clear economic benefit. Clinical trial registered with www.clinicaltrials.gov (NCT 01752556).
General practitioners play a passive role in obstructive sleep apnea (OSA) management. Simplification of the diagnosis and use of a semiautomatic algorithm for treatment can facilitate the ...integration of general practitioners, which has cost advantages.
To determine differences in effectiveness between primary health care area (PHA) and in-laboratory specialized management protocols during 6 months of follow-up.
A multicenter, noninferiority, randomized, controlled trial with two open parallel arms and a cost-effectiveness analysis was performed in six tertiary hospitals in Spain. Sequentially screened patients with an intermediate to high OSA probability were randomized to PHA or in-laboratory management. The PHA arm involved a portable monitor with automatic scoring and semiautomatic therapeutic decision-making. The in-laboratory arm included polysomnography and specialized therapeutic decision-making. Patients in both arms received continuous positive airway pressure treatment or sleep hygiene and dietary treatment alone. The primary outcome measure was the Epworth Sleepiness Scale. Secondary outcomes were health-related quality of life, blood pressure, incidence of cardiovascular events, hospital resource utilization, continuous positive airway pressure adherence, and within-trial costs.
In total, 307 patients were randomized and 303 were included in the intention-to-treat analysis. Based on the Epworth Sleepiness Scale, the PHA protocol was noninferior to the in-laboratory protocol. Secondary outcome variables were similar between the protocols. The cost-effectiveness relationship favored the PHA arm, with a cost difference of €537.8 per patient.
PHA management may be an alternative to in-laboratory management for patients with an intermediate to high OSA probability. Given the clear economic advantage of outpatient management, this finding could change established clinical practice.Clinical trial registered with www.clinicaltrials.gov (NCT02141165).
C5-unsubstituted-C6-aryl-1,4-dihydropyridines were prepared by a CAN-catalyzed multicomponent reaction from chalcones, β-dicarbonyl compounds, and ammonium acetate. These compounds were able to block ...Ca2+ entry after a depolarizing stimulus and showed an improved Cav1.3/Cav1.2 selectivity in comparison with nifedipine. Furthermore, they were able to protect neuroblastoma cells against Ca2+ overload and oxidative stress models. Their selectivity ratio makes them highly interesting for the treatment of neurological disorders where Ca2+ dyshomeostasis and high levels of oxidative stress have been demonstrated. Furthermore, their low potency toward the cardiovascular channel subtype makes them safer by reducing their probable side effects, in comparison to classical 1,4-dihydropyridines. Some compounds afforded good protective profile in a postincubation model that simulates the real clinical situation of ictus patients, offering a therapeutic window of opportunity of great interest for patient recovery after a brain ischemic episode. Good activities were also found in acute ischemia/reperfusion models of oxygen and glucose deprivation.
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