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Multinuclear (di/tri) copper(II) complexes bridged through hydroxyl groups are very interesting coordination complexes owing to their potential applications in various fields. In this work, three novel dinuclear (μ-hydroxo)-bridged copper(II) complexes in the crystal form, namely, [Cu 2 (3,5-DIFLB) 2 (H 2 tea ) 2 ](H 2 O) (1), [Cu 2 (4-ClB) 2 (H 2 tea ) 2 ](H 2 O) (2), and [Cu 2 (4-ETHB) 2 (H 2 tea ) 2 ](H 2 O) 2 (3) (where DIFLB = difluorobenzoate, CLB = chlorobenzoate, ETHB = ethoxybenzoate, and H 3 tea = triethanolamine), were isolated at room temperature using methanol and water in a 4 : 1 v/v ratio as a solvent. Furthermore, all three complexes (1-3) were characterised using spectroscopic (UV-vis, DRS, and FT-IR), electrochemical (CV) and single-crystal X-ray diffraction techniques. Structural insights gained by packing analysis revealed the role of steric constraints of substituents and various non-covalent interactions in lattice stabilization, which were indeed supported by theoretical and molecular electrostatic potential illustrations. Hirshfeld surface analysis provided quantitative verification about various non-covalent interactions (interatomic contacts) involved in the packing of molecules. Interestingly, as a potential application, complexes 1-3 all exhibited remarkable visible light-mediated photo-Fenton degradation of approximately 98% for 50 ppm concentration of organic dyes (fuchsin basic (FB) and methyl orange (MO)) in 90 minutes with the optimized conditions of 1 mg mL -1 of dye solution. In all the cases, dye degradation by these materials was ascribed to the symbiotic relations among the molecular structures of complexes 1-3, which were endowed with various electron-withdrawing and electron-releasing substituents and ionic strength, with respect to the structure, shape and interacting patterns of dye molecules. The adsorption mechanism indicates that various weak interactions between the donor and acceptor groups of complexes and dyes, such as electrostatic, hydrogen bonding, and direct coordination to metal sites, play a crucial role, which is confirmed by molecular dynamics (MD) simulations. Theoretical studies by DFT-based descriptors, molecular electrostatic potentials, and band gaps provided deep insights into various electronic and reactivity parameters. For subsequent processes of dye degradation, complexes 1-3 were stable and recoverable. The successful integration of experimental and theoretical approaches sheds light on copper-based dinuclear stable coordination complexes, showcasing a significant step towards the development of novel heterogeneous photo-Fenton catalysts.

In this article, we deal with the nonlocal elliptic problems of the Kirchhoff type involving the Hardy potential and critical nonlinearity on a bounded domain in R 3 . Under an appropriate condition on the nonhomogeneous term and using variational methods, we obtain two distinct solutions. [ABSTRACT FROM AUTHOR]

We have prepared and characterized three coordination polymers formulated as [Dy 2 (C 6 O 4 Cl 2 ) 3 (fma) 6 ] ⋅ 4.5fma (1) and [Dy 2 (C 6 O 4 X 2 ) 3 (fma) 6 ] ⋅ 4fma ⋅ 2H 2 O with X=Br (2) and Cl (3), where fma=formamide and C 6 O 4 X 2 2- =3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion with X=Cl (chloranilato) and Br (bromanilato). Compounds 1 and 3 are solvates obtained with slow and fast precipitation methods, respectively. Compounds 2 and 3 are isostructural and only differ in the X group of the anilato ligand. The three compounds present (6,3)-gon two-dimensional hexagonal honey-comb structures. Magnetic measurements indicate that the three compounds show slow relaxation of the magnetization at low temperatures when a continuous magnetic field is applied, although with different relaxation times and energy barriers depending on X and the crystallisation molecules. Compounds 1-3 represent the first examples of anilato-based lattices with formamide and field-induced slow relaxation of the magnetization., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Autism spectrum disorder (ASD) are neurodevelopmental conditions characterised by deficits in social communication and interaction and repetitive behaviours. Maternal immune activation (MIA) during the mid-pregnancy is a known risk factor for ASD. Although reported in 15% of affected individuals, little is known about the specificity of their clinical profiles. Adaptive skills represent a holistic approach to a person's competencies and reflect specifically in ASD, their strengths and difficulties. In this study, we hypothesised that ASD individual with a history of MIA (MIA + ) could be more severely socio-adaptively impaired than those without MIA during pregnancy (MIA - ). To answer this question, we considered two independent cohorts of individuals with ASD (PARIS study and FACE ASD) screened for pregnancy history, and used supervised and unsupervised machine learning algorithms. We included 295 mother-child dyads with 14% of them with MIA + . We found that ASD-MIA + individuals displayed more severe maladaptive behaviors, specifically in their socialization abilities. MIA + directly influenced individual's socio-adaptive skills, independent of other covariates, including ASD severity. Interestingly, MIA + affect persistently the socio-adaptive behavioral trajectories of individuals with ASD. The current study has a retrospective design with possible recall bias regarding the MIA event and, even if pooled from two cohorts, has a relatively small population. In addition, we were limited by the number of covariables available potentially impacted socio-adaptive behaviors. Larger prospective study with additional dimensions related to ASD is needed to confirm our results. Specific pathophysiological pathways may explain these clinical peculiarities of ASD- MIA + individuals, and may open the way to new perspectives in deciphering the phenotypic complexity of ASD and for the development of specific immunomodulatory strategies., (© 2023. Springer Nature Limited.)

We exploit the high versatility of the solvent ethylene glycol (eg = CH 2 OH-CH 2 OH) acting as a ligand with three different coordination modes: terminal (κ O ), chelate (κ 2 O,O' ), and bridge (1κ O ,2κ O' ) to prepare a novel family of six different coordination polymers with Dy III and three different anilato ligands (3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion = C 6 O 4 X 2 2- , with X = H, Cl, and Br). With the X = H derivative (dhbq 2- ), we have prepared [Dy 2 (dhbq) 3 (eg) 2 (μ-eg)]·4eg·2H 2 O ( 1 ), a 3D diamond-like network with a chelate and bridging eg molecules. With the X = Cl derivative (chloranilato), we have prepared [Dy 2 (C 6 O 4 Cl 2 ) 3 (eg) 4 ]·2eg·H 2 O ( 2 ) and [Dy 2 (C 6 O 4 Cl 2 ) 3 (μ-eg)(H 2 O) 4 ]·2eg·7H 2 O ( 3 ). Compound 2 has a 2D (6,3)-gon brick-wall lattice and contains a chelate and a terminal eg molecule. Compound 3 has a 3D diamond-like topology as 1 , although now the chelate eg has been replaced by two water molecules. Finally, with the X = Br derivative (bromanilato), we have obtained [Dy 2 (C 6 O 4 Br 2 ) 3 (eg) 2 (CH 3 OH) 2 ]·2eg·4CH 3 OH ( 4 ), [Dy 2 (C 6 O 4 Br 2 ) 3 (eg) 4 ]·4eg ( 5 ), and [Dy 2 (C 6 O 4 Br 2 ) 3 (eg) 3 (H 2 O)]·2eg·H 2 O ( 6 ). Compound 4 has a 2D (6,3)-gon herringbone topology and contains a chelate eg and a MeOH molecule. Compounds 5 and 6 have a 2D (6,3)-gon brick-wall topology with a chelate and a terminal eg molecules (in 5 and in one of the two independent Dy centers of 6 ). The other Dy center in 6 has a chelate eg and a water molecule. All the compounds show slow relaxation of the magnetization at low temperatures (in compounds 1 , 2 , and 5 with no applied DC field). The magnetization of compounds 1 - 6 relaxes through Orbach and direct mechanisms when a DC field is applied and through an Orbach and/or quantum tunneling mechanism when no DC field is applied., Competing Interests: The authors declare no competing financial interest., (© 2023 American Chemical Society.)

In spectral diffuse solar irradiance measurements, when diffusing devices used are neither perfectly Lambertian nor have an ideal cosine response, significant errors may spoil the collected data. An optical method permits the determination of a spectral correction factor (SCF) which fully compensates for the diffusers' imperfection when the sky radiance is isotropic. A study of the errors introduced when using such a isotropic SCF in anisotropic radiance conditions is presented for two common flat-plate diffusers fitted with a shadow-ring or a tracking disk. The wavelength band explored is 0.29 - 0.90 [[micro]meter] and the clear sky radiance model used is Kittler's. The relevance of several diffuse irradiance spectra measured on clear sky days with isotropic SCF is analysed by comparison with Brine-Iqbal model spectra and total diffuse measurements. A remarkable coherence is found for small solar zenith angles when using a tracking disk and a diffuser with an isotropic SCF smaller than 1.2.

The combination of Co(III) and Dy(III) with a compartmental Schiff base ligand (H 3 L=3-[(2-Hydroxy-3-methoxy-benzylidene)-amino]-propane-1,2-diol), presenting three different coordinating pockets, has allowed the synthesis of two novel Co(III)-Dy(III) complexes: [Co 2 Dy(HL) 4 ]NO 3  ⋅ 2CH 3 CN (1), a rare example of trinuclear linear Co III 2 Dy III complex (and the first with slow relaxation of magnetization in absence of a DC field) and [Co 2 Dy 2 (μ 3 -OH) 2 (HL) 2 (OAc) 6 ] ⋅ 4.6H 2 O (2), the first tetranuclear Co III 2 Dy III 2 cluster with a rhomb-like structure where the Co(III) ions are connected along the short diagonal of the rhomb. 1 presents two different relaxation processes: a fast relaxation dominated by Quantum tunnelling (QT) and a slow relaxation with an energy barrier of 40 K. 2 shows two close relaxation processes without applied DC fields that follow QT and Orbach mechanisms whereas for H DC =500 Oe, the QT is cancelled and a direct term appears. Here we present the synthesis, X-ray structure and magnetic characterization of these two Co(III)-Dy(III) single-ion/molecule magnets., (© 2021 Wiley-VCH GmbH.)

Herein, we present the synthesis and structural characterisation of two layered MOFs with the asymmetric ligand 3-chloro,6-cyano-2,5-dihydroxy-1,4-benzoquinone dianion (C6O4(CN)Cl2− = chlorocyananilato). These compounds, formulated as (H3O)[Eu(C6O4(CN)Cl)2(H2O)]·34H2O (1) and (H3O)[Dy(C6O4(CN)Cl)2(H2O)]·44H2O (2), are isostructural and show a (4,4)-layered square structure with the crystallisation water molecules located between the layers. The lanthanoid ions are surrounded by four bis-bidentate chlorocyananilato ligands that connect each LnIII centre with other four, giving rise to square cavities formed by LnIII centres in the vertices and chlorocyananilato ligands as the sides. There is an additional coordinated water molecule that occupies the caped position of the capped square antiprismatic coordination geometry around the LnIII centres. The magnetic properties show the presence of a field-induced slow relaxation of the magnetisation in the DyIII derivative at low temperatures that follows Direct and Orbach relaxation mechanisms with an energy barrier of 36(3) K. [ABSTRACT FROM AUTHOR]

Autism spectrum disorder (ASD) is a very heterogeneous disorder. Obsessive compulsive disorder (OCD) comorbidity, frequent in ASD, could be useful to define a specific ASD subtype. Our objective was to explore if adults with ASD and comorbid OCD could present a specific clinical profile of ASD in 89 high functioning-adult ASD patients. We found that adults with ASD and comorbid OCD showed a lower verbal IQ and a more severe impairments in social cognition. ASD with comorbid OCD present a specific clinical profile which could constitute a possible subtype of ASD., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The synthesis, characterization, crystal structure and detailed magnetic properties of a pyrazine (pyz) and azido (N 3 ) bridged cobalt(II) compound of formula [Co(N 3 ) 2 (pyz)] (1) are reported. Compound 1 shows a layered structure formed by Co(II) chains with double μ-N 3 (κN 1 ,N 1 ) bridges that are further connected by μ-(pyrazine-κN 1 ,N 4 ) bridges. The layers present weak van der Waals interactions between azido terminal groups. The magnetic properties show the presence of a metamagnetic behaviour in 1 with two critical fields of 200 and 400 mT at low temperatures. AC magnetic measurements show the presence of a long-range 2D ferromagnetic order at T c ≈ 8.0-7.0 K for dc fields above 200 mT and a long-range 3D ferromagnetic order at T c ≈ 4.5 K for dc fields above 400 mT.

In this paper, we study a berth allocation problem (BAP) in the automotive transshipment (also called Ro-Ro) terminal of Le Havre seaport. Despite the vast literature on the BAP, very few work deals with automotive transshipment terminals. The main objective of the problem we consider is to define incoming ships berthing positions in the Ro-Ro terminal, for minimising the total handling time while considering several operational constraints. In particular, we introduce the BAP with car flow crossings. We discuss mathematical models for car flow crossings and present integer programming formulations of the problem with and without car flow crossings. Then, we solve the problem using CPLEX 12.5 and discuss some computational issues. [ABSTRACT FROM AUTHOR]

Background: Vitamin C (ascorbic acid, AscH2) has been shown to enhance immunity. Here, we studied its immunomodulatory effect on human endothelial cells (ECs) during S. aureus infection., Materials and Methods: The ex vivo effects of AscH2 were performed on primary human umbilical vein endothelial cells (HUVECs) infected or not with S. aureus., Results: AscH2 treatment induced a marked downregulation of nitric oxide (NO) production and a moderate upregulation of arginase activity in S. aureus-infected HUVECs (respectively, p < 0.05 and p > 0.05). Although the upregulated release levels of soluble intercellular adhesion molecular 1 (sICAM-1/sCD54) and sE-selectin (sCD62E) molecules were not significantly different between treated and untreated S. aureus-infected HUVECs, AscH2 treatment induced reversing effect on sICAM-1 release when comparing to uninfected control HUVECs. Moreover, AscH2 treatment appears to have a significant effect on preventing HUVEC necrosis induced by S. aureus infection (p < 0.05). Furthermore, AscH2 treatment induced a significant upregulation of cell protective redox biomarker in S. aureus-infected, as shown by superoxide dismutase (SOD) activity (p < 0.05), but not by catalase activity (p > 0.05). Additionally, S. aureus infection markedly downregulated total bound calcium ions ( b Ca 2+ ) levels as compared to control HUVECs, whereas, AscH2 treatment induced a slight upregulation of b Ca 2+ levels in infected HUVECs as compared to infected and untreated HUVECs (p > 0.05). On the other hand, AscH2 treatment downregulated increased total cellular cholesterol content ( tcc CHOL) levels in HUVECs induced by S. aureus infection (p < 0.05). In addition, AscH2 treatment markedly reversed S. aureus effect on upregulation of intracellular glucose ( i GLU) levels within infected HUVECs (p < 0.05). Moreover, AscH2 treatment significantly downregulated S. aureus growth (p < 0.05), and significantly upregulated bacterial internalization and intracellular killing by HUVECs (p < 0.05), as well as their cell cycle activation (p < 0.01). Finally, AscH2 treatment has a slight effect on the production of interleukin 6 (IL-6), but induced a marked downregulation of that of IL-1β in S. aureus-infected HUVECs (respectively, p > 0.05, and p < 0.05)., Conclusions: Our outcomes demonstrated that, during S. aureus infection, AscH2 treatment promotes human ECs survival and function, as well as prevents inflammatory response exacerbation, while inducing bactericidal activity., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu 2 (L)(DMF) 2 } n , where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(H 2 O) 3 ]·H 2 O} n (complex 2). On the other hand, ultrasound is required to induce the nanostructuration. Remarkably, different morphologies are obtained using different solvents and interconversion from one morphology to another seems to occur upon solvent exchange. Both complexes 1 and 2, as well as the corresponding nanostructures, have been fully characterized by different means such as infrared spectroscopy, x-ray diffraction and microscopy., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Introduction: Stroke is a public health problem worldwide. Community stroke knowledge is crucial to guide the prevention approach. We aimed to evaluate the level of stroke knowledge among the visitors to Emergency Centres (ECs) in the southern region of Tunisia concerning factors of risk, symptoms, and treatment of stroke., Methods: A multicenter cross-sectional survey about stroke knowledge; conducted in five ECs for 10 days. All the visitors to these ECs were invited to participate in this survey. In each center, one investigator had to conduct the questionnaire. We used the stroke knowledge test (SKT)., Results: We enrolled 839 participants aged at 44 ± 7 years and with an M/F sex-ratio at 0.9. Relatives and mass media were the most reported sources of information about stroke. In 32.3% of cases, the participants had a university schooling level. The upper quartile had an SKT score of 55% or over (n = 247; 29.4%). The SKT score was significantly higher in young, female participants, in rural centers, with a university level of schooling and with no reported chronic diseases. Receiving information about stroke through the medium of television or via relatives was an independent predictor of a high SKT score compared with other knowledge sources., Conclusion: This study emphasises the urgent need for improving the population's knowledge about stroke in Tunisia. These findings may reflect the lack of government policies for education and training on stroke. A national educating program is necessary to implement to increase stroke knowledge., Competing Interests: The authors declared no conflict of interest., (© 2018 Published by Elsevier Ltd. CC BY-NC-ND 4.0.)

The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: C 6 O 4 X 2 2- , with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy 2 (C 6 O 4 H 2 ) 3 (dmso) 2 (H 2 O) 2 ]·2dmso·18H 2 O ( 1 ) and [Dy 2 (C 6 O 4 Cl 2 ) 3 (dmso) 4 ]·2dmso·2H 2 O ( 2 ) show distorted hexagonal honeycomb layers with the solvent molecules (dmso and H 2 O) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers. The magnetic measurements of compounds 1 , 2 and [Dy 2 (C 6 O 4 (CN)Cl) 3 (dmso) 6 ] ( 3 ), a recently reported related compound, show that the three compounds present slow relaxation of the magnetization. In compound 1 the SIM behaviour does not need the application of a DC field whereas 2 and 3 are field-induced SIM (FI-SIM) since they show slow relaxation of the magnetization when a DC field is applied. We discuss the differences observed in the crystal structures and magnetic properties based on the X group of the anilato ligands (H, Cl and Cl/CN) in 1 - 3 and in the recently reported derivative [Dy 2 (C 6 O 4 Br 2 ) 3 (dmso) 4 ]·2dmso·2H 2 O ( 4 ) with X = Br, that is also a FI-SIM.

Two dinuclear cobalt(ii) complexes, [(dmso)CoIIL1(μ-(m-NO2)C6H4COO)CoII(NCS)] (1) and [(dmso)CoIIL2(μ-(m-NO2)C6H4COO)CoII(NCS)] (2) [dmso = dimethylsulfoxide, H2L1 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-methoxyphenol) and H2L2 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)] have been synthesized and structurally characterized by single-crystal X-ray diffraction, magnetic-susceptibility measurements and various spectroscopic techniques. Each complex contains a cobalt(ii) center with a slightly distorted octahedral geometry and a second cobalt(ii) center with a distorted trigonal prismatic one. To obtain insight into the physical nature of weak non-covalent interactions, we have extensively used the Bader's quantum theory of atoms-in-molecules (QTAIM). In addition, the non-covalent interaction reduced density gradient (NCI-RDG) methods established the presence of such non-covalent intermolecular interactions. Variable temperature magnetic susceptibility measurements show that both cobalt centers in each complex are in the high spin state (S = 3/2) and both complexes show weak ferromagnetic couplings through the double phenoxido bridges (J = 3.36(3) cm-1 in 1 and 4.56(2) cm-1 in 2). The magnetic properties of both complexes can be fitted to a Co(ii) dimer model including similar orbital reduction factors (α = -0.94(1) for 1 and -0.85(1) for 2) although different zero field splitting parameters D(1) = 11.0(4) cm-1 and D(2) = 19.5(4) cm-1 in 1 and D(1) = 8.2(4) cm-1 and D(2) = -1.3(4) cm-1 in 2. AC magnetic measurements reveal that the CoII2 unit in complex 2 exhibits field-induced slow relaxation of the magnetization at low temperatures and high frequencies.

Background: Neonatal sepsis remains an important cause of morbidity and mortality. The ability to quickly and accurately diagnose neonatal sepsis based on clinical assessments and laboratory blood tests remains difficult, where haemoculture is the gold standard for detecting bacterial sepsis in blood culture. It is also very difficult to study because neonatal samples are lacking., Methods: Forty-eight newborns suspected of sepsis admitted to the Neonatology Department of the Mother-Child Specialized Hospital of Tlemcen. From each newborn, a minimum of 1-2 ml of blood was drawn by standard sterile procedures for blood culture. The miRNA-23b level in haemoculture was evaluated by RT-qPCR., Results: miR-23b levels increased in premature and full-term newborns in early onset sepsis (p < 0.001 and p < 0.005 respectively), but lowered in late onset sepsis in full-term neonates (p < 0.05) compared to the respective negative controls. miR-23b levels also increased in late sepsis in the negative versus early sepsis negative controls (p < 0.05). miR-23b levels significantly lowered in the newborns who died from both sepsis types (p < 0.0001 and p < 0.05 respectively). In early sepsis, miR-23b and death strongly and negatively correlated (correlation coefficient = - 0.96, p = 0.0019). In late sepsis, miRNA-23b and number of survivors (correlation coefficient = 0.70, p = 0.506) positively correlated., Conclusions: Lowering miR-23b levels is an important factor that favours sepsis development, which would confirm their vital protective role, and strongly suggest that they act as a good marker in molecular diagnosis and patient monitoring.

A series of multifunctional 2D frameworks prepared with Dy(iii) and the bromanilato ligand, formulated as: [Dy 2 (C 6 O 4 Br 2 ) 3 (G) n ]·nG with G = H 2 O, dimethylformamide (dmf) and dimethylsulfoxide (dmso), can exchange the coordinated and non-coordinated solvent molecules (G) in a reversible way. These multifunctional frameworks show field induced slow relaxation of the magnetization and luminescence that can be easily and reversibly modified by solvent exchange.

The combination of two 8-aminoquinoline-based Schiff base ligands (L1 and L2) with SCN - and Ni(II) has led to the synthesis of two new one-dimensional thiocyanato-bridged coordination polymers: [Ni(L1)(NCS) 2 ] n ( 1 ) and [Ni(L2)(NCS) 2 ] n ( 2 ). Both compounds are isostructural and consists of regular zigzag thiocyanato-bridged chains with very weak S···S interchain interactions. The measured room-temperature conductivities of compounds 1 and 2 (7.0 × 10 -5 and 2.0 × 10 -5 S m -1 , respectively) are indicative of semiconductor behavior which increases in the presence of photoillumination (3.5 × 10 -4 and 4.9 × 10 -4 S m -1 , respectively). The measured I - V characteristics of compound 1 and 2 based thin film metal-semiconductor (MS) junction devices under irradiation and nonirradiation conditions show a nonlinear rectifying behavior, typical of a Schottky diode (SD). The rectification ratios ( I on / I off -based devices, respectively) increase to 44.19 and 79.42, respectively, upon light irradiation. The photoinduced behavior has been analyzed by thermionic emission theory, and to determine the diode parameters, the Cheung's method has been employed. These diode parameters indicate that compound 1 - and 2 -based devices, respectively) increase to 44.19 and 79.42, respectively, upon light irradiation. The photoinduced behavior has been analyzed by thermionic emission theory, and to determine the diode parameters, the Cheung's method has been employed. These diode parameters indicate that compound 2 has a better performance in comparison to compound 1 and that these materials are good candidates for applications in electrochemical devices. Magnetic measurements show that both compounds present ferromagnetic Ni-Ni intrachain and weak antiferromagnetic interchain interactions. The isothermal magnetizations at 2 K show that both compounds are metamagnets with critical fields of ca. 130 mT in 1 and 90 mT in 2 at 2 K. In the ferromagnetic phase (above the critical field), both compounds exhibit a long-range ferromagnetic order with critical temperatures of around 3.5 K in 1 and 3.0 K in 2 . DC and AC measurements with different applied DC fields confirm the metamagnetic behaviors and have allowed the determination of the magnetic phase diagram in both compounds.

The amygdala and raphe nuclei, which play crucial roles in mood regulation, are influenced by serotonergic neurotransmission. Alterations in this neurotransmission are associated with mood disorders. Therefore, using immunohistochemistry and quantitative methods this study was designed to evaluate potential alterations in the expression of serotoninergic markers in the amygdala and raphe nuclei of mice with oestrogen receptor β (ERβ) knock out which exhibit increased anxiety as evidenced by reduced locomotion and increased thigmotaxis. These alterations could either contribute to heightened anxiety or serve as a compensatory strategy for reducing it. The results show that in ERβ knock-out mice, 5-HT1B expression is significantly increased in the amygdala, while 5-HTT expression is significantly decreased in both the amygdala and raphe nuclei. Furthermore, ERβ deficiency does not affect TPH2. In conclusion, serotonin signalling is altered in the amygdala and raphe nuclei of ERβ knock-out females. It seems that an increase in 5-HTT levels has been associated with reduced anxiety, whereas a decrease in 5-HT1B receptors may encourage fear. However, further studies are required to determine the exact role of ERβ in anxiety-related behaviour., (© 2024 Federation of European Neuroscience Societies and John Wiley & Sons Ltd.)

New manganese(II) and nickel(II) 1-D zigzag coordination polymers [M2+(pQ2−)·2(solv)]n (M2+ = Mn2+, solv = N,N'-dimethylacetamide (1) and M = Ni2+, solv = N,N'-dimethylformamide (2); pQ2− - dianionic form of 2,5-di-hydroxy-3,6-di-tert-butyl-para-quinone) have been synthesized and characterized. Both compounds 1 and 2 are isomorphic. Their physicochemical properties such as thermal stability, gas sorption, redox and magnetic properties are described. [ABSTRACT FROM AUTHOR]

Two tetranuclear mixed-valence cobalt(III/II) complexes having the general formula [(μ 1,3 -N 3 ){Co II (L n )(μ-O 2 CC 6 H 4 NO 2 )Co III (N 3 )} 2 ]PF 6 (where H 2 L 1 and H 2 L 2 are two reduced Schiff base ligands) have been synthesized and characterized. The structures of both complexes show cobalt(II) and cobalt(III) centers with a distorted octahedral geometry with cobalt(III) and cobalt(II) centers located at the inner N 2 O 2 and outer O 4 cavities of the reduced Schiff base ligands, respectively. The oxidation states of both cobalt centers have been confirmed by bond valence sum (BVS) calculations. The magnetic properties show that both compounds behave as cobalt(II) dimers connected through an end-to-end azido bridging ligand and show moderate antiferromagnetic Co(II)-Co(II) couplings of -11.0 and -14.4 cm -1 for 1 and 2 , respectively, as also corroborated by DFT calculations, J theo = -13.07 cm -1 for 1 and -12.49 cm -1 for 2 . The calculated spin densities of both complexes at the cobalt(II) centers are -2.75 and +2.75, respectively, clearly supporting that they are the magnetic centers., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

We report the synthesis and characterization of six novel heterometallic molecule-based 2D magnets with the bromanilato ligand (C 6 O 4 Br 2 2- = 1,3-dibromo-2,5-dihydroxy-1,4-benzoquinone dianion) and six different benzene derivative molecules. The compounds, formulated as (NBu 4 )[MnCr(C 6 O 4 Br 2 ) 3 ]·1.75C 6 H 5 Br (1), (NBu 4 )[MnCr(C 6 O 4 Br 2 ) 3 ]·C 6 H 5 X with X = Cl (2), I (3) and CH 3 (4) and (NBu 4 )[MnCr(C 6 O 4 Br 2 ) 3 ]·2C 6 H 5 X with X = CN (5) and NO 2 (6), present the classical hexagonal honeycomb-(6,3) lattice with alternating Mn(ii) and Cr(iii) ions. The layers are packed in an eclipsed way along the a direction giving rise to hexagonal channels where the benzene derivative molecules are located with π-π interactions between the benzene and anilato rings. The interlayer space contains the NBu 4 + cations needed to compensate the anionic charge of the [Mn II Cr III (C 6 O 4 Br 2 ) 3 ] - layers. The Mn-Cr exchange coupling through the bromanilato ligands is antiferromagnetic, leading to a long range ferrimagnetic order in the six compounds with ordering temperatures around 10 K. These ordering temperatures can be slightly modified in the range 9.5-11.4 K by simply changing the benzene-derivative solvent molecule. Here we discuss the possible structural and electronic reasons for this tuning effect of the solvent molecule and the important structural role played by the solvent molecules. We also show that it is possible to exchange the solvent molecules inside the hexagonal channels post-synthetically causing a tiny change in the ordering temperature and coercive field. Furthermore, we also show that it is possible to further change the ordering temperatures by simply removing the solvent molecules by heating the sample at low pressures to obtain a de-solvated phase.

A new multidentate ligand (H 3 L) was synthesized by the condensation reaction of 4-tert-butyl-2,6-diformylphenol and 2-amino-4-nitrophenol. The reaction of the ligand with hydrated lanthanide nitrate produced two isostructural trinuclear coordination clusters: [DyLn 3 L 3 (DMF) 3 (H 2 O) 2 ] ⋅ 3.8DMFLn=Dy (1) and Nd (2) (DMF=N, N-dimethylformamide). Single-crystal X-ray diffraction analysis revealed that there are three lanthanide ions arranged in an almost perfect linear fashion in both complexes. Magnetic studies show single-molecule-magnet (SMM) behavior in the Dy derivative with τ 0 =1.7×10 -6  s and a thermal energy barrier of 7.0 cm -1 . Both complexes were used as catalysts towards the Friedel-Crafts alkylation reaction of indole with different aldehydes with yields varying from 59-98 %. Complex 1 showed better catalytic efficiency than complex 2. This is the first report of using trinuclear lanthanide coordination clusters as catalysts for the Friedel-Crafts alkylation reaction., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report the synthesis and characterization of the first fluorescent oxalato-based canted antiferromagnet. Compound [DOC][MnFe(C2O4)3] (1) (DOC = 3,3'-diethyloxacarbocyanine) combines the well-known canted antiferromagnetic [MnFe(C2O4)3]- honeycomb layers with a fluorescent cationic cyanine-type fluorescent dye. Besides the expected spin canted antiferromagnetic order in the oxalato layer at ca. 29 K, we show the key role played by the anionic oxalato lattice in the optical properties of the cation since it provides isolation of dye cations in the hexagonal cavities of the oxalato-based matrix. The emission of the DOC+ dye shows a redshift and a broadening of the emission as well as an increase in the lifetime compared to the emission of the DOC+ cations in solution. These facts are attributed to the isolation effect of the oxalato-based matrix.

We show the key role that the size and shape of the solvent molecules may play in the dimensionality and structure of a series of lanthanoid-chloranilato coordination polymers. We report the synthesis, structure and magnetic properties of six different coordination polymers prepared with Er(iii) and chloranilato (C6O4Cl22- = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) and six different solvents: [Er2(C6O4Cl2)3(H2O)6]·10H2O (1), [Er2(C6O4Cl2)3(FMA)6]·4FMA·2H2O (2) (FMA = formamide = NH2CHO), [Er2(C6O4Cl2)3(DMSO)4]·2DMSO·2H2O (3) (DMSO = dimethy sulfoxide = Me2SO), [Er2(C6O4Cl2)3(DMF)6] (4) (DMF = dimethylformamide = Me2NCHO), [Er2(C6O4Cl2)3(DMA)4] (5) (DMA = dimethylacetamide = Me2NC(Me)O) and [Er2(C6O4Cl2)3(HMPA)(H2O)3]·H2O (6) (HMPA = hexamethylphosphormamide = (Me2N)3PO). We show how the different solvent molecules modulate and determine important structural parameters such as the coordination number and geometry, the shape and distortions of the cavities, the presence of solvent molecules in these cavities, the interlayer space and even the dimensionality of the structure.

Studies the effects of antidepressants in the prophylaxis of depressive illness and in the treatment of acute episodes. Identification of delayed pharmacological effects of antidepressants; Down-regulation of β[sub 1]-adrenoceptor; Effect of chronic antidepressant treatments on serotonin signal parameters.