Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions.

2,8-Dithia-5-aza-2,6-pyridinophane () has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (). In order to further explore the coordination chemistry of , and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb()(ClO)]·½CHCN, [Cu()](ClO)·CHCN and [Cd()(NO)]NO were determined by X-ray diffraction analysis. The electrochemical response of towards the metal ions Cu, Zn, Cd, Hg, and Pb was investigated by cyclic voltammetry (CV) in CHCl/CHCN 0.

Navigating post-ICU care: understanding family members' experiences - a qualitative study.

Background: Comprehending and addressing the needs of caregivers during the post-intensive care unit (ICU) phase is vital for establishing sustainable support systems and improving the overall quality of life (QoL) for both patients and caregivers.

Objective: To explore the experiences of family members (FMs) caring for loved ones three-months after ICU discharge and their related QoL.

Methods And Measures: A qualitative, descriptive research was conducted.

Crystal structure of 4,4'-(disulfanedi-yl)dipyridinium chloride triiodide.

4,4'-(Disulfanedi-yl)dipyridinium chloride triiodide, CHNS ·Cl·I , () was synthesized by reaction of 4,4'-di-pyridyl-disulfide with ICl in a 1:1 molar ratio in di-chloro-methane solution. The structural characterization of by SC-XRD analysis was supported by elemental analysis, FT-IR, and FT-Raman spectroscopic measurements.

The Italian Family Satisfaction in the Intensive Care Unit Questionnaire: A Psychometric Evaluation Using the Rasch Model.

Quality measurement of the intensive care unit (ICU) should include families' perspectives, their satisfaction with the care process and outcomes, and the evaluation of actions to improve their psychological health and wellbeing. The current study was designed to validate the Italian version of the Family Satisfaction in the Intensive Care Unit (FS-ICU) using the Rasch model. Results included reliability and separation for items and persons, item fit statistics, unidimensionality, and item characteristic curve.

Green Preparation of Antimicrobial 1D-Coordination Polymers: and by Ultrasonication of Zn(II) Salts and 4,4'-Bipyridine.

We report on the green preparation of one-dimensional metal coordination polymers by sonochemical approach. The spacer ligand 4,4'-bipyridine was ultrasonicated with chloride or acetate zinc salts to obtain and , respectively. Benign solvents such as ethanol and water were selected as reaction media, and the synthesis took place in a few minutes-a very short time compared to conventional methods where some days' synthesis is required.

Grafting of the 2,8-dithia-5-aza-2,6-pyridinophane macrocycle on SBA-15 mesoporous silica for the removal of Cu and Cd ions from aqueous solutions: synthesis, adsorption, and complex stability studies.

Silica-based mesoporous materials have received growing attention in metal recovery from industrial processes, although, in general, the adsorption of metal ions by silanols is rather poor. Nevertheless, a great improvement of metal ion removal from aqueous solutions can be achieved by grafting metal-chelators on the particles' surface. Combining the metal-chelating properties of organic ligands with the high surface area of mesoporous silica particles makes these hybrid nanostructured materials a new horizon in metal recovery, sensing and controlled storage of metal ions in industrial and mining processes.

Glyphosate sensing in aqueous solutions by fluorescent zinc(II) complexes of [9]aneN-based receptors.

Herein we describe the binding abilities of Zn(II) complexes of [12]aneN- (L1) and [9]aneN-based receptors (L2, L3) towards the herbicides -(phosphonomethyl)glycine (glyphosate, HPMG) and 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid (glufosinate, HGLU), and also aminomethylphosphonic acid (HAMPA), the main metabolite of HPMG, and phosphate. All ligands form stable Zn(II) complexes, whose coordination geometries allow a possible interaction of the metal center with exogenous anionic substrates. Potentiometric studies evidenced the marked coordination ability of the L2/Zn(II) system for the analytes considered, with a preferential binding affinity for HPMG over the other substrates, in a wide range of pH values.

Can Serendipity Still Hold Any Surprises in the Coordination Chemistry of Mixed-Donor Macrocyclic Ligands? The Case Study of Pyridine-Containing 12-Membered Macrocycles and Platinum Group Metal Ions Pd, Pt, and Rh.

This study investigates the coordination chemistry of the tetradentate pyridine-containing 12-membered macrocycles - towards Platinum Group metal ions Pd, Pt, and Rh. The reactions between the chloride salts of these metal ions and the three ligands in MeCN/HO or MeOH/HO (1:1 /) are shown, and the isolated solid compounds are characterized, where possible, by mass spectroscopy and H- and C-NMR spectroscopic measurements. Structural characterization of the 1:1 metal-to-ligand complexes [Pd()Cl][PdCl], [Pt()Cl](BF), [Rh()Cl](PF), and [Rh()Cl](BF)·MeCN shows the coordinated macrocyclic ligands adopting a folded conformation, and occupying four coordination sites of a distorted square-based pyramidal and octahedral coordination environment for the Pd/Pt, and Rh complexes, respectively.

Switching-On Fluorescence by Copper (II) and Basic Anions: A Case Study with a Pyrene-Functionalized Squaramide.

The new symmetric acyclic -bis(1-pyrenyl) squaramide () functionalized with the pyrene moiety as a fluorogenic fragment has been designed and its ability to selectively detect specific anions and metals investigated. selectively binds Cl both in solution (DMSO 0.5% HO and MeCN) and in the solid state, and allows to selectively detect Cu in MeCN with the formation of a 2:1 metal-receptor complex, with a green intense emission appreciable by naked eye under the UV lamp.

Simple squaramide receptors for highly efficient anion binding in aqueous media and transmembrane transport.

A family of acyclic squaramide receptors (L1-L5) have been synthesised with the aim to bind anions in a competitive solvent mixture and to evaluate how the presence of additional H-bond donor groups on the squaramide scaffold could affect the affinity towards anions and the transmembrane transport ability.

Aza- and Mixed Thia/Aza-Macrocyclic Receptors with Quinoline-Bearing Pendant Arms for Optical Discrimination of Zinc(II) or Cadmium(II) Ions.

The synthesis and coordination properties of two fluorescent chemosensors, featuring [9]aneN (1,4,7-triazacyclononane; L1) and [12]aneNS (1-aza-4,7,10-trithiacyclododecane; L2) as receptor units, and a quinoline pendant arm with an amide group as a functional group spacer are described. The optical responses of L1 and L2 in the presence of several metal ions were analysed in MeCN/H O (1 : 4 v/v) solutions. A selective chelation enhancement of fluorescence (CHEF) effect was observed in the presence of Zn in the case of L1, and in the presence of Cd in the case of L2, following the formation of a 1 : 1 and a 1 : 2 metal/ligand complex, respectively, which was also confirmed by potentiometric measurements.

Heavy metal tolerance of orchid populations growing on abandoned mine tailings: A case study in Sardinia Island (Italy).

Understanding how environmental pollutants influence plant occurrence, growth, and development is key for effective management plans and potential bioremediation. Rare plants, such as orchids, may occur in modified habitats and on soils containing heavy metals, yet their ecological and physiological responses to heavy metals is poorly understood. We investigated the influence of heavy metal pollution on orchid growth rates and interactions with soil fungal mutualists by comparing a large population of the orchid Epipactis helleborine (L.

Are preconceptional stressful experiences crucial elements for the aetiology of autism spectrum disorder? Insights from an animal model.

Autism spectrum disorders (ASD) are a group of neurodevelopmental disorders characterized by changes in social interactions, impaired language and communication, fear responses and presence of repetitive behaviours. Although the genetic bases of ASD are well documented, the recent increase in clinical cases of idiopathic ASD indicates that several environmental risk factors could play a role in ASD aetiology. Among these, maternal exposure to psychosocial stressors during pregnancy has been hypothesized to affect the risk for ASD in offspring.

[9]aneN-based fluorescent receptors for metal ion sensing, featuring urea and amide functional groups.

We describe here the synthesis and coordination properties of three new derivatives of [9]aneN3 containing phenyl/quinoline pendant arm derivatives (L1, L2 and L3, respectively) also featuring urea (L1-L2) or amide (L3) functions as "non-innocent" spacers. At first, L1, L2 and L3 were studied considering the interaction with a series of anions (AcO-, BzO-, H2PO4-, F-, and Cl-) by means of 1H NMR measurements. Subsequently, the optical responses of L2 and L3 in the presence of several metal ions Cd2+, Co2+, Cu2+, Fe3+, Hg2+, K+, Mg2+, Mn2+, Ni2+, Zn2+ and Pb2 were analysed in MeCN/H2O (4 : 1 v/v).

A Fluorescent Sensor Array Based on Heteroatomic Macrocyclic Fluorophores for the Detection of Polluting Species in Natural Water Samples.

The development of a novel all-solid-state optical sensor array based on heteroatomic macrocyclic fluorophores (diaza-crown ether, metallocorrole and pyridinophans) for the photographic analysis of liquid media, is presented. The sensitivity of the new optical system toward a number of different species (cations: Li, K, Na, , Mg, Ca, Co, Cu, Zn, Cd, Pb and anions: , , Cl, Br, ) was evaluated both in single selective sensor mode and in multisensory arrangement. The satisfactory PLS1 regression models between sensor array optical response and analyte concentration were obtained for Cd, Cu, Zn, and ions in all the range of tested concentrations.

Dyspnoea, thoracic pain and fever in a young caucasian female: A case report.

Introduction: The diagnostic approach to patients with mediastinal pathology is not always simple and an improper diagnostic work-up can lead to significant diagnosis delay.

Presentation Of Case: We report on the case of a young woman who was admitted to the Emergency Department complaining of thoracic pain, dyspnoea, fever and productive cough. The physical examination showed a painful swelling over the sternum's upper left margin, which had become evident 4 months earlier.

Juvenile social isolation affects maternal care in rats: involvement of allopregnanolone.

Rationale: Social isolation of rats immediately after weaning is thought to represent an animal model of anxiety-like disorders. Socially isolated virgin females showed a significant decrease in allopregnanolone levels, associated with increased anxiety-related behavior compared with group-housed rats.

Objectives: The present study investigates whether post-weaning social isolation affects maternal behavior and assesses neuroactive steroid levels in adult female rats during pregnancy and postpartum.

A new class of silica-supported chromo-fluorogenic chemosensors for anion recognition based on a selenourea scaffold.

The first example of a chemosensor (L) containing a selenourea moiety is described here. L is able to colorimetrically sense the presence of CN and S in HO : MeCN (75 : 25, v/v). Moreover, when L is loaded into functionalised mesoporous silica nanoparticles an increase in the selectivity towards S occurs via a selective fluorescence response.

Di- and Triphosphate Recognition and Sensing with Mono- and Dinuclear Fluorescent Zinc(II) Complexes: Clues for the Design of Selective Chemosensors for Anions in Aqueous Media.

The synthesis of a new ligand (L1) containing two 1,4,7-triazacyclononane ([9]aneN ) moieties linked by a 4,5-dimethylenacridine unit is reported. The binding and fluorescence sensing properties toward Cu , Zn , Cd , and Pb of L1 and receptor L2, composed of two [9]aneN macrocycles bridged by a 6,6''-dimethylen-2,2':6',2''-terpyridine unit, have been studied by coupling potentiometric, UV/Vis absorption, and emission measurements in aqueous media. Both receptors can selectively detect Zn thanks to fluorescence emission enhancement upon metal binding.

Sex differences in the outcome of juvenile social isolation on HPA axis function in rats.

Women are more likely than men to suffer from anxiety disorders and major depression. These disorders share hyperresponsiveness to stress as an etiological factor. Thus, sex differences in brain arousal systems and their regulation by chronic stress may account for the increased vulnerability to these disorders in women.

Re(I) derivatives functionalised with thioether crowns containing the 1,10-phenanthroline subunit as a new class of chemosensors.

A series of luminescent fac-[Re(CO)3(L)(NN)](+) complexes, where L is a pyridine or an imidazole and NN is the 1,10-phenanthroline subunit of mixed donor pentadentate thioether crowns have been synthesised and their luminescence properties have been analysed. Then, heterometallic Re(i)/Au(i) complexes, with the Au(i) fragment bonded directly to the imidazole ligand, and heterometallic Re(i)/Ag(i) complexes, with the silver fragment coordinating the S-donor thioether linker of the rings have also been prepared. Analysis of their luminescence properties showed a considerable blue shift of the emission maxima for the Re(i)/Ag(i) derivatives, upon coordination of the silver centre to the S-donor atoms of the aliphatic chain of the macrocyclic units.

Silver ion imprinted polymer nanobeads based on a aza-thioether crown containing a 1,10-phenanthroline subunit for solid phase extraction and for voltammetric and potentiometric silver sensors.

A new nano-sized silver(I) ion-imprinted polymer (IIP) was prepared via precipitation copolymerization using ethyleneglycol dimethacrylate, as a cross-linking agent in the presence of Ag(+) and an aza-thioether crown containing a 1,10-phenanthroline subunit as a highly selective complexing agent. The imprint silver(I) ion was removed from the polymeric matrix using a 1.0M HNO3 solution.

High-throughput automatic flow method for determination of trace concentrations of aluminum in dialysis concentrate solutions using salicylaldehyde picolinoylhydrazone as a turn-on fluorescent probe.

A simple and expedient flow-based assembly capitalizing on programmable flow is herein proposed for reliable determination of trace level concentrations of aluminum as a potential contaminant in dialysis concentrate solutions without any prior sample clean-up/preconcentration procedure. Using salicylaldehyde picolinoylhydrazone in weakly acidic media as a turn-on fluorescent probe, the manifold is devised to handle three samples concurrently in stopped-flow reaction mode for simultaneous improvement of the analytical sensitivity and sample throughput. Analytical parameters influencing the sensitivity and repeatability of the assays, namely, probe concentration, reaction temperature and reaction time were investigated using a multivariate optimization protocol composed of a full factorial screening design followed by a Doehlert matrix model.

Silica-based nanoparticles: a versatile tool for the development of efficient imaging agents.

This review describes the recent advances in the development of imaging agents based on silica nanoparticles. Different techniques (magnetic resonance imaging, optical imaging, positron emission tomography, X-ray computed tomography, and ultrasound imaging) are described as well as the possibility of combining together different imaging techniques in the same nanoplatform and simultaneously performing imaging and therapy.

Maternal separation attenuates the effect of adolescent social isolation on HPA axis responsiveness in adult rats.

Adverse early life experiences that occur during childhood and adolescence can have negative impacts on behavior later in life. The main goal of our work was to assess how the association between stressful experiences during neonatal and adolescent periods may influence stress responsiveness and brain plasticity in adult rats. Stressful experiences included maternal separation and social isolation at weaning.