Magnetic Anisotropy of Homo- and Heteronuclear Terbium(III) and Dysprosium(III) Trisphthalocyaninates Derived from Paramagnetic 1H-NMR Investigation.

1H-NMR spectroscopy of lanthanide complexes is a powerful tool for deriving spectral-structural correlations, which provide a clear link between the symmetry of the coordination environment of paramagnetic metal centers and their magnetic properties. In this work, we have first synthesized a series of homo- (M = M* = Dy) and heteronuclear (M ≠ M* = Dy/Y and Dy/Tb) triple-decker complexes [(BuO)8Pc]M[(BuO)8Pc]M*[(15C5)4Pc], where BuO- and 15C5- are, respectively, butoxy and 15-crown-5 substituents on phthalocyanine (Pc) ligands. We provide an algorithmic approach to assigning the 1H-NMR spectra of these complexes and extracting the axial component of the magnetic susceptibility tensor, χax. We show how this term is related to the nature of the lanthanide ion and the shape of its coordination polyhedron, providing an experimental basis for further theoretical interpretation of the revealed correlations.

Phthalocyanine aggregates in the photodynamic therapy: dogmas, controversies, and future prospects.

Photodynamic therapy (PDT), a rapidly developing method for the treatment of cancer and bacterial diseases, is based on the photosensitization of oxygen to generate reactive oxygen species (ROS) that destroy specific biological targets. Among the various photosensitizers, phthalocyanines (Pc) have attracted particular attention due to their excellent photophysical properties, most of which meet the therapeutic requirements. The statement that aggregation of Pc-based photosensitizers is undesirable because it suppresses ROS generation has become commonplace in PDT. In this review, we have collected and discussed a number of works whose results refute this well-established axiom and show that aggregated forms of phthalocyanines can still exhibit photodynamic activity, in some cases in synergy with the photothermal and optoacoustic effects. In addition, ROS generation can be induced by aggregates under the conditions of sonodynamic therapy.

Site-Selective Solvation-Induced Conformational Switching of Heteroleptic Heteronuclear Tb(III) and Y(III) Trisphthalocyaninates for the Control of Their Magnetic Anisotropy.

In the present work, we report the synthesis of isomeric heteronuclear terbium(III) and yttrium(III) triple-decker phthalocyaninates [(BuO)8Pc]M[(BuO)8Pc]M*[(15C5)4Pc] (M = Tb, M* = Y or M = Y, M* = Tb, [(BuO)8Pc]2--octa-n-butoxyphthalocyaninato-ligand, [(15C5)4Pc]2--tetra-15-crown-5-phthalocyaninato-ligand). We show that these complexes undergo solvation-induced switching: the conformers in which both metal centers are in square-antiprismatic environments are stabilized in toluene, whereas in dichloromethane, the metal centers M and M* are in distorted prismatic and antiprismatic environments, respectively. This conclusion follows from the detailed analysis of lanthanide-induced shifts in 1H NMR spectra, which makes it possible to extract the axial component of the magnetic susceptibility tensor χaxTb and to show that this term is particularly sensitive to conformational switching when terbium(III) ion is placed in the switchable "M" site. This result provides a new tool for controlling the magnetic properties of lanthanide complexes with phthalocyanine ligands.

Solvation-Induced Conformational Switching of Trisphthalocyanates for Control of Their Magnetic Properties.

Stabilization of different conformers of sandwich phthalocyaninates by changing the solvation environment has been demonstrated with the examples of new heteroleptic yttrium(III) and terbium(III) triple-decker complexes [(BuO)8Pc]M[(BuO)8Pc]M[(15C5)4Pc] (where M = Y or Tb, [(BuO)8Pc]2- = octa-n-butoxyphthalocyaninato ligand, and [(15C5)4Pc]2- = tetra-15-crown-5-phthalocyaninato ligand). To this end, we have performed a comprehensive crystallographic characterization of two solvates formed by the Y(III) complex with either toluene or dichloromethane. In the solvate with toluene, both pairs of Pc ligands are in staggered conformations, providing both metal cations with a square-antiprismatic environment. In contrast, in the solvate with dichloromethane, only one cation between the BuO- and 15C5-substituted ligands remains in a square-antiprismatic polyhedron, while the pair of BuO-substituted ligands switches to a gauche conformation. In both solvates, the staggered conformations are stabilized by weak interactions of peripheral substituents with solvent molecules. Detailed analysis of the 1H NMR spectra of the isostructural Tb(III) complex in aliphatic and aromatic solvents demonstrates that the stabilization of the corresponding conformations by solvation is also valid in the solution state, resulting in an increase in the axial component of the magnetic susceptibility tensor as the symmetry decreases from staggered to gauche. Thus, solvation-induced conformational switching of lanthanide trisphthalocyaninates can be used as a tool to control their magnetic properties.

Rediscovery of Gryllomorpha miramae Medvedev, 1933 (Orthoptera: Gryllidae: Gryllomorphinae) in Ukraine.

Gryllomorpha miramae Medvedev, 1933 was collected in Zaporizhzhia and Kherson Regions of Ukraine. These are the first records of the species within Ukraine since more than 60 years from previous (and the first) record of the species within Zaporizhzhia Region. The species was found within intact and damaged steppe habitats. Our investigation shows that middle-age larvae demonstrate typical for the species coloration and shape of denticles of outer surface of hind tibia. This contribution provides first COI sequence for G. miramae.

Templating Effect of Water-Soluble Anionic Phthalocyaninate on the Electropolymerization of 3,4-Ethylenedioxythiophene.

The electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) was performed in the presence of a water-soluble anionic copper and zinc octa(3',5'-dicarboxyphenoxy)phthalocyaninate containing 16 ionogenic carboxylate groups. The influences of the central metal atom in the phthalocyaninate and EDOT-to-carboxylate group ratio (1:2, 1:4, and 1:6) on the course of electropolymerization were studied using electrochemical methods. It has been shown that the polymerization of EDOT in the presence of phthalocyaninates proceeds at a higher rate compared to that in the presence of a low-molecular-weight electrolyte (sodium acetate). Studies of the electronic and chemical structure using UV-Vis-NIR and Raman spectroscopies showed that the use of copper phthalocyaninate leads to a higher content of the latter in PEDOT composite films. The 1:2 EDOT-to-carboxylate group ratio was found to be optimal for a higher content of phthalocyaninate in the composite film.

Narrowly defined taxa on a global scale: The phylogeny and taxonomy of the genera Catriona and Tenellia (Nudibranchia, Trinchesiidae) favours fine-scale taxonomic differentiation and dissolution of the "lumpers & splitters" dilemma.

By applying morphological and molecular data on two genera of the nudibranch molluscs it is shown that the tension between taxonomic practice and evolutionary processes persists. A review of the related genera Catriona and Tenellia is used to demonstrate that the fine-scale taxonomic differentiation is an important tool in the integration of morphological and molecular data. This is highlighted by the hidden species problem and provides strong argument that the genus must be kept as a maximally narrowly-defined entity. Otherwise, we are forced to compare a highly disparate species under the putatively lumped name "Tenellia". We demonstrate this in the present study by applying a suite of delimitation methods and describing a new species of Tenellia from the Baltic Sea. The new species possesses fine-scale morphological distinguishing features, which were not investigated before. The true, narrowly defined genus Tenellia represents a peculiar taxon with a clearly expressed paedomorphic characters and predominantly brackish-water habitats. The phylogenetically related genus Catriona, of which three new species are described here, clearly demonstrates different features. A lumping decision to call many morphologically and evolutionary different taxa as "Tenellia" will downgrade the taxonomic and phylogenetic resolution of the entire family Trinchesiidae to just a single genus. The dissolution of the dilemma of "lumpers & splitters", which still significantly affects taxonomy, will further help to make systematics a true evolutionary discipline.

Treatment of COVID-19 patients with a SARS-CoV-2-specific siRNA-peptide dendrimer formulation.

BACKGROUND: Severe acute respiratory syndrome corona virus (SARS-CoV-2) infection frequently causes severe and prolonged disease but only few specific treatments are available. We aimed to investigate safety and efficacy of a SARS-CoV-2-specific siRNA-peptide dendrimer formulation MIR 19® (siR-7-EM/KK-46) targeting a conserved sequence in known SARS-CoV-2 variants for treatment of COVID-19. METHODS: We conducted an open-label, randomized, controlled multicenter phase II trial (NCT05184127) evaluating safety and efficacy of inhaled siR-7-EM/KK-46 (3.7 mg and 11.1 mg/day: low and high dose, respectively) in comparison with standard etiotropic drug treatment (control group) in patients hospitalized with moderate COVID-19 (N = 52 for each group). The primary endpoint was the time to clinical improvement according to predefined criteria within 14 days of randomization. RESULTS: Patients from the low-dose group achieved the primary endpoint defined by simultaneous achievement of relief of fever, normalization of respiratory rate, reduction of coughing, and oxygen saturation of >95% for 48 h significantly earlier (median 6 days; 95% confidence interval [CI]: 5-7, HR 1.75, p = .0005) than patients from the control group (8 days; 95% CI: 7-10). No significant clinical efficacy was observed for the high-dose group. Adverse events were reported in 26 (50.00%), 25 (48.08%), and 28 (53.85%) patients from the low-, high-dose and control group, respectively. None of them were associated with siR-7-EM/KK-46. CONCLUSIONS: siR-7-EM/KK-46, a SARS-CoV-2-specific siRNA-peptide dendrimer formulation is safe, well tolerated and significantly reduces time to clinical improvement in patients hospitalized with moderate COVID-19 compared to standard therapy in a randomized controlled trial.

The Tribe Hyrtanellini Allen, 1980 (Ephemeroptera: Ephemerellidae) of Western and Central Asia with Description of a New Species.

A new species, Serratella leonidi Martynov & Palatov, sp. nov., is described from Tajikistan based on immature stage. Based on larval material from Iran including the topotypes, Serratella elissa Jacobus, Zhou & McCafferty, 2009 is complementary described, and its generic placement is clarified. The delimitation of three genera that are members of the tribe Hyrtanellini Allen, 1980, namely Serratella Edmunds, 1959, Torleya Lestage, 1917 and Quatica Jacobus & McCafferty, 2008 is briefly discussed. The phylogenetic reconstruction of Hyrtanellini based on the COI gene showed the relations of representatives of these genera on the one hand, and distinct delimitation of Serratella leonidi sp. nov. and S. elissa on the other. A list of species from Western and Central Asia attributed to Hyrtanellini, their currently known distribution and a key for the determination of the larvae are proposed.

Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities.

The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide complexes in solution, using NMR is a difficult task, since several paramagnetic centers act simultaneously on the resulting chemical shift of a particular nucleus. In this paper, we have demonstrated the possibility of molecular structure determination in solution on the example of binuclear triple-decker lanthanide(III) complexes with tetra-15-crown-5-phthalocyanine Ln2[(15C5)4Pc]3 {where Ln = Tb (1) and Dy (2)} by quantitative analysis of the pseudo-contact lanthanide-induced shifts (LIS). The symmetry of complexes was used for the simplification of the calculation of pseudo-contact shifts on the base of the expression for the magnetic susceptibility tensor in the arbitrary oriented magnetic axis system. Good agreement between the calculated and experimental shifts in the 1H NMR spectra indicates the similarity of the structure for the complexes 1 and 2 in solution of CDCl3 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu2[(15C5)4Pc]3. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes.

Substitution pattern in ruthenium octa-n-butoxyphthalocyanine complexes influence their reactivity in N-H carbene insertions.

Ruthenium phthalocyanine complexes bearing n-OBu substituents in the peripheral or non-peripheral positions are efficient catalysts for the selective double or single carbene insertion to the amine N-H bonds. This complementary reactivity of two Ru complexes can be used for the synthesis of asymmetric tertiary amines and diamines bearing different substituents and has been demonstrated by two examples of readily available primary amines using different carbene precursors in successive reactions.

Redox-Triggered Switching of Conformational State in Triple-Decker Lanthanide Phthalocyaninates.

Double- and triple-decker lanthanide phthalocyaninates exhibit unique physical-chemical properties, particularly single-molecule magnetism. Among other factors, the magnetic properties of these sandwiches depend on their conformational state, which is determined via the skew angle of the phthalocyanine ligands. Thus, in the present work we report the comprehensive conformational study of substituted terbium(III) and yttrium(III) trisphthalocyaninates in solution depending on the substituents at the periphery of molecules, redox-states and nature of solvents. Conjunction of UV-vis-NIR spectroscopy and quantum-chemical calculations within simplified time-dependent DFT in Tamm-Dancoff approximation provided the spectroscopic signatures of staggered and gauche conformations of trisphthalocyaninates. Altogether, it allowed us to demonstrate that the butoxy-substituted complex behaves as a molecular switcher with controllable conformational state, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. The analysis of noncovalent interactions within the reduced density gradient approach allowed to shed light on the nature of factors stabilizing certain conformers.

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications.

The unique properties of natural tetrapyrrolic compounds have inspired the rapid growth of research interest in the design and synthesis of artificial porphyrinoids and their metal complexes as a basis of modern functional materials. A special role in the design of such materials is played by sandwich complexes formed by tetrapyrrolic macrocycles with rare earth elements, especially lanthanides. The development of synthetic approaches to the functionalization of tetrapyrrolic compounds and their rare earth complexes has facilitated the intensive development of new applications over the last decade. As a way of expanding the functionalities of rare earth complexes, sophisticated examples have been obtained, including mixed-ligand complexes, π-extended analogues, covalently linked and fused sandwiches, complexes with less-common tetrapyrrols, sandwiches with non-tetrapyrrolic macrocycles and even complexes containing up to six stacked ligands. This review intends to offer a general overview of the preparation of such sophisticated REE tetrapyrrolic sandwiches over the last decade as well as emphasizes the current challenges and perspectives of their application in areas such as single-molecule magnetism (SMM), organic field-effect transistors (OFET), conductive materials and nonlinear optics (NLO).

A catalogue of the types of rove beetles (Coleoptera: Staphylinidae) deposited in the collection of Johan Heinrich Hochhuth in the National Museum of Natural History of the National Academy of Sciences of Ukraine.

Type specimens of Staphylinidae (Coleoptera) from the collection of J.H. Hochhuth (18101872) deposited in National Museum of Natural History of the National Academy of Sciences of Ukraine (Kyiv) are currently being catalogued and illustrated. This catalogue presents information about 103 type specimens (14 holotypes, 80 lecto- and paratypes, and nine syntypes) belonging to 67 nominal species. Several lectotypes are designated: Conurus erythrocephalus Hochhuth, 1849, Aleochara solida Hochhuth, 1849, Trogophloeus kiesenwetterii Hochhuth, 1851, Ocypus pullus Hochhuth, 1849, Philonthus armeniacus Hochhuth, 1851, P. interpunctatus Hochhuth, 1860, and P. subopacus Hochhuth, 1851.

Persistence of plasmids targeted by CRISPR interference in bacterial populations.

CRISPR-Cas systems provide prokaryotes with an RNA-guided defense against foreign mobile genetic elements (MGEs) such as plasmids and viruses. A common mechanism by which MGEs avoid interference by CRISPR consists of acquisition of escape mutations in regions targeted by CRISPR. Here, using microbiological, live microscopy and microfluidics analyses we demonstrate that plasmids can persist for multiple generations in some Escherichia coli cell lineages at conditions of continuous targeting by the type I-E CRISPR-Cas system. We used mathematical modeling to show how plasmid persistence in a subpopulation of cells mounting CRISPR interference is achieved due to the stochastic nature of CRISPR interference and plasmid replication events. We hypothesize that the observed complex dynamics provides bacterial populations with long-term benefits due to continuous maintenance of mobile genetic elements in some cells, which leads to diversification of phenotypes in the entire community and allows rapid changes in the population structure to meet the demands of a changing environment.

Low-Symmetry Phthalocyanines Bearing Carboxy-Groups: Synthesis, Spectroscopic and Quantum-Chemical Characterization.

The synthesis and characterization of A3B-type phthalocyanines, ZnPc1-4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units "A" and either one or two carboxylic anchors on isoindoline unit "B" are reported. A comparison of molecular modelling with the conventional time dependent-density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.

Octopus-Type Crown-Bisphthalocyaninate Anchor for Bottom-Up Assembly of Supramolecular Bilayers with Expanded Redox-Switching Capability.

Achievement of information storage at molecular level remains a pressing task in miniaturization of computing technology. One of the promising approaches for its practical realization is development of nanoscale molecular switching materials including redox-active systems. The present work demonstrates a concept of expansion of a number of available redox-states of self-assembled monolayers through supramolecular approach. For this, the authors synthesized an octopus-like heteroleptic terbium(III) bisphthalocyaninate bearing one ligand with eight thioacetate-terminated "tentacles" (octopus-Pc) and a ligand with four crown-ether moieties (H2 [(15C5)4 Pc]). It is shown that octopus-Pc forms stable monolayers on gold, where its face-on orientation allows for subsequent binding of crown-phthalocyanine molecules via potassium ion bridges. This chemistry is utilized to form a heterogeneous bilayer, in which a single molecule thick adlayer brings an additional redox-state to the system, thus expanding the multistability of the system as a whole. All four redox states available to this system exhibit characteristic absorbance in visible range, allowing for the switching to be easily read out using optical density measurements. The proposed approach can be used in wide range of switchable materials-single-molecule magnets, conductive, and optical devices, etc.

Contribution to the knowledge of Teloganodidae (Ephemeroptera, Ephemerelloidea) of India.

Two new species of Dudgeodes Sartori, 2008 and a new species of Teloganodes Eaton, 1882 are described from India; they are Dudgeodesselvakumari Martynov & Palatov, sp. nov. from Himalayan region (Uttarakhand), Dudgeodesmolinerii Sivaruban, Martynov, Srinivasan, Barathy & Isack, sp. nov., and Teloganodesbarathyae Sivaruban, Martynov, Srinivasan & Isack, sp. nov. from the Tamil Nadu part of the Western Ghats. Thus, for now, the Teloganodidae fauna of India includes 11 species. Dudgeodesselvakumari sp. nov. appears to be significantly extend northward the known distribution of Dudgeodes. Partial COI sequences were used as an initial clustering method to show the relationships of D.selvakumari sp. nov. with other sequenced operational taxonomic units (OTU) of the genus.

Ultrasensitive Optical Fingerprinting of Biorelevant Molecules by Means of SERS-Mapping on Nanostructured Metasurfaces.

The most relevant technique for portable (on-chip) sensors is Surface Enhanced Raman Scattering (SERS). This strategy crashes in the case of large (biorelevant) molecules and nano-objects, whose SERS spectra are irreproducible for "homeopathic" concentrations. We suggested solving this problem by SERS-mapping. We analyzed the distributions of SERS parameters for relatively "small" (malachite green (MG)) and "large" (phthalocyanine, H2Pc*) molecules. While fluctuations of spectra for "small" MG were negligible, noticeable distribution of spectra was observed for "large" H2Pc*. We show that the latter is due to a random arrangement of molecules with respect to "hot spot" areas, which have limited sizes, thus amplifying the lines corresponding to vibrations of different molecule parts. We have developed a method for engineering low-cost SERS substrates optimized for the best enhancement efficiency and a measurement protocol to obtain a reliable Raman spectrum, even for a countable number of large molecules randomly distributed over the substrate.

Transcriptomics provides a robust framework for the relationships of the major clades of cladobranch sea slugs (Mollusca, Gastropoda, Heterobranchia), but fails to resolve the position of the enigmatic genus Embletonia.

BACKGROUND: The soft-bodied cladobranch sea slugs represent roughly half of the biodiversity of marine nudibranch molluscs on the planet. Despite their global distribution from shallow waters to the deep sea, from tropical into polar seas, and their important role in marine ecosystems and for humans (as targets for drug discovery), the evolutionary history of cladobranch sea slugs is not yet fully understood. RESULTS: To enlarge the current knowledge on the phylogenetic relationships, we generated new transcriptome data for 19 species of cladobranch sea slugs and two additional outgroup taxa (Berthella plumula and Polycera quadrilineata). We complemented our taxon sampling with previously published transcriptome data, resulting in a final data set covering 56 species from all but one accepted cladobranch superfamilies. We assembled all transcriptomes using six different assemblers, selecting those assemblies that provided the largest amount of potentially phylogenetically informative sites. Quality-driven compilation of data sets resulted in four different supermatrices: two with full coverage of genes per species (446 and 335 single-copy protein-coding genes, respectively) and two with a less stringent coverage (667 genes with 98.9% partition coverage and 1767 genes with 86% partition coverage, respectively). We used these supermatrices to infer statistically robust maximum-likelihood trees. All analyses, irrespective of the data set, indicate maximal statistical support for all major splits and phylogenetic relationships at the family level. Besides the questionable position of Noumeaella rubrofasciata, rendering the Facelinidae as polyphyletic, the only notable discordance between the inferred trees is the position of Embletonia pulchra. Extensive testing using Four-cluster Likelihood Mapping, Approximately Unbiased tests, and Quartet Scores revealed that its position is not due to any informative phylogenetic signal, but caused by confounding signal. CONCLUSIONS: Our data matrices and the inferred trees can serve as a solid foundation for future work on the taxonomy and evolutionary history of Cladobranchia. The placement of E. pulchra, however, proves challenging, even with large data sets and various optimization strategies. Moreover, quartet mapping results show that confounding signal present in the data is sufficient to explain the inferred position of E. pulchra, again leaving its phylogenetic position as an enigma.