Removal of Anionic Methyl Orange Dye from Water by Poly[2-methyl-1H-indole] Derivatives: Investigation of Kinetics and Isotherms of Adsorption.

The adsorption properties toward methyl orange (MO) were evaluated for poly[2-methyl-1H-indole] and its derivatives. The influence of pH, ionic strength of solution, composition, and amount of sorbent on the adsorption of MO dye was investigated; the kinetics of dye adsorption was studied. The adsorption isotherms were analyzed using different models of sorption equilibrium. The presence of chemical interaction between polyindoles and dye was proved by IR and UV spectroscopy methods. The sorption of MO with polymers is realized mainly due to the formation of electrostatic interactions between the sulfogroup of the dye and the imino group of the sorbent. Microphotographs demonstrate the change in the morphology of polyindoles after adsorption, which further confirms the structural changes in the polymers. It was found that the main factors affecting the sorption capacity of the studied materials are the position and nature of substituents in the polymers and the sorption conditions. For example, polyindoles containing a methoxy group in their structure (o-OMePIn and m-OMePIn) have the best sorption activity. These polymers are effective in adsorbing dyes, which means that they can be used in wastewater treatment.

Photoconductivity of Thin Films Obtained from a New Type of Polyindole.

The optoelectronic properties of a new poly(2-ethyl-3-methylindole) (MPIn) are discussed in this paper. The absorption and photoluminescence spectra were studied. The electronic spectrum of MPIn showed a single absorption maximum at 269 nm that is characteristic of the entire series of polyindoles. The fluorescence spectra show that the emission peaks of the test sample are centered around 520 nm. The photoconductivity of thin film samples of MPIn polyindole was studied by measuring the current-voltage characteristics under ultraviolet radiation with a wavelength of 350 nm. Samples of phototransistors were obtained, where thin films of MPIn polyindole were used as a transport layer, and their characteristics were measured and analyzed. The value of the quantum efficiency and the values of the mobility of charge carriers in thin polyindole films were estimated.

Polymerization of new aniline derivatives: synthesis, characterization and application as sensors.

This work is focused on modifying aniline monomers with various characteristics that allows one to study the effect of the substituent on the respective polymer. A series of new polyaniline (PANI) derivatives based on an ortho-substituted aniline derivative, 2-(1-methylbut-2-en-1-yl)aniline, were synthesized and characterized. The structures and composition of the polymers that we synthesized were confirmed by elemental analysis, proton nuclear magnetic resonance (1H NMR) spectroscopy, carbon nuclear magnetic resonance (13C NMR) spectroscopy, Fourier-transform infrared spectroscopy (FT-IR), and ultraviolet-visible spectroscopy (UV). Characterization by FT-IR and UV-visible spectroscopy techniques indicated that the polymers exist in protonated emeraldine forms. Scanning electron microscope (SEM) results revealed that the surface morphology of the resulting polymers changed from a heterogeneous hierarchical to spherical structure upon changing the substituent in the aniline monomers. The polymers are soluble in common organic solvents, so they can be used to make films. The electrical properties of the polymers were studied and their high sensitivity to moisture and ammonia was demonstrated. The results of the studies showed the prospects of using thin polymer films in the design of chemical sensors. The impact of the substituent on the polymer characteristics is rationalized in terms of steric and electronic effects.

Evaluation of Cytotoxicity and α-Glucosidase Inhibitory Activity of Amide and Polyamino-Derivatives of Lupane Triterpenoids.

A series of two new and twenty earlier synthesized branched extra-amino-triterpenoids obtained by the direct coupling of betulinic/betulonic acids with polymethylenpolyamines, or by the cyanoethylation of lupane type alcohols, oximes, amines, and amides with the following reduction were evaluated for cytotoxicity toward the NCI-60 cancer cell line panel, α-glucosidase inhibitory, and antimicrobial activities. Lupane carboxamides, conjugates with diaminopropane, triethylenetetramine, and branched C3-cyanoethylated polyamine methyl betulonate showed high cytotoxic activity against most of the tested cancer cell lines with GI50 that ranged from 1.09 to 54.40 µM. Betulonic acid C28-conjugate with triethylenetetramine and C3,C28-bis-aminopropoxy-betulin were found to be potent micromolar inhibitors of yeast α-glucosidase and to simultaneously inhibit the endosomal reticulum α-glucosidase, rendering them as potentially capable to suppress tumor invasiveness and neovascularization, in addition to the direct cytotoxicity. Plausible mechanisms of cytotoxic action and underlying disrupted molecular pathways were elucidated with CellMinner pattern analysis and Gene Ontology enrichment analysis, according to which the lead compounds exert multi-target antiproliferative activity associated with oxidative stress induction and chromatin structure alteration. The betulonic acid diethylentriamine conjugate showed partial activity against methicillin-resistant S. aureus and the fungi C. neoformans. These results show that triterpenic polyamines, being analogs of steroidal squalamine and trodusquemine, are important substances for the search of new drugs with anticancer, antidiabetic, and antimicrobial activities.

Effect of structural factors on the physicochemical properties of functionalized polyanilines.

This review discusses the physical and physicochemical properties of polyaniline (PANI) derivatives. The most important methods for the preparation of functionalized polyanilines are presented. The presence of various substituents in its structure changes the polymer characteristics significantly due to steric and electronic effects of the functional groups. This review describes the relationship between the properties of functionalized polyanilines depending on the nature, number and position of the substituents at the aromatic ring.

Experimental and theoretical substantiation of differences of geometric isomers of copper(II) α-amino acid chelates in ATR-FTIR spectra.

Stereo and structural isomerism of the copper(II) chelate complexes define their biological activity. At the same time, the identification of the geometric isomers of such complexes is a nontrivial task of modern coordination chemistry. In the presented work we have studied the trans- and cis-isomers of chelates bis(S-valinato)copper(II), (R,S-valinato)copper(II) and other mixed ligand copper(II) amino acid complexes with the joint use of experimental by ATR-FTIR spectroscopy and DFT simulations. Using DFT simulations (method M06/6 311+G(d)) the optimum conformers of the geometric isomers of copper(II) a-amino acid chelate complexes were found and their characteristic stretching vibrations were established in the mid-wave region of the IR spectra. The experimental ATR-FTIR bands of the compounds well agree with the theoretical estimates. Such a joint use allows to determine of cis- and trans-isomers of copper(II) N,O-amino acid chelates in the mid-wave region of the ATR-FTIR spectrum.

Quantitative structure-property relationship modeling of the C60 fullerene derivatives as electron acceptors of polymer solar cells: Elucidating the functional groups critical for device performance.

Using the GUSAR 2013 program, we have performed a quantitative analysis of the "structure-power conversion efficiency (PCE)" on the series of 100 methano[60]fullerenes previously tested as acceptor components of bulk-heterojunction polymer organic solar cells (PSCs) utilizing the same donor polymer, viz. poly(3-hexylthiophene). Based on the MNA and QNA descriptors and self-consistent regression implemented in the program, six statistically significant consensus models for predicting the PCE values of the methano[60]fullerene-based PSCs have been constructed. The structural fragments of the fullerene compounds leading to an increase in the device performances are determined. Based on these structural descriptors, we have designed the three methano[60]fullerenes included in the training sets and characterized by poor optoelectrical properties is performed. As a result, two new compounds with potentially moderate efficiency have been proposed. This result opens opportunities of using the GUSAR 2013 program for modeling of the "structure-PCE" relationship for diverse compounds (not only fullerene derivatives).

Nucleophilic cyclopropanation of [60]fullerene by the addition-elimination mechanism.

Information on the synthesis of monofunctionalized methanofullerenes C60 obtained by the addition-elimination mechanism is generalized. The main reagents for cyclopropanation, mechanisms and optimal conditions for the processes, and the prospects for practical application of the products are considered.

Luminescence of aromatic hydrocarbon molecules in the sonication of terbium sulfate suspensions.

The sonication of terbium sulfate suspensions in benzene, toluene, and p-xylene induces intense UV luminescence (260-320 nm). The luminescence bands coincide with the fluorescence spectra of these aromatic hydrocarbons, but it is not observed in their sonoluminescence spectra. Furthermore, the spectra of ultrasound-initiated luminescence of the suspensions defined as sonotriboluminescence, which is 103 times more intense than the sonoluminescence of hydrocarbons, exhibit also emission from the ∗Tb3+ ion. The luminescence of ∗N2, which is observed during traditional triboluminescence of terbium sulfate in air, is hardly detectable in the case of sonolysis of terbium sulfate suspensions in aromatic hydrocarbons, but can be observed on decreasing the temperature of the suspensions, which decreases the saturated vapor pressure of the liquids. A possible mechanism of excitation of aromatic hydrocarbon molecules during sonotriboluminescence is discussed.

Quantitative structure-activity relationship of the thymidylate synthase inhibitors of Mus musculus in the series of quinazolin-4-one and quinazolin-4-imine derivatives.

A quantitative structure-activity relationship analysis of the 2-methylquinazolin-4-one and quinazolin-4-imine derivatives, well-known antifolate thymidylate synthase (TYMS) inhibitors, has been performed in the range IC50 = 0.4÷380000.0 nmoL/L using the GUSAR 2013 program. Based on the MNA and QNA descriptors using the self-consistent regression, 6 statistically significant consensus models for predicting the IC50 numerical values have been constructed. These models demonstrate high and moderate prognostic accuracies for the training and external validation test sets, respectively. The molecular fragments of TYMS inhibitors regulating their antitumor activity are identified. The obtained data open opportunities for developing novel promising inhibitors of TYMS.

Theoretical Models for Quantitative Description of the Acid-Base Equilibria of the 5,6-Substituted Uracils.

The acidities of 18 5,6-substituted uracils have been numerically estimated as pKa values in terms of three theoretical models. The first scheme includes the calculation of the gas-phase acidity of uracil with the G3MP2B3 method and taking into account the solvent effect using the polarizable continuum approximation PCM(SMD)-TPSS/aug-cc-pVTZ. The second model is one step and implies calculation of the free Gibbs energies of the hydrate complex of uracil (and its anion) with 5 water molecules by the TPSS/aug-cc-pVTZ method. This model accounts for the solvent effect corresponding to both specific and nonspecific solvation. The third scheme required high time and computational resources and includes the strong features of the two previous schemes. Here, the theoretical estimation of pKa is performed by the CBS-QB3 composite method. As in the second approach, both specific (as pentahydrate) and nonspecific solvent effects are determined. We have analyzed the advantages and model restrictions of the considered schemes for the pKa calculations. All models have systematic errors, which have been corrected with the linear empirical regression relations. In the presented model, the absolute mean deviations of the pKa values of uracils dissociating via the N1-H bonds diminish to 0.25, 0.28, and 0.23 pKa units (respectively, for I, II, and III models), which corresponds to ∼0.3 kcal/mol on the energy scale. The applicability of our computational schemes to uracils dissociating via N3-H, O-H (orotic acids) and C-H bonds is discussed.

Controlled stabilization of anionic forms of the uracil derivatives: A DFT study.

Relative stabilities of the N1/N3/О5/О6 anions of 42 substituted uracils in gas phase and aqueous solutions have been theoretically studied using approximation IEFPCM (SMD) - TPSS/aug-cc-pVTZ. The specific solvation of uracil and its anions has been simulated with the first hydrate shell made up with 5 water molecules. The nonspecific solvation has been accounted in terms of the SMD model. We have found a series of relative stability under conditions of both specific and nonspecific hydration. The series is ranked according to the increase of the relative stability of the N3 anion. In gas phase, the N1 anion is significantly more stable than its N3 counterpart: the ΔGgas values vary in the range from 19.54 (5OH6СН3U) to 83.14 (5NO26NH2U) kJ/mol that is caused by a more effective delocalization of the excess charge through the uracil framework in the N1 anion. The hydration pronouncedly diminishes ΔG to the range from -0.02 (5OH6СН3U) to 38.16 (5Br6NO2U) kJ/mol due to the fact that the polar solvent is prone to stabilize more polar anionic states of uracils. Therefore, less polar uracil anions are more stable. We have defined the main factor influencing the N1/N3/О5/О6 distribution of anions, viz. the presence of the substituents in 5 and 6 positions of the pyrimidine ring. Herewith, the most favorable mechanism of the influence of 5-substituents has been previously defined as resonant whereas, as we found in this work, the inductive mechanism is more pronounced in the case of 6-substituents.

Enhancing 4-propylheptane dissociation with nickel nanocluster based on molecular dynamics simulations.

In the present work, a 0.4nm nickel cluster has been theoretically studied. Its equilibrium structural parameters have been calculated by the DFT method based on the PBEH1PBE hybrid functional and split-valence basis set Lanl2DZ including effective core potentials. We have systematically considered diverse spin states of this cluster and find out its ground state. The relative stability of these states depends on the HOMO-LUMO gap. The interaction of the Ni6 with 4-propylheptane С10Н22 has been studied to simulate the process of catalytic cracking of hydrocarbons. The optimization of this structure has been performed by the ωPBE/Lanl2DZ_ecp method (the TeraChem V.1.9 program package) with no symmetry restrictions; the electron shells of the metal were described by effective core pseudopotentials. For visualization and quantitative estimation of the bonding bonds between the nickel nanocluster and 4-propylheptane, the analysis of weak interactions based on RGD has been performed. To confirm the proposition about the formation of Ni-H bonds, we have scrutinized critical points of electronic density. Values of laplasian of electronic density and Bader atomic charge distribution in the global minimum of the total energy have been estimated by the AIMAll 15.05.18 program suite. Finally, we have simulated interaction of Ni6 with 4-propylheptane in terms of the Born-Oppenheimer ab initio molecular dynamics. The results of the molecular dynamics simulation provide pair radial distribution function CH at 1500°C and a detailed picture of the processes occurring in the system.