Humic-based bionanocomposites containing stable paramagnetic gold nanoparticles for prospective use in pharmaceuticals

Structural peculiarities and supramolecular organization of medicinally promising nanocomposites, synthesized from humic substances, which essentially differ depending on decomposition degree, have been studied using electron spin resonance, transmission electron, and confocal laser scanning microscopy techniques and some other modern physical–chemical methods. It is shown that stable zero-valent gold nanoparticle of about 10–17?nm in size are formed in a natural macromolecular matrix. The nanocomposites obtained turn out to be stable in aggregative state for a long time and preserve their properties that are extremely important for prospective medicinal substances.     

New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Nondissipative curves in Hilbert spaces having a limit of the corresponding correlation function

In this work a class of nondissipative curves in Hilbert spaces whose correlation functions have a limit ast± is presented. These curves correspond to a class of nondissipative basic operators that are a coupling of a dissipative operator and an antidissipative one. The wave operators and the scattering operator for the couple (A ^*, A) ( ) are obtained. The present work is a continuation and a generalization of the investigations of K.Kirchev and V.Zolotarev [1, 2, 3] on the model representations of curves in Hilbert spaces where the respective semigroup generator is a dissipative operator. This article includes four parts. A new form of the triangular model of M.S. Livic ([4, 5]) for the considered operators is introduced in the first part by the help of a suitable representation of the selfadjoint operatorL. This allows us to describe the studied class of nondissipative curves. The second part studies some results concerning the application of the analogue for multiplicative integrals of the well-known Privalov's theorem ([6]) about the limit values in the scalar case. This analogue is a reconstruction of measure by limit values in Stieltjes-Perron's style and it is obtained by L.A. Sakhnovich ([7]). Another problem, considered in the second part is the analogue inC ^m of the classical gamma-function and several properties for further consideration. In the third part the asymptotics of the studied curves corresponding to the nondissipative operators-couplings of a dissipative and an antidissipative operator with absolutely continuous real spectra and the limits of their correlation functions are obtained In the fourth part a scattering theory of a couple (A ^*, A) with a nondissipative operatorA from is constructed as in the selfadjoint case ([8, 9, 10]) and in the dissipative case ([7]). These results show an interesting new effect: the studied nondissipative case is near to the dissipative one.Partially supported by Grant MM-810/98 of MESC     

Chinese companies distress prediction: an application of data envelopment analysis

Bankruptcy prediction is a key part in corporate credit risk management. Traditional bankruptcy prediction models employ financial ratios or market prices to predict bankruptcy or financial distress prior to its occurrence. We investigate the predictive accuracy of corporate efficiency measures along with standard financial ratios in predicting corporate distress in Chinese companies. Data Envelopment Analysis (DEA) is used to measure corporate efficiency. In contrast to previous applications of DEA in credit risk modelling where it was used to generate a single efficiency—Technical Efficiency (TE), we assume Variable Returns to Scale, and decompose TE into Pure Technical Efficiency and Scale Efficiency. These measures are introduced into Logistic Regression to predict the probability of distress, along with the level of Returns to Scale. Effects of efficiency variables are allowed to vary across industries through the use of interaction terms, while the financial ratios are assumed to have the same effects across all sectors. The results show that the predictive power of the model is improved by this corporate efficiency information.     

Fluorescent core-shell polymer particles containing luminophore dyes: synthesis and optical response to acetone

Monodisperse dye-containing crosslinked particles are promising for application in novel optical chemical sensors due to their intrinsic sensitivity. However, preparation of these particles in aqueous media still remains a challenge, since luminophores inhibit radical processes or else cannot embed into polymer chains because of difference in monomer reactivity ratios. In this work, novel dye-containing monodisperse crosslinked particles were prepared and characterized. In order to obtain dye-containing monodisperse crosslinked particles, we studied seed copolymerization of styrene in the presence of divinylbenzene. The influence of nature and concentration of the used comonomers and co-solvents on shape, size distributions and surface characteristics of the particles formed was investigated. Shapes and diameters of the particles were analyzed by DLS, TEM and SEM. The data of SEM and optical spectroscopy studies demonstrated that the synthesized particles were able to self-assemble into thin-film three-dimensional ordered structures. Finally, the structures under study are promising for development of sensor devices with optical response to acetone.     

Fluorolactonization of norbornenecarboxylic acids and their methyl esters with F-TEDA-BF4 and XeF2

The selective fluorolactonization was achieved by treatment of cis-5-norbornene-2,3-endo-dicarboxylic acid or its monomethyl and dimethyl esters with F-TEDA-BF₄ or XeF₂. The reactions of 5-norbornene-endo-2-carboxylic acid and its monomethyl ester with F-TEDA-BF₄ or XeF₂ proceed in a non-selective manner to give fluorolactonization, addition and rearrangement products. The basic factor responsible for selectivity of the fluorolactonization is the presence of two endo-oriented carboxyl groups in the substrate molecule. The electrophilicity and type of the fluorinating agent is of secondary importance in this regard. It is postulated that the fluorolactonization of norbornenecarboxylic acids and their methyl esters with F-TEDA-BF₄ or XeF₂ is realized mainly via “open” fluoronorbornyl carbocation intermediates which in the reaction with XeF₂ are postulated as the tight ion pairs.     

Polarographic determination of α-amylase activity

The enzyme α-amylase splits blue starch in fragments bearing electroactive groups which exhibit two waves in the pulse polarograms. This behaviour is the basis of the polagraphic determination of bacterial and human serum α-amylase activity. The differential pulse mode is more sensitive by a factor of 25 as compared with normal pulse polarography. With serum α-amylase, protein adsorption disturbs the determination of low activities.     

Electrochemical dissolution of magnetite in acid solutions

The present paper deals with the electrochemical behavior of magnetite microcrystals in an acid medium. A voltammetric method employing a carbon-paste electroactive electrode (CPEE) with an organic binder was used. It was found that the cathodic voltammograms, which were recorded at different scan rates, formed a set bounded in the space of i–E parameters by a generalizing voltammetric curve corresponding to the effective potential scan rate _eff. In other words, all curves are situated under one enveloping curve, just as the smaller dolls sit in the largest doll of a Russian doll. Reverse currents (a cathodic current in the anodic direction of the potential scan) were observed on the cyclic voltammogram. Forward and reverse currents obey the same laws and have one and the same generalizing curve, which could be taken as the magnetite characteristic.     

A molecular keypad lock: a photochemical device capable of authorizing password entries

This paper describes a new concept in the way information can be protected at the molecular scale. By harnessing the principles of molecular Boolean logic, we have designed a molecular device that mimics the operation of an electronic keypad lock, e.g., a common security circuit used for numerous applications, in which access to an object or data is to be restricted to a limited number of persons. What distinguishes this lock from a simple molecular logic gate is the fact that its output signals are dependent not only on the proper combination of the inputs but also on the correct order by which these inputs are introduced. In other words, one needs to know the exact passwords that open this lock. The different password entries are coded by a combination of two chemical and one optical input signals, which can activate, separately, blue or green fluorescence output channels from pyrene or fluorescein fluorophores. The information in each channel is a single-bit light output signal that can be used to authorize a user, to verify authentication of a product, or to initiate a higher process. This development not only opens the way for a new class of molecular decision-making devices but also adds a new dimension of protection to existing defense technologies, such as cryptography and steganography, previously achieved with molecules.     

A Comparative Study of Biocathodes Based on Multiwall Carbon Nanotube Buckypapers Modified with Three Different Multicopper Oxidases

14 Single‐ and multi‐walled carbon nanotubes from different sources were characterized in detail, and the characteristics obtained were carefully analyzed. The carbon material with the highest capacitance, and also other superior properties (“Taunit‐M” from “NanoTechCenter”, Russia), was chosen for further modification and fabrication of buckypaper based electrodes. These electrodes were biomodified with plant and fungal laccases, as well as fungal bilirubin oxidase. The designed biocathodes were investigated in simple buffers and also in a complex physiological fluid (human serum). Biocathodes based on immobilized fungal laccase were bioelectrocatalytically inactive in chloride containing media at neutral pH. In spite of the quite high current densities realized using biodevices based on plant laccase and fungal bilirubin oxidase, the limited thermal stability of the enzymes renders the biocathodes inadequate for practical applications in implanted situations.