Mental health of children with special educational needs in the context of long-term crisis challenges: as seen by parents.

OBJECTIVE: Aim: To study the peculiarities of the mental health of children with special educational needs after 1.5 years of full-scale war in Ukraine. PATIENTS AND METHODS: Materials and Methods: The mental health of children with special educational needs (SEN) as well as the peculiarities of the impact of hostilities on their emotional and volitional sphere was assessed through the anonymous survey of their parents using the questionnaire developed by the authors (25 questions). The research, which was conducted in 2023 using a Google form, involved 466 parents having children with SEN aged 6 to 10. RESULTS: Results: It was found that among the surveyed families raising children with SEN, 30.7 % of children were in the combat zone or zone of temporary occupation for a week to a month, 19.1 % - for more than a month; 36.9 % of children experienced relocation, 23.4 % were separated from their parents, 19.7 % witnessed hostilities; 49.4 % of children experienced an unstable psycho-emotional state ("emotional swings") during 1.5 years of war in Ukraine, 40.1 % - restlessness, 38.6 % - anxiety; 23.2 % of parents noted that their children were "hooked" on computer games and social networks, 11.2 % - had problems with sleep, 10.5 % - demonstrated the emergence or increase in cognitive problems. CONCLUSION: Conclusions: The negative impact of prolonged stress during the war on the mental health of children with SEN has been revealed, which requires psychological support for such children from parents and psychologists.

Impact of Deuteration and Temperature on Furan Ring Dynamics.

Despite significant progress in conformational analysis of cyclic molecules, the number of computational studies is still limited while most of that available in the literature data have been obtained long time ago with outdated methods. In present research, we have studied temperature driven conformational changes of the furan ring at three different temperatures. Additionally, the effect of deuteration on the ring dynamics is discussed; in addition, the aromaticity indices following the Bird and HOMA schemes are computed along all trajectories. Our ab initio molecular dynamic simulations revealed that deuteration has changed the furan ring dynamics and the obvious consequences; in addition, the shape and size of molecule are expected to be different.

Hybrid compound based on diethylenetriaminecopper(ii) cations and scarce V-monosubstituted ß-octamolybdate as water oxidation catalyst.

Herein, we report on a new hybrid compound (NH4){[Cu(dien)(H2O)2]2[ß-VMo7O26]}·1.5H2O (1), where dien = diethylenetriamine, containing an extremely rare mixed-metal pseudo-octamolybdate cluster. An ex situ EPR spectroscopy provided insights into the formation of paramagnetic species in reaction mixture and in solution of 1. The magneto-structural correlations revealed weak antiferromagnetic exchange interactions between the [Cu(dien)]2+ cations transmitted by intermolecular pathways. The cyclic voltammetry showed the one-electron process associated with the Cu3+/Cu2+ oxidation followed by the multi-electron catalytic wave due to water oxidation with a faradaic yield of 86%. The title compound was thus employed in homogeneous water oxidation catalysis using tris(bipyridine)ruthenium photosensitizer. At pH 8.0, efficiency of the catalytic system attained 0.19 turnovers per second supported by the relatively mild water oxidation overpotential of 0.54 V.

Remote pacemaker control of chimera states in multilayer networks of neurons.

Networks of coupled nonlinear oscillators allow for the formation of nontrivial partially synchronized spatiotemporal patterns, such as chimera states, in which there are coexisting coherent (synchronized) and incoherent (desynchronized) domains. These complementary domains form spontaneously, and it is impossible to predict where the synchronized group will be positioned within the network. Therefore, possible ways to control the spatial position of the coherent and incoherent groups forming the chimera states are of high current interest. In this work we investigate how to control chimera patterns in multiplex networks of FitzHugh-Nagumo neurons, and in particular we want to prove that it is possible to remotely control chimera states exploiting the multiplex structure. We introduce a pacemaker oscillator within the network: this is an oscillator that does not receive input from the rest of the network but is sending out information to its neighbors. The pacemakers can be positioned in one or both layers. Their presence breaks the spatial symmetry of the layer in which they are introduced and allows us to control the position of the incoherent domain. We demonstrate how the remote control is possible for both uni- and bidirectional coupling between the layers. Furthermore we show which are the limitations of our control mechanisms when it is generalized from single-layer to multilayer networks.

Effect of topology upon relay synchronization in triplex neuronal networks.

Relay synchronization in complex networks is characterized by the synchronization of remote parts of the network due to their interaction via a relay. In multilayer networks, distant layers that are not connected directly can synchronize due to signal propagation via relay layers. In this work, we investigate relay synchronization of partial synchronization patterns like chimera states in three-layer networks of interacting FitzHugh-Nagumo oscillators. We demonstrate that the phenomenon of relay synchronization is robust to topological random inhomogeneities of small-world type in the layer networks. We show that including randomness in the connectivity structure either of the remote network layers or of the relay layer increases the range of interlayer coupling strength where relay synchronization can be observed.

Two populations of coupled quadratic maps exhibit a plentitude of symmetric and symmetry broken dynamics.

We numerically study a network of two identical populations of identical real-valued quadratic maps. Upon variation of the coupling strengths within and across populations, the network exhibits a rich variety of distinct dynamics. The maps in individual populations can be synchronized or desynchronized. Their temporal evolution can be periodic or aperiodic. Furthermore, one can find blends of synchronized with desynchronized states and periodic with aperiodic motions. We show symmetric patterns for which both populations have the same type of dynamics as well as chimera states of a broken symmetry. The network can furthermore show multistability by settling to distinct dynamics for different realizations of random initial conditions or by switching intermittently between distinct dynamics for the same realization. We conclude that our system of two populations of a particularly simple map is the most simple system that can show this highly diverse and complex behavior, which includes but is not limited to chimera states. As an outlook to future studies, we explore the stability of two populations of quadratic maps with a complex-valued control parameter. We show that bounded and diverging dynamics are separated by fractal boundaries in the complex plane of this control parameter.

Crystal structure of poly[(µ3-4-amino-1,2,5-oxa-diazole-3-hydroxamato)thallium(I)].

The title compound represents the thallium(I) salt of a substituted 1,2,5-oxa-diazole, [Tl(C3H3N4O3)] n , with amino- and hydroxamate groups in the 4- and 3- positions of the oxa-diazole ring, respectively. In the crystal, the deprotonated hydroxamate group represents an inter-mediate between the keto/enol tautomers and forms a five-membered chelate ring with the thallium(I) cation. The coordination sphere of the cation is augmented to a distorted disphenoid by two monodentately binding O atoms from two adjacent anions, leading to the formation of zigzag chains extending parallel to the b axis. The cohesion within the chains is supported by π-π stacking [centroid-centroid distance = 3.746 (3) Å] and inter-molecular N-H⋯N hydrogen bonds.

A binuclear CuII/CaII thio-cyanate complex with a Schiff base ligand derived from o-vanillin and ammonia.

The new heterometallic complex, aqua-1κO-bis-(µ2-2-imino-methyl-6-meth-oxy-phenolato-1κ2 O 1,O 6:2κ2 O 1,N)bis-(thio-cyanato-1κN)calcium(II)copper(II), [CaCu(C8H8NO2)2(NCS)2(H2O)], has been synthesized using a one-pot reaction of copper powder, calcium oxide, o-vanillin and ammonium thio-cyanate in methanol under ambient conditions. The Schiff base ligand (C8H9NO2) is generated in situ from the condensation of o-vanillin and ammonia, which is released from the initial NH4SCN. The title compound consists of a discrete binuclear mol-ecule with a {Cu(µ-O)2Ca} core, in which the Cu⋯Ca distance is 3.4275 (6) Å. The coordination geometries of the four-coordinate copper atom in the [CuN2O2] chromophore and the seven-coordinate calcium atom in the [CaO5N2] chromophore can be described as distorted square planar and penta-gonal bipyramidal, respectively. In the crystal, O-H⋯S hydrogen bonds between the coordinating water mol-ecules and thio-cyanate groups form a supra-molecular chain with a zigzag-shaped calcium skeleton.

Aminofluoresceins Versus Fluorescein: Ascertained New Unusual Features of Tautomerism and Dissociation of Hydroxyxanthene Dyes in Solution.

Within the course of this spectroscopic research, we revealed novel features of the protolytic behavior, which extend the knowledge of the chemistry of xanthene dyes and rationalize the utilization of these compounds. In addition to the well-known tautomerism of the molecular form, H2R, of fluorescein dyes, new aspects of tautomeric transformation of anions are disclosed. First, for the dyes bearing the substituents in the phthalic acid residue, 4'- and 5'-aminofluoresceins and 4'-fluorescein isothiocyanate, the monoanion HR- exists in non-hydrogen-bond donor solvents not only as a tautomer with the ionized carboxylic and nonionized OH group but also as a "phenolate" ion with a nonionized COOH group. Such state of HR- ions is typical for dyes bearing halogen atoms or NO2 groups in the xanthene moiety but was not observed until now in the case of substitution in the phthalic residue. Second, the possibility of the existence of the HR- species in DMSO in the form of colorless lactone is deduced for the 5'-aminofluorescein using the visible and infrared spectra. This results in a dramatic difference in medium effects. For instance, whereas for fluorescein in DMSO, the inversion of the stepwise ionization constants takes place and the Ka1/Ka2 value equals 0.08, the same ratio for 5'-aminofluorescein is as high as ∼800. In addition, the pKa values of sulfonefluorescein, erythrosin, methyl ether of fluorescein, and phenol red were obtained to verify the acidity scale in DMSO and to support the detailed scheme of protolytic equilibria of fluorescein dyes.

Aminofluoresceins Versus Fluorescein: Peculiarity of Fluorescence.

In this article, we examined the fluorescent properties of 4'- and 5'-aminofluorescein, unsubstituted fluorescein, and its 4'-nitro derivative in a set of solvent systems. Fluorescence lifetimes, quantum yields, time-resolved fluorescence spectra, and quantum chemical calculations allowed clarifying the reasons of the emitting properties in this dye series. In water, the dianions R2- of aminofluoresceins are practically nonfluorescent; in alcohols, the quantum yields are low. In dimethylsulfoxide (DMSO), acetonitrile, and other non-hydrogen bond donor solvents, the bright fluorescence of R2- ions is quenched either on adding small amounts of water which hydrate the carboxylate group or under conditions of protonation of this group (COO- → COOH). The last observation is possible owing to the peculiarities of the tautomerism of the 5'-aminofluorescein monoanion, HR-, which exists in DMSO as an equilibrium mixture of a colorless lactone and colored "phenolate" tautomer with an ionized xanthene moiety and unionized carboxylic group. In contrast, the R2- anion of 4'-nitrofluorescein demonstrates spectral behavior different from that of the amino derivatives. It practically does not emit in aprotic solvents; however, in alcohols or water media, its quantum yield increases to some extent. Such changing spectral properties are explained in terms of the excited-state interfragmental charge transfer.

Controlling chimera states via minimal coupling modification.

We propose a method to control chimera states in a ring-shaped network of nonlocally coupled phase oscillators. This method acts exclusively on the network's connectivity. Using the idea of a pacemaker oscillator, we investigate which is the minimal action needed to control chimeras. We implement the pacemaker choosing one oscillator and making its links unidirectional. Our results show that a pacemaker induces chimeras for parameters and initial conditions for which they do not form spontaneously. Furthermore, the pacemaker attracts the incoherent part of the chimera state, thus controlling its position. Beyond that, we find that these control effects can be achieved with modifications of the network's connectivity that are less invasive than a pacemaker, namely, the minimal action of just modifying the strength of one connection allows one to control chimeras.

About the Aromaticity of symm-Triaminotrinitrobenzene.

Aromaticity and structural features of the isolated symm-triaminotrinitrobenzene (TATB) were examined using the nonempirical ab initio quantum chemical method and molecular dynamics at the Car-Parrinello level. Different criteria of the aromaticity were combined with the study of conformational flexibility of molecule and analysis of the electron density distribution. It was found that the cooperative effect of the resonance-assisted hydrogen bonds results in the ultimate decreasing aromaticity of the benzene ring in TATB. Values of the HOMA index indicate that it could be classified as low-aromatic in equilibrium state at zero temperature but completely nonaromatic at room temperature. An extremely high flexibility of the molecule is also not typical for aromatic rings. The electron delocalization in H-bonded O═N-C═C-N-H quasi-aromatic rings was found to be greater than that in the benzene ring of TATB.

Robustness of chimera states in nonlocally coupled networks of nonidentical logistic maps.

We investigate the dynamics of nonlocally coupled time-discrete maps with emphasis on the occurrence and robustness of chimera states. These peculiar, hybrid states are characterized by a coexistence of coherent and incoherent regions. We consider logistic maps coupled on a one-dimensional ring with finite coupling radius. Domains of chimera existence form different tongues in the parameter space of coupling range and coupling strength. For a sufficiently large coupling strength, each tongue refers to a wave number describing the structure of the spatial profile. We also analyze the period-adding scheme within these tongues and multiplicity of period solutions. Furthermore, we study the robustness of chimeras with respect to parameter inhomogeneities and find that these states persist for different widths of the parameter distribution. Finally, we explore the spatial structure of the chimera using a spatial correlation function.

Optimal design of tweezer control for chimera states.

Chimera states are complex spatio-temporal patterns which consist of coexisting domains of spatially coherent and incoherent dynamics in systems of coupled oscillators. In small networks, chimera states usually exhibit short lifetimes and erratic drifting of the spatial position of the incoherent domain. A tweezer feedback control scheme can stabilize and fix the position of chimera states. We analyze the action of the tweezer control in small nonlocally coupled networks of Van der Pol and FitzHugh-Nagumo oscillators, and determine the ranges of optimal control parameters. We demonstrate that the tweezer control scheme allows for stabilization of chimera states with different shapes, and can be used as an instrument for controlling the coherent domains size, as well as the maximum average frequency difference of the oscillators.

Chimera states in brain networks: Empirical neural vs. modular fractal connectivity.

Complex spatiotemporal patterns, called chimera states, consist of coexisting coherent and incoherent domains and can be observed in networks of coupled oscillators. The interplay of synchrony and asynchrony in complex brain networks is an important aspect in studies of both the brain function and disease. We analyse the collective dynamics of FitzHugh-Nagumo neurons in complex networks motivated by its potential application to epileptology and epilepsy surgery. We compare two topologies: an empirical structural neural connectivity derived from diffusion-weighted magnetic resonance imaging and a mathematically constructed network with modular fractal connectivity. We analyse the properties of chimeras and partially synchronized states and obtain regions of their stability in the parameter planes. Furthermore, we qualitatively simulate the dynamics of epileptic seizures and study the influence of the removal of nodes on the network synchronizability, which can be useful for applications to epileptic surgery.