Unraveling of Functional Activity of Primary Hippocampal Neuron-Glial Networks in Photodynamic Therapy Based on Tetracyanotetra(aryl)porphyrazines.

The current efforts in photodynamic therapy (PDT) of brain cancer are focused on the development of novel photosensitizers with improved photodynamic properties, targeted specific localization, and sensitivity to the irradiation dose, ensuring the effectiveness of PDT with fewer side effects for normal nerve tissue. Here, we characterize the effects of four photosensitizers of the tetracyanotetra(aryl)porphyrazine group (-) on the functional activity of neuron-glial networks in primary hippocampal cultures in their application in normal conditions and under PDT. The data revealed that the application of - leads to a significant decrease in the main parameters of the functional calcium activity of neuron-glial networks and pronounced changes in the network characteristics.

Complexes of 1-(2-R(F, CH, Cl)-phenyl)-1,4-dihydro-5H-tetrazole-5-thiones with cadmium chloride: Synthesis, molecular, crystal structures and computational investigation approach.

New complex compounds (I) - (IV) were synthesized by the reaction of 1-(2-fluorofluorophenyl) -1,4-dihydro-5H-tetrazole-5-thione (HL), 1-(2-methylphenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL) and 1-(2-chlorochlorophenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL) with cadmium chloride. By X-ray diffraction analysis, molecular and crystal structures of complexes (I), (II), (III) and (IV) are determined. (CIF files CCDC № 2,003,797 (I), 1,993,454 (II), 2,151,359 (III), 2,098,997 (IV)).

Cycloaddition of isoselenocyanates to sodium and magnesium metallacycles.

Heterocumulenes SeCNR (R = CHOMe-2, CHMe-2) undergo facile cycloaddition to [(H-dpp-bian)Na(EtO)] (1) (H-dpp-bian = N-protonated 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) resulting in cycloadducts [(H-dpp-bian)Na(SeCNR)(DME)] (2, 3), which are the first cycloadducts derived from a sodium metallacycle reported so far. A comparative reaction of [(dpp-bian)Mg(THF)] (10) with SeCNR gives magnesium cycloadducts [(dpp-bian)Mg(SeCNR)(Solv)] (11, 12), which undergo fast decomposition at room temperature. New compounds are characterized by NMR, EPR, and IR spectroscopy, and elemental and X-ray diffraction analysis.

2-Imino-2,3-dihydrobenzoxazole-a useful platform for designing rare- and alkaline earth complexes with variable di- and trianionic O,N,N, ligands.

The reactions of 2-imino-2,3-dihydrobenzoxazole LH with M[N(SiMe)](THF) (M = Yb and Ca) and Y(CHSiMe)(THF) proceed with the opening of the dihydrobenzoxazole ring and the elimination of HN(SiMe) or SiMe. Besides, in the case of Yb[N(SiMe)](THF), an electron transfer from Yb(II) to L takes place and Yb(III) complex 1 is coordinated by a dianionic phenolate ligand containing a pendant radical-anionic diazabutadiene fragment form. When LH is reacted with Ca[N(SiMe)](THF), C-H bond activation of a methyl fragment by imino nitrogen occurs and affords a dimeric calcium complex 2.

Magnetically induced ring currents in metallocenothiaporphyrins.

The magnetically induced current-density susceptibility tensor (CDT) of the lowest singlet and triplet states of the metallocenothiaporphyrins, where the metal is V, Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, or Rh, have been studied with the gauge-including magnetically induced currents (GIMIC) method. The compounds containing V, Mn, Co, Tc or Rh were studied as cations because the neutral molecules have an odd number of electrons. The calculations show that the aromatic nature of most of the studied molecules follows the Hückel and Baird rules of aromaticity.

Reduction of CO with Aluminum Hydrides Supported with Ar-BIAN Radical-Anions (Ar-BIAN = 1,2-Bis(arylimino)acenaphthene).

The reactions of HAlCl with [(dpp-Bian)Na(EtO)] and [(Ar-Bian)Na(THF)] produce respective aluminum hydrides supported by radical-anionic 1,2-bis(arylimino)acenaphthene ligands, [(dpp-Bian)AlH] ( and [(Ar-Bian)AlH(THF)] () (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene); Ar-Bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene). The reaction of with CO proceeds with reduction of both C═O bonds and results in diolate [{(dpp-Bian)Al(μ-OCH)}] (). Complex reacts with CO to carbonate [{(Ar-Bian)Al(μ-OCHOCO)}] () that is a result of the insertion of CO into the Al-O bond in diolate species formed initially.

Amine-boranes reactions promoted by lanthanide(II) ions.

The catalytic activity in amine-borane dehydrogenation is shown for the first time for Ln(II) species using complexes [{(Bu-CH)CH}M·L] (M = Yb, Sm, L = (DME), TMEDA). The protonation of M(II)-C bonds with HNRRBH affords amidoborane complexes [M(NRRBH)L], which under excess HNMeBH transform to [NMeBHNMeBH] derivatives, both serving as the dehydrocoupling intermediates.

The Identification of Cu-O-C Bond in Cu/MWCNTs Hybrid Nanocomposite by XPS and NEXAFS Spectroscopy.

The results of the research of a composite based on multi-walled carbon nanotubes (MWCNTs) decorated with CuO/CuO/Cu nanoparticles deposited by the cupric formate pyrolysis are discussed. The study used a complementary set of methods, including scanning and transmission electron microscopy, X-ray diffractometry, Raman, and ultrasoft X-ray spectroscopy. The investigation results show the good adhesion between the copper nanoparticles coating and the MWCNT surface through the oxygen atom bridge formation between the carbon atoms of the MWCNT outer graphene layer and the oxygen atoms of CuO and CuO oxides.

Biological Response to a Novel Hybrid Polyoligomer: and Models.

Unlabelled: is to evaluate biocompatibility of a novel hybrid polyoligomer in and models.

Materials And Methods: Cytotoxicity of the material was investigated using the MTT assay with human dermal fibroblasts as test cultures. To study direct interaction of the hybrid polyoligomer with cells, the fibroblasts were cultured on the polymer samples for 96 h, the cultures were assessed every 24 h using fluorescence microscopy.

Red Light-Emitting Water-Soluble Luminescent Iridium-Containing Polynorbornenes: Synthesis, Characterization and Oxygen Sensing Properties in Biological Tissues In Vivo.

New water-soluble polynorbornenes - containing oligoether, amino acid groups and luminophoric complexes of iridium(III) were synthesized by ring-opening metathesis polymerization. The polymeric products in organic solvents and in water demonstrate intense photoluminescence in the red spectral region. The polymers and with 1-phenylisoquinoline cyclometalating ligands in iridium fragments reveal 4-6 fold higher emission quantum yields in solutions than those of and that contain iridium complexes with 1-(thien-2-yl)isoquinoline cyclometalating ligands.

Cyanoarylporphyrazines with High Viscosity Sensitivity: A Step towards Dosimetry-Assisted Photodynamic Cancer Treatment.

Despite the significant relevance of photodynamic therapy (PDT) as an efficient strategy for primary and adjuvant anticancer treatment, several challenges compromise its efficiency. In order to develop an "ideal photosensitizer" and the requirements applied to photosensitizers for PDT, there is still a need for new photodynamic agents with improved photophysical and photobiological properties. In this study, we performed a detailed characterization of two tetracyanotetra(aryl)porphyrazine dyes with 4-biphenyl () and 4-diethylaminophenyl () groups in the periphery of the porphyrazine macrocycle.

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF)CH-mian (complex ) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl(dpp-mian)(CHCN)] () and [VOCl(3,5-(CF)CH-bian)(HO)][VOCl(3,5-(CF)CH-bian)]·2.85DME () from [VOCl(CHCN)(HO)] () or [VCl(THF)]. The structure of all compounds was determined using X-ray structural analysis.

Luminescence thermochromism in novel mixed Eu(II)-Cu(I) iodide.

A new mixed Eu(II)-Cu(I) iodide [Eu(DME)][CuI] (1) was synthesized by the reaction of an organosulphide salt of Eu(II) and CuI in DME media. X-ray analysis revealed that 1 is an ate-complex consisting of Eu(DME) dications and tetraiododicuprate dianions. Upon UV light excitation ( = 365 nm), the compound exhibits intense double-peaked photoluminescence (PL) at 445 and 500 nm.

Reactions of Iso(thio)cyanates with Dialanes: Cycloaddition, Reductive Coupling, or Cleavage of the C═S or C═O Bond.

The dialanes [(dpp-Bian)Al-Al(dpp-Bian)] () and [(dpp-dad)Al(THF)-(THF)Al(dpp-dad)] () (dpp-Bian = 1,2-[(2,6-PrCH)NC]CH, dpp-dad = [(2,6-PrCH)NC(CH)]) react with some isothiocyanates, isocyanates, and diphenylketene via [2 + 4] cycloaddition of the C═O or C═S bond across the C═C-N-Al fragment to afford complexes [L(X═C-Y)Al-Al(X═C-Y)L] with an intact Al-Al single bond (, L = dpp-Bian, X = PhN, Y = O; , L = dpp-Bian, X = PhC, Y = O; , L = dpp-dad, X = BnN, Y = S; , L = dpp-dad, X = BuN, Y = O; , L = dpp-dad, X = PrN, Y = S; and , L = dpp-dad, X = CyN, Y = S). A mixed C═N and C═O mode cycloadduct, [(dpp-Bian)(TosN═C-O)Al-Al(TosN-C═O)(dpp-Bian)] , was obtained in the reaction of with tosylisocyanate. Heating the solution of resulted in a thermal transformation and a change of the cycloaddition mode from C═O to C═N to give the product [(dpp-Bian)(PhN-C═O)Al(O)Al(PhN-C═O)(dpp-Bian)] .

Perfluorinated Trialkoxysilanol with Dramatically Increased Brønsted Acidity.

The Brønsted acidity of the perfluorinated trialkoxysilanol {(F C) CO} SiOH is more than 13 orders of magnitude higher than that of orthosilicic acid, Si(OH) , and even more for most previously known silanols. It is easily deprotonated by simple amines and pyridines to give the conjugate silanolates [OSi{OC(CF ) } ] , which possess extremely short Si-O bonds, comparable to those of silanones.

Main-group metal complexes of α-diimine ligands: structure, bonding and reactivity.

α-Diimine ligands, in particular 1,4-diazabutadiene (dad) and bis(iminoacenaphthene) (bian) derivatives, have been widely used for coordination with various metals, including main-group, transition, and lanthanide and actinide metals. In addition to their tunable steric and electronic properties, the dad and bian ligands are redox-active and can readily accept one or two electrons, converting into the radical-anionic (L˙) or dianionic (enediamido, L) form, respectively. This non-innocence brings about rich electronic structures and properties of the ligands and complexes thereof.

Development of Biodegradable Polymer Blends Based on Chitosan and Polylactide and Study of Their Properties.

Composite materials of various compositions based on chitosan and polylactide were obtained in the form of films or porous bulk samples. Preliminarily, poly-d,l-lactide was synthesized by ring-opening polymerization of lactide in the presence of Ti(OPr). Polylactide obtained at components molar ratio [lactide]:[Ti(OPr)] = 3:1 had the best molecular weight characteristics at a high product yield.

Lewis Superacidic Tellurenyl Cation-Induced Electrophilic Activation of an Inert Carborane.

The aryltellurenyl cation [2-(tBuNCH)C H Te] , a Lewis super acid, and the weakly coordinating carborane anion [CB H ] , an extremely weak Brønsted acid (pK =131.0 in MeCN), form an isolable ion pair complex [2-(tBuNCH)C H Te][CB H ], in which the Brønsted acidity (pK 7.4 in MeCN) of the formally hydridic B-H bonds is dramatically increased by more than 120 orders of magnitude.

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.

Activation and modification of carbon dioxide by redox-active low-valent gallium species.

The activation of carbon dioxide by metallylene [(dpp-bian)GaNa(DME)2] (dpp-bian = 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene) under mild conditions is described. Furthermore, the reaction of the activation complex [(dpp-bian)Ga(CO2)2Ga(dpp-bian)][Na(DME)2]2 (2) with diphenylketene, cyclohexyl isocyanate, and phenyl isocyanate leads to the elimination of carbon monoxide and the formation of derivatives of oxocarboxylic acid [(dpp-bian)GaOC(O)C(Ph)2C(CPh2)O][Na(DME)2] (6) and carbamate derivatives [(dpp-bian)GaN(Cy)C(O)N(Cy)C(O)O]2[Na(DME)2]2 (7) and [(dpp-bian)GaN(Ph)C(O)O]2[Na(DME)2]2 (8), respectively. Complexes have been characterized by NMR, IR spectroscopy, elemental analysis, and X-ray diffraction analysis.

The localization of the photosensitizer determines the dynamics of the secondary production of hydrogen peroxide in cell cytoplasm and mitochondria.

Photodynamic therapy (PDT) is based on the production of the cytotoxic reactive oxygen species (ROS) by light irradiation of a photosensitizer dye in the presence of molecular oxygen. Along with photochemical ROS production, it becomes evident that PDT induces massive secondary production of ROS which is registered long after the irradiation is completed. We created cell lines of human epidermoid carcinoma with the cytoplasmic and mitochondrial localization of protein sensor HyPer sensitive to hydrogen peroxide to compare its concentration in two cellular compartments.

Interaction of dicoordinate phosphorus with boranes: chemistry of 3a,6a-diaza-1,4-diphosphapentalene as masked phosphinidene.

Treatment of 3a,6a-diaza-1,4-diphosphapentalene (DDP) with an excess of PhBCl2 yields the corresponding bis(borane) adduct DDP(PhBCl2)2 (14), demonstrating the availability of two lone pairs on the phosphorus center. The reaction between DDP and B(C6F5)3 yields (1 : 1) phosphino-borane complex 16. The free lone electron pair on the pyramidal P atom in 16 participates in the intramolecular non-covalent interactions P(1)F(1) and P(1)F(6) giving additional 3.

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.

Catechol-Containing Schiff Bases on Thiacalixarene: Synthesis, Copper (II) Recognition, and Formation of Organic-Inorganic Copper-Based Materials.

For the first time, a series of catechol-containing Schiff bases, tetrasubstituted at the lower rim thiacalix[4]arene derivatives in three stereoisomeric forms, , , and , were synthesized. The structure of the obtained compounds was proved by modern physical methods, such as NMR, IR spectroscopy, and HRMS. Selective recognition (K difference by three orders of magnitude) of copper (II) cation in the series of d-metal cations (Cu, Ni, Co, Zn) was shown by UV-vis spectroscopy.