Long-living transients in ecological models: Recent progress, new challenges, and open questions.

Traditionally, mathematical models in ecology placed an emphasis on asymptotic, long-term dynamics. However, a large number of recent studies highlighted the importance of transient dynamics in ecological and eco-evolutionary systems, in particular 'long transients' that can last for hundreds of generations or even longer. Many models as well as empirical studies indicated that a system can function for a long time in a certain state or regime (a 'metastable regime') but later exhibits an abrupt transition to another regime not preceded by any parameter change (or following the change that occurred long before the transition).

Reaction-diffusion waves in biology: new trends, recent developments.

Reaction-diffusion systems are widely used in the description of propagation phenomena in biological systems, where chemical and biological processes combine to produce spatial and temporal patterns. This paper explores the recent trends and developments in the study of reaction-diffusion waves, highlighting their relevance to diverse biological contexts such as population dynamics, ecology or biomedical applications. Progress in mathematical techniques and computational methods advances our ability to model these systems, providing deeper insights into wave propagation, stability, and bifurcations.

Mathematical model of oxygen minimum zones in the vertical distribution of oxygen in the ocean.

Processes determining the amount and spatial distribution of dissolved oxygen in the ocean have been a focus of intense research over the last two decades. Anomalies known as Oxygen Minimum Zones (OMZs) have been attracting growing attention, in particular because their growth is believed to be a result of the global environmental change. Comprehensive understanding of factors contributing to and/or controlling the emergence and evolution of OMZs is still lacking though.

Using Coordination Chemistry to Control "Click" Reactions: The Selective Formation of Asymmetrically Ligated Polyoxometalates.

The Cu(I)-catalyzed azide-alkyne cycloaddition reaction between (NBu)[VO((OCH)CCHN)] and 3-ethynylpyridine led to the formation of products capable of forming poorly soluble coordination compounds with transition metal ions such as Cu(I) and Zn(II). The formation of these poorly soluble phases is an important feature that was used to determine the course of reactions, allowing the selective preparation of symmetric bis-pyridyltriazolyl and asymmetric monopyridyltriazolyl derivatives with relatively high yields and high substrate conversions. The asymmetric compound (NBu)[VO((OCH)CCH-NCH-CHN)((OCH)CCHN)] (V) was utilized in the subsequent "click" postfunctionalization reaction with 1,4-diethynylbenzene, resulting in a covalently bound V-V dimer.

A two-timescale model of plankton-oxygen dynamics predicts formation of oxygen minimum zones and global anoxia.

Decline of the dissolved oxygen in the ocean is a growing concern, as it may eventually lead to global anoxia, an elevated mortality of marine fauna and even a mass extinction. Deoxygenation of the ocean often results in the formation of oxygen minimum zones (OMZ): large domains where the abundance of oxygen is much lower than that in the surrounding ocean environment. Factors and processes resulting in the OMZ formation remain controversial.

Bioorthogonal chemistry of polyoxometalates - challenges and prospects.

Bioorthogonal chemistry has enabled scientists to carry out controlled chemical processes in high yields while minimizing hazardous effects. Its extension to the field of polyoxometalates (POMs) could open up new possibilities and new applications in molecular electronics, sensing and catalysis, including inside living cells. However, this comes with many challenges that need to be addressed to effectively implement and exploit bioorthogonal reactions in the chemistry of POMs.

Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di--butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from MLCT/LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM.

X/Y platinum(II) complexes: some features of supramolecular assembly halogen bonding.

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction.

Increasing the redox switching capacity of Lindqvist-type hexavanadates by organogold post-functionalisation.

The covalent attachment of organogold(I) moieties to the Lindqvist-type polyoxovanadate results in a measurable charge re-distribution across the formed Au-{V6}-Au linkages. Scanning probe microscopy studies of these hybrid compounds on the Au(111) surface demonstrate the increase in the number of switching states with stepwise increase in molecular conductance, compared with unfunctionalised hexavanadates.

Homoleptic Alkynylpyridinium Au(I) Complexes as Organometallic 'D-π-A' Chromophores.

A series of terminal acetylenes bearing methylpyridinium acceptor group attached to the alkynyl unit with different π-conjugated aromatic linker have been synthetized. These alkynylpyridinium salts are efficient 'push-pull' chromophores demonstrating bright UV-vis fluorescence with quantum yields up to 70 %. The homoleptic bis-alkynyl Au(I) complexes based on these alkynylpyridinium ligands demonstrate complicated photophysical behavior including dual emission in solution.

Homoleptic Alkynylphosphonium Au(I) Complexes as Push-Pull Phosphorescent Emitters.

A series of compounds - bearing terminal alkynyl sites connected with a phosphonium group via different π-conjugated linkers have been synthesized. The compounds themselves are efficient push-pull emitters and exhibit bright fluorescence in blue and near-UV regions. - were used as alkynyl ligands to obtain a series of homoleptic bis-alkynyl Au(I) complexes -.

Dynamical modelling of street protests using the Yellow Vest Movement and Khabarovsk as case studies.

Social protests, in particular in the form of street protests, are a frequent phenomenon of modern world often making a significant disruptive effect on the society. Understanding the factors that can affect their duration and intensity is therefore an important problem. In this paper, we consider a mathematical model of protests dynamics describing how the number of protesters change with time.

Post-Functionalization of Organometallic Complexes via Click-Reaction.

CuAAC (Cu catalyzed azide-alkyne cycloaddition) click-reaction is a simple and powerful method for the post-synthetic modification of organometallic complexes of transition metals. This approach allows the selective introduction of additional donor sites or functional groups to the periphery of the ligand environment. This is especially important if a metalloligand with free donor sites, which are of the same nature as the primary site for the coordination of the primary metal, has to be created.

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu and Au@Ag Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag(PyP)]X and [Au@Cu(PyP)]X [X = NO, ClO, OTf, BF, SbF], containing unprecedented Au-centered Ag and Cu tetrahedral cores supported by tris(2-pyridyl)phosphine (PyP) ligands. The [Au@Ag] clusters are synthesized controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag] precursors by the reaction with Au()Cl, while the [Au@Cu] cluster is assembled through the treatment of a pre-organized [Au(PyP)] metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions.

Knowledge gaps and missing links in understanding mass extinctions: Can mathematical modeling help?

Extinction of species, and even clades, is a normal part of the macroevolutionary process. However, several times in Earth history the rate of species and clade extinctions increased dramatically compared to the observed "background" extinction rate. Such episodes are global, short-lived, and associated with substantial environmental changes, especially to the carbon cycle.

The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes.

In this work we show, using the example of a series of [Cu(Xantphos)(N^N)] complexes (N^N being substituted 5-phenyl-bipyridine) with different peripheral N^N ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with -Si(CH), -Au(PR), and -CHN(CH)CH fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer.

A predictive model and a field study on heterogeneous slug distribution in arable fields arising from density dependent movement.

Factors and processes determining heterogeneous ('patchy') population distributions in natural environments have long been a major focus in ecology. Existing theoretical approaches proved to be successful in explaining vegetation patterns. In the case of animal populations, existing theories are at most conceptual: they may suggest a qualitative explanation but largely fail to explain patchiness quantitatively.

Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers.

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane--dimethylsiloxane) (N-PDMS) was synthesized for incorporation of azide function in polysiloxane chain.

Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized.

Oscillations and Pattern Formation in a Slow-Fast Prey-Predator System.

We consider the properties of a slow-fast prey-predator system in time and space. We first argue that the simplicity of the prey-predator system is apparent rather than real and there are still many of its hidden properties that have been poorly studied or overlooked altogether. We further focus on the case where, in the slow-fast system, the prey growth is affected by a weak Allee effect.

Towards Building a Sustainable Future: Positioning Ecological Modelling for Impact in Ecosystems Management.

As many ecosystems worldwide are in peril, efforts to manage them sustainably require scientific advice. While numerous researchers around the world use a great variety of models to understand ecological dynamics and their responses to disturbances, only a small fraction of these models are ever used to inform ecosystem management. There seems to be a perception that ecological models are not useful for management, even though mathematical models are indispensable in many other fields.

Effects of stochasticity on the length and behaviour of ecological transients.

There is a growing recognition that ecological systems can spend extended periods of time far away from an asymptotic state, and that ecological understanding will therefore require a deeper appreciation for how long ecological transients arise. Recent work has defined classes of deterministic mechanisms that can lead to long transients. Given the ubiquity of stochasticity in ecological systems, a similar systematic treatment of transients that includes the influence of stochasticity is important.