Bridge-Dependent Donor-Metal-Acceptor-Metal-Donor (D-M-A-M-D) Systems: From Charge Transfer to Electron Transfer in Dioxolene-Ge-Diimine Complexes.

Synthesis and structural characterization of a family of germanium-dioxolene complexes with ditopic N-donor ligands (L-L) (L=1,2-bis(pyridin-2-ylmethylene)hydrazine L=1,6-bis-(pyridin-2-yl)-2,5-diaza-1,5-hexadiene, L=N,N-bis(pyridin-2-ylmethylene)-1,4-benzenediamine, L=N,N-bis(pyridin-2-ylmethylene)-(biphenyl)-4,4-diamine, L=2,2'-azopyridine) is reported. The reaction of germanium bis-catecholate with bridging ligands L - L, differing by the nature of the linker between pyridine sites gives rise to dinuclear digermanium complexes (36CatGe)L (36Cat=dianion of 3,6-di-tert-butylcatechol) 1-4 of DMAMD type (donor-metal-acceptor-metal-donor) with a charge transfer in the UV-Vis region. In opposite, the interaction of the 36CatGe with 2,2'-azopyridine (L) results in the two-electron transfer from the donor 36Cat ligands to the azopyridine bridge forming stable open-shell complex 5 [(36SQ)(36CatGe)](L) (36SQ=radical-anionic semiquinonate ligand).

Optimization of Total DNA Extraction from Dried Blood Samples.

While dried blood spots are a convenient source of genetic material, they are usually associated with a lower DNA yield than from a native sample. The study evaluated the DNA yield from dried blood samples prepared on glass fibre and cellulose membranes and investigated the reasons for the yield reduction. The extraction of total DNA from membrane-dried blood samples was optimized by spin-column extraction method.

Porogen Concentration Effect on the Pore Structure and Properties Evolution of Polymer Monolith Based on Oligocarbonate Dimethacrylate OCM-2.

Porous polymer monolith materials of 2-mm thickness were obtained by visible light-induced radical polymerization of oligocarbonate dimethacrylate (OCM-2) in the presence of 1-butanol (10 to 70 wt %) as a porogenic additive. The pore characteristics and morphology of polymers were studied by mercury intrusion porosimetry and scanning electron microscopy. Monolithic polymers with both open and closed pores up to 100 nm in size are formed when the alcohol content in the initial composition is up to 20 wt %.

Novel Rigidochromic and Anti-Kasha Dual Emission Fluorophores Based on D-π-A Dyads as the Promising Materials for Potential Applications Ranging from Optoelectronics and Optical Sensing to Biophotonics and Medicine.

Today we see an increasing demand for new fluorescent materials exhibiting various sensory abilities due to their broad applicability ranging from the construction of flexible devices to bioimaging. In this paper, we report on the new fluorescent pigments AntTCNE, PyrTCNE, and PerTCNE which consist of 3-5 fused aromatic rings substituted with tricyanoethylene fragments forming D-π-A diad. Our studies reveal that all three compounds exhibit pronounced rigidochromic properties, i.

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes.

A series of new charge transfer (CT) chromophores of "α-diimine-M-catecholate" type (where M is 3d-row transition metals-Cu, Ni, Co) were derived from 4,4'-di--butyl-2,2'-bipyridyl and 3,6-di--butyl--benzoquinone () in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric () and () chromophores, while dimeric complex () units two substantially distorted heteroleptic D-M-A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores - undergo an effective photoinduced intramolecular charge transfer (λ = 500-715 nm, extinction coefficient up to 10 M·cm) with a concomitant generation of a less polar excited species, the energy of which is a finely sensitive towards solvent polarity, ensuring a pronounced negative solvatochromic effect.

Novel Antireflection Coatings Obtained by Low-Temperature Annealing in the Presence of Tetrabutylammonium Bromide and Gold Nanoparticles.

In this work, nanoporous antireflective coatings on silicate glass were obtained from silicon dioxide sol compositions by the sol-gel method in the presence of quaternary ammonium salt (tetrabutylammonium bromide) at different annealing temperatures (200-250 °C). Varying the salt concentration from 3 to 5 wt.%, we achieved the transmittance of the coatings of about 97% at 250 °C in comparison with 91% for clean glass in the wavelength range from 400 to 1100 nm.

Magnetically bistable cobalt-dioxolene complexes with a tetradentate N-donor base.

Synthesis and magnetic characterization of a family of cobalt-dioxolene complexes [(MeTPA)Co(36-DBCat)] (1), [(MeTPA)Co(36-DBCat)](PF) (2) and [(MeTPA)Co(diox-(OMe))](BPh) (3) (MeTPA = bis(6-methyl-2-pyridyl)methyl-(2-pyridylmethyl)amine; 36-DBCat = dianion of 3,6-di--butylcatechol; diox-(OMe) - 2,5-di--butyl-3,3,4-trimethoxy-6-oxocyclohexa-1,4-dienolate) is reported. The neutral complex 1 is found to form hexa- (CoON, 1a) and pentacoordinated (CoON, 1b) isomers. Variable temperature single crystal X-ray diffraction analysis of 1a and 1b clearly indicates the presence of the high-spin divalent metal ion and the dianionic catecholate form of the dioxolene ligand.

Spin transitions in ferric catecholate complexes mediated by outer-sphere counteranions.

A family of ionic ferric catecholate complexes 1-4 bearing a disubstituted 3,6-di--butyl-catecholate ligand (3,6-DBCatH) and tetradentate tris(2-pyridylmethyl)amine (TPA) was prepared and its spin transitions were investigated. Variation of the outer-sphere counteranions (PF, BPh, ClO, BF) is accompanied by changes in the magnetic behavior of the compounds under consideration. The crystal structures of complexes 1, 3 and 4 were determined by single crystal X-ray diffraction analysis at 100 K and 293 K.

Towards Asymmetrical Methylene Blue Analogues: Synthesis and Reactivity of 3-'-Arylaminophenothiazines.

The search for new ways to obtain analogues of the well-known Methylene Blue dye is an important synthetic task. Herein, we proposed and developed an approach to the synthesis of 3-'-arylaminophenothiazines and asymmetrical 3,7-di('-arylamino)phenothiazines. This approach included the optimization of synthetic strategy by quantification analysis of the positive charge distribution in the cation of 3-'-arylaminophenothiazine derivative.

Genetic Diversity, Population Structure and Phylogeny of Indigenous Goats of Mongolia Revealed by SNP Genotyping.

Mongolian goats are of great interest for studying ancient migration routes and domestication, and also represent a good model of adaptability to harsh environments. Recent climatic disasters and uncontrolled massive breeding endangered the valuable genetic resources of Mongolian goats and raised the question of their conservation status. Meanwhile, Mongolian goats have never been studied on genomic scale.

Square-Planar Heteroleptic Complexes of α-Diimine-Ni-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer.

Two heteroleptic Ni complexes combined the redox-active catecholate and 2,2'- bipyridine ligand platforms were synthesized to observe a photoinduced intramolecular ligand-to-ligand charge transfer (LL'CT, HOMO → LUMO). A molecular design of compound [Ni(3,6-Cat)(bipy)]∙CHCN () on the base of bulky 3,6-di--butyl--benzoquinone () was an annelation of the ligand with an electron donor glycol fragment, producing derivative [Ni(3,6-Cat)(bipy)]∙CHCl (), in order to influence the energy of LL'CT transition. A substantial longwave shift of the absorption peak was observed in the UV-Vis-NIR spectra of compared with those in .

Complexes of Metal Halides with Unreduced -(Imino)quinones.

A series of complexes of metal halides with unreduced quinone-type ligands have been synthesized and characterized in detail. The 3,6-di--butyl--benzoquinone () and 4,6-di--butyl--aryl-substituted -iminobenzoquinones (-) (aryl is 2,6-dimethylphenyl in , 2-methyl-6-ethylphenyl in , 2,6-diethylphenyl in , and 2,6-diisopropylphenyl in ) were used to obtain the molecular complexes with metal 12 group halides as well as with indium(III) iodide. The molecular structures of five complexes, bearing an unreduced form of redox-active ligand, have been established by single-crystal X-ray analysis.

Heteroleptic La Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers.

Three new 3D metal-organic frameworks of lanthanum based on mixed anionic ligands, [(La(pQ)(BDC))·4DMF], [(La(pQ)(DHBDC))·4DMF], [(La(CA)(BDC))·4DMF] (pQ-dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA-dianion of chloranilic acid, BDC-1,4-benzenedicarboxylate, DHBDC-2,5-dihydroxy-1,4-benzenedicarboxylate and DMF-N,N'-dimethylformamide), were synthesized using solvothermal methodology. Coordination polymers demonstrate the rare or topology of a 3D framework. The homoleptic 2D-coordination polymer [(La(pQ))·4DMF] was obtained as a by-product in the course of synthetic procedure optimization.

The (Dioximate)Ni/I System: Ligand Oxidation and Binding Modes of Triiodide Species.

Reinvestigation of (-benzoquinonedioximate)Ni/I systems demonstrated that the reaction itself and also the crystallization conditions dramatically affect the identity of generated species. Crystallization (CHCl, 20-25 °C) of the nickel(II) dioximate complex [Ni(bqoxH)] (bqoxH = -benzoquinonedioxime) with I in the 1:(1-10) molar ratios of the reactants led to several (-benzoquinonedioximate)Ni derivatives and/or iodine adducts [Ni(I)(bqoxH)(bqoxH)]·/I, [Ni(I)(bqoxH)(bqoxH)]·[Ni(bqoxH)], and [Ni(I)(bqox)(bqoxH)]·I; the latter one, featuring the anion-radical bqox ligand, is derived from the formal (-2H/1)-oxidation of bqoxH. In these three adducts, various types of noncovalent interactions were identified experimentally and their existence was supported theoretically.

Tetrahedral nickel(ii) and cobalt(ii) bis-o-iminobenzosemiquinonates.

The new bis-o-iminobenzosemiquinonate nickel and cobalt complexes (imSQt-Bu)2M (M = Ni (1), Co (2)), where imSQ is a radical anion of 4,6-di-tert-butyl-N-(tert-butyl)-o-iminobenzoquinone, were synthesized and characterized in detail. The molecular structures of 1 and 2 have been established by single-crystal X-ray analysis. The metal atoms in 1 and 2 have a distorted tetrahedral environment, and the dihedral angles between the planes of two radical imSQ ligands are approximately 80° in both complexes.

Control of therapeutic IgG antibodies galactosylation during cultivation process and its impact on IgG1/FcγR interaction and ADCC activity.

Therapeutic monoclonal antibodies (mAbs) are within the fastest growing group of pharmaceuticals on the global market. IgG1 subclass is the most potent effector in Fc-related functions. The N-linked glycosylation of mAbs Fc-domain significantly influences its therapeutic activity and the presence of this modification is largely dependent on producer cell and parameters of manufacturing process.

Cobalt complexes with hemilabile o-iminobenzoquinonate ligands: a novel example of redox-induced electron transfer.

The tetracoordinated square-planar CoIII complex (imSQC(O)Ph)CoIII(APC(O)Ph) (1) bearing a radical anion and the closed-shell o-amidophenolate forms of the functionalized o-aminophenol H2LC(O)Ph were synthesized. The intermediate spin state (SCo = 1) CoIII center was found for compound 1. The cyclic voltammogram of derivative 1 contains two oxidative processes and one reductive redox process as well as an additional multi-electron wave at high negative potentials above -2 V, which can involve both the ligand and metal center.

PFN2a, a new partner of RARα in the cytoplasm.

Retinoic acid receptors (RARs) are classically considered as nuclear ligand-dependent regulators of transcription. Here we highlighted a novel face of the RARα subtype: RARα is present in low amounts in the cytoplasm of mouse embryonic fibroblasts (MEFs) where it interacts with profilin2a (PFN2A), a small actin-binding protein involved in filaments polymerization. The interaction involves the N-terminal proline-rich motif (PRM) of RARα and the SH3-like domain of PFN2a.

Redox-Active Ligand-Assisted Two-Electron Oxidative Addition to Gallium(II).

The reaction of digallane (dpp-bian)Ga-Ga(dpp-bian) (2) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with allyl chloride (AllCl) proceeded by a two-electron oxidative addition to afford paramagnetic complexes (dpp-bian)Ga(η -All)Cl (3) and (dpp-bian)(Cl)Ga-Ga(Cl)(dpp-bian) (4). Treatment of complex 4 with pyridine induced an intramolecular redox process, which resulted in the diamagnetic complex (dpp-bian)Ga(Py)Cl (5). In reaction with allyl bromide, complex 2 gave metal- and ligand-centered addition products (dpp-bian)Ga(η -All)Br (6) and (dpp-bian-All)(Br)Ga-Ga(Br)(dpp-bian-All) (7).

The hypothalamic-pituitary-thyroid axis and personality in a sample of healthy subjects.

Thyroid hormones influence various brain pathologies, including psychiatric disorders. However, the relationship between these hormones and the psychological state in the normal, non-clinical population is poorly understood. We aimed to test whether serum levels of thyroid hormones are associated with personality in the healthy population.

Gallium Hydrides with a Radical-Anionic Ligand.

The reaction of ClGaH with a sodium salt of the dpp-Bian radical-anion (dpp-Bian)Na (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords paramagnetic gallane (dpp-Bian)Ga(Cl)H (1). Oxidation of (dpp-Bian)Ga-Ga(dpp-Bian) (2) with NO results in the dimeric oxide (dpp-Bian)Ga(μ-O)Ga(dpp-Bian) (3). A treatment of the oxide 3 with phenylsilane affords paramagnetic gallium hydrides (dpp-Bian)GaH (4) and (dpp-Bian)Ga{OSi(Ph)H}H (5) depending on the reagent's stoichiometry.

[The Effects of Chronic Combined Stress: Changes in Behavior of Rats with Various Responses to Novelty].

We studied the effect of chronic combined stress (model of experimental neurosis) on behavior of rats with different basal strategies of behavior in novelty conditions. Chronic stress resulted in decreases in the body weight and testosterone contents in the blood and neocortex in all animals. Animals with initially low orient- ing-exploratory response in the "open field" test did not exhibit substantial alterations of behavior during repeated testing in this test of the "dark-light chamber" test; however, the depression-like behavior was more expressed in the second forced swim test.

Ligand "Brackets" for Ga-Ga Bond.

The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward acenaphthenequinone (AcQ), sulfur dioxide, and azobenzene was investigated. The reaction of 1 with AcQ in 1:1 molar ratio proceeds via two-electron reduction of AcQ to give (dpp-Bian)Ga(μ2-AcQ)Ga(dpp-Bian) (2), in which diolate [AcQ](2-) acts as "bracket" for the Ga-Ga bond. The interaction of 1 with AcQ in 1:2 molar ratio proceeds with an oxidation of the both dpp-Bian ligands as well as of the Ga-Ga bond to give (dpp-Bian)Ga(μ2-AcQ)2Ga(dpp-Bian) (3).

Chronic combined stress induces selective and long-lasting inflammatory response evoked by changes in corticosterone accumulation and signaling in rat hippocampus.

Hippocampus is believed to be selectively vulnerable to stress. We hypothesized that this phenomenon may be mediated by relatively high vulnerability to neuroinflammation related to impairments of local glucocorticoid metabolism and signaling. We have evaluated inflammatory responses induced by acute or chronic combined stress in the cerebral cortex and hippocampus as well as circulating and brain corticosterone (CS) levels as well as expression of corticosterone target genes.

Nuclear and extranuclear effects of vitamin A.

Vitamin A or retinol is a multifunctional vitamin that is essential at all stages of life from embryogenesis to adulthood. Up to now, it has been accepted that the effects of vitamin A are exerted by active metabolites, the major ones being 11-cis retinal for vision, and all trans-retinoic acid (RA) for cell growth and differentiation. Basically RA binds nuclear receptors, RARs, which regulate the expression of a battery of target genes in a ligand dependent manner.