C-F?M interaction in anionic α-fluorovinyl rhenium oxycarbene complexes and their β-fluoroenolate analogs

The C-F?M⁺ interaction in anionic σ-(α-fluorovinyl)rhenium oxycarbene complexes, [RCFCFReC(O)R′(CO)₄]M (1-6), M = Na, Li, K is studied by ¹⁹F NMR in THF and Et₂O. The coordination of α-F to M⁺ results in an upfield shift of the corresponding ¹⁹F NMR signal and a decrease of ¹J_CF. The maximum shift is found for the Li salt of complex 4 in Et₂O (Δδ_Fα = 36.4 ppm), in which case a ⁷Li-¹⁹F spin-spin coupling is also observed (J_LiF = 40 Hz). The ΔE of C-F?M⁺ interaction and its effect on ¹⁹F shielding was further studied by DFT calculations using β-fluoroenolates as models, which confirmed a strong impact of CF-bond environment on the coordination ability of fluorine in these F,O-chelates. A compound with a β-fluoroenolate backbone but without rhenium, o-(α-fluorovinyl)phenolate 12, was prepared and studied by ¹⁹F NMR, and similarly showed indications of C-F?M⁺ interaction in THF solution. It is concluded that the donor ability of fluorine in the studied system is enhanced because of the conjugation of α-fluorovinyl group with the enolate π-system and back donation from the transition metal.     

Deoxygenation of some α-dicarbonyl compounds by tris(diethylamino)phosphine in the presence of fullerene C60

The reactions of such cyclic α-diketones as acenaphthenequinone, aceanthrenequinone, and N-alkylisatins, with hexaethyltriaminophosphine in the presence of the fullerene C(60), lead to the formation of methanofullerene derivatives under mild conditions. This process proceeds via deoxygenation of the dicarbonyl compound by the P(III) derivative and is likely to involve the intermediate formation of α-ketocarbenes. The structure of some methanofullerenes has been confirmed by NMR and XRD. The electrochemical behavior of the methanofullerenes was also investigated.     

Quantum-Like Representation Algorithm for Trichotomous Observables

We study the problem of representing statistical data (of any origin) by a complex probability amplitude. This paper is devoted to representation of data collected from measurements of two trichotomous observables. The complexity of the problem eventually increases compared to the case of dichotomous observables. We see that only special statistical data (satisfying a number of nonlinear constraints) have the quantum-like representation.     

Synthesis and properties of fluorescent hybrid nanocomposites based on copolyacrylates with dansyl semicarbazide units

Our study examined a series of hybrid composites containing copolyacrylate with semicarbazide-dansyl groups prepared by conventional radical polymerization of monomers in the organic montmorillonite modified with alkyl chains of variable length or using the sol-gel technique. The structure and the chemical composition of the copolymers N‐methacryloyloxyethylcarbamoyl-5-(dimethylaminonaphtalene-1-sulfonohydrazine)-co-methyl metahacrylate (DnsSA-co-MMA) and N‐methacryloyloxyethylcarbamoyl-5-(dimethylaminonaphtalene-1-sulfonohydrazine)-co-dodecylacrylamide (DnsSA-co-DA) as well as their nanocomposites (HC-P1, HC-P2, HC-P3, HC-P4) were confirmed by spectral analysis (¹H NMR, FTIR, UV/vis), thermal methods and atomic force microscopy. To quantify the effect of the inorganic component compared to pure photopolymers we evaluated the properties of hybrid composites, including dielectric characterization. Additionally, these materials have been tested in experiments of fluorescence quenching by acids (HCl, p-toluenesulfonic acid, 1-S-camphorsulfonic acid), metallic cation (Cu²⁺) and nitrobenzene. The results suggest that such nanocomposites could find applications as fluorescence-based chemosensors in homogeneous organic solutions or thin films.     

Functional differential inclusions generated by functional differential equations with discontinuities

Given a functional differential equation with a discontinuity, a construction of its extension in the shape of a functional differential inclusion is offered. This construction can be regarded as a generalization of the famous Filippov approach to study ordinary differential equations with discontinuities. Some basic properties of the solutions of the introduced functional differential inclusions are studied. The developed approach is applied to analysis of gene regulatory networks with general delays.     

EPR of Spin Transitions in Complexes of Cu(hfac)2 with tert-Butylpyrazolylnitroxides

Polymer chain complexes [Cu(hfac)₂L^R] _n exhibit thermally and light-induced magnetic anomalies in many aspects similar to a spin crossover. These compounds attracted significant attention in the field of molecular magnetism and have been extensively studied by electron paramagnetic resonance (EPR) during the last several years. All compounds studied so far were based on copper(II) ions bridged by pyrazolyl-substituted nitronylnitroxides. The present work reports the first EPR study of complexes of Cu(hfac)₂ with tert-butylpyrazolylnitroxides—a new type of nitroxide ligand expected to modify exchange interaction pathways and physical properties of the crystals. The Q-band EPR spectra of three representative novel compounds are principally different from those studied previously, supporting the assumption that the magnetic motif of the compound has changed. Dominant intercluster exchange interactions are now found along the structural polymer chains. This complicates the EPR detection of phase transitions to some extent; however, theoretical modeling of the observed spectral changes allows for unambiguous assignment of different spin states and transitions between them. The magnitudes of intercluster exchange interaction were estimated to be ca. 0.1–1.5 cm^?1 for the studied compounds.     

Photosystem 2 effective fluorescence cross-section of cyanobacterium Synechocystis sp. PCC6803 and its mutants

The effective fluorescence cross-section of photosystem 2 (PS2) was defined by measurements of chlorophyll a fluorescence induction curves for the wild type of the unicellular cyanobacterium Synechocystis sp. PCC6803, C-phycocyanin deficient mutant (CK), and mutant that totally lacks phycobilisomes (PAL). It was shown that mutations lead to a strong decrease of the PS2 effective fluorescence cross-section. For instance, the effective fluorescence cross-section of PS2 for wild type, CK and PAL mutants excited at λ(ex)=655 nm were found to be 896, 220 and 83 ?(2) respectively. Here we present an estimation of energy transfer efficiency from phycobilisomes to the pigment-protein complexes of PS2. It was shown that the PS2 fluorescence enhancement coefficient reaches a maximum value of 10.7 due to the energy migration from phycobilisomes. The rate constant of energy migration was found to be equal to 1.04 × 10(10) s(-1).     

Inclusion complex formation of ��- and ��-cyclodextrins with riboflavin and alloxazine in aqueous solution: thermodynamic study

Possibility of encapsulation of riboflavin and alloxazine by ??- and ??-cyclodextrins in aqueous solution was studied by ¹H NMR and solubility methods. Thermodynamic parameters of 1:1 inclusion complex formation (K, ??_cG⁰, ??_cH⁰ and ??_cS⁰) were obtained and analyzed in terms of influence of reagent??s structure on complexation process. It was shown that ??-cyclodextrin displays low binding affinity to riboflavin and alloxazine. On the contrary, ??-cyclodextrin forms with riboflavin and alloxazine more stable inclusion complexes. Binding is accompanied by the negative enthalpy and entropy changes that are determined by predominance of van der Waals interactions and possible H-bonding. The presence of ribityl substituent in riboflavin molecule prevents the deep penetration of this compound into macrocyclic cavity. Proposed on the basis of ¹H NMR data the partial insertion of the hydrophobic part of riboflavin and alloxazine molecules into the ??-cyclodextrin cavity causes the enhancement of aqueous solubility of the encapsulated substances. In comparison with ??-cyclodextrin, the solubilizing effect of ??-cyclodextrin is more pronounced due to its higher binding affinity to alloxazine and riboflavin.     

Catalytic hydrofunctionalization of alkynes through P-H bond addition: the unique role of orientation and properties of the phosphorus group in the insertion step

The puzzling question of alkyne insertion into Pd-P and Pd-H bonds leading to the formation of new Pd-C, C-P, and C-H bonds was explored by theoretical calculations at the CCSD(T) and B3LYP levels of theory. The key factors responsible for selectivity of catalytic hydrofunctionalization of alkynes were resolved and studied in details for the models of hydrophosphorylation, hydrophosphinylation, and hydrophospination reactions. In contrast with the generally accepted mechanistic picture, the calculations have shown that several pathways are possible depending on the nature and geometrical arrangement of the phosphorus group. It was found that the product of alkyne insertion into the metal-hydrogen bond should be easily formed under kinetic-control conditions, while the product of alkyne insertion into the metal-phosphorus bond may be formed in certain cases under thermodynamic control. For the first time, the calculations have revealed the role of the oxygen atom in the reactivity of P=P(O)R(2) groups and the role of the interactions involving the lone pair of the P=PR(2) group in the reagent. The fundamental properties of the Pd-P, C-P, and P-H bonds were reported, and the larger bond strength upon increasing the number of oxygen atoms bound to phosphorus (P=PR(2), P(O)R(2), and P(O)(OR)(2)) have been shown. The relationship between bond energy, acidity, and reactivity of the studied phosphorus compounds has been determined.     

Tailoring (bio)chemical activity of semiconducting nanoparticles: critical role of deposition and aggregation

The impact of deposition and aggregation on (bio)chemical properties of semiconducting nanoparticles (NPs) is perhaps among the least studied aspects of aquatic chemistry of solids. Employing a combination of in situ FTIR and ex situ X-ray photoelectron spectroscopy (XPS) and using the Mn(II) oxygenation on hematite (α-Fe(2)O(3)) and anatase (TiO(2)) NPs as a model catalytic reaction, we discovered that the catalytic and sorption performance of the semiconducting NPs in the dark can be manipulated by depositing them on different supports or mixing them with other NPs. We introduce the electrochemical concept of the catalytic redox activity to explain the findings and to predict the effects of (co)aggregation and deposition on the catalytic and corrosion properties of ferric (hydr)oxides. These results offer new possibilities for rationally tailoring the technological performance of semiconducting metal oxide NPs, provide a new framework for modeling their fate and transport in the environment and living organisms, and can be helpful in discriminating between weakly and strongly adsorbed species in spectra.