A theoretical study of the limits of the acidity of carbon acids in phase transfer catalysis in water and in liquid ammonia

The acidities of a large number of carbon acids have been theoretically calculated for the gas-phase and for DMSO solution. The gas-phase values, both ΔH and ΔG, are very well correlated with the available experimental data. From the calculated ΔG values in DMSO and the pKas in the same solvent, a homogeneous set of pK _a (DMSO) values was devised that was used to generate pK _a (water). These last pK _as were used to establish the limits of the acidity of carbon acids for reactions under PTC conditions both alkylations and H/D exchange. A step further led to the pK _as in liquid ammonia and from them to the virtual use of PTC using liquid ammonia instead of water.      

Interfacial behavior of water bound to nitrocellulose containing residual nitric and sulfuric acids

To prepare nitrocellulose (NC), microcrystalline cellulose was treated in a mixture of nitric and sulfuric acids. Prepared NC containing a small amount of acids was studied at a different hydration degree (h = 10–1000 mg g^?1) in different dispersion media (chloroform-d, acetone-d₆ or their mixtures) using low-temperature ¹H NMR spectroscopy. The hydration degree and the presence of residual acids affected the temperature dependence of the chemical shifts of proton resonance of water bound to NC. The Gibbs free energy of bound water became less negative with increasing hydration rate. The chloroform and acetone media affect the behavior of bound-to-NC water unfrozen at T<273 K differently. Quantum chemical calculations were performed using ab initio (HF/6-31G(d,p)), DFT (B3LYP/6-31G(d,p)) and semiempirical PM7 methods to analyze the interfacial behavior of water interacting with NC containing residual amounts of nitric and sulfuric acids.      

The influence of (5′R) and (5′S)-5′,8-cyclo-2′-deoxyadenosine for the electronic properties of nucleosides pairs. The theoretical quantum mechanics studies

Oxidatively generated damage to DNA frequently appears in the human genome as the effect of aerobic metabolism or as the result of exposure to exogenous oxidizing agents such as ionization radiation. In this paper, for the first time, the electronic properties of nucleoside pairs containing 5′,8-cyclo-2′-deoxyadenosine (cdA) in their 5′R and 5′S diastereomeric forms (cdA(R)::T and cdA(S)::T) as the simplest model of ds-DNA have been discussed. The following values of the selected electronic parameters, measured in eV, were found for cdA(R)::T, cdA(S)::T, and dA::T, respectively, adiabatic/vertical electron affinity: 0.39/0.24, 0.35/0.18, 0.33/0.21; and adiabatic/vertical ionization potential: 7.27/7.50, 7.7.25/7.49, 7.03/7.27. Moreover, based on the results of the relaxation energy, the presence of cdA(S)::T should provide the highest barrier for electron transfer in ds-DNA. Analyses of hydrogen bond length deviations reveal that the formation of cationic forms results in higher elongation than that of anionic forms. Moreover, during the electron attachment or detachment for the investigated cdA(R)::T, cdA(S)::T, and dA::T nucleoside pairs, the same scheme of changes in hydrogen bond length was noted.      

Magnetic resonance study of carbon encapsulated Ni nanoparticles

Magnetic resonance study of six samples consisting of carbon encapsulated nickel nanoparticles or carbon nanotubes ended with such nickel nanoparticles was carried out at room temperature. Samples of Ni/C were prepared by carburization of nanocrystalline nickel by ethylene (C₂H₄) and methane (CH₄). Hydrocarbons decomposition on nickel nanoparticles was done at temperatures 500, 600 and 700°C. Magnetic resonance spectra of samples designated as CH₄/500, CH₄/600, CH₄/700, C₂H₄/500, C₂H₄/600 and C₂H₄/700 were obtained by Bruker E 500 spectrometer. The integrated intensities of the resonance spectra were correlated with the carburization conditions (temperature, type of hydrocarbon) during samples preparation. A core-shell model of the investigated samples allowed rough estimation of appropriate shell sizes.      

Enzyme-catalyzed kinetic resolution of N-Boc-trans-3-hydroxy-4-phenylpyrrolidine

The first enzyme-catalyzed kinetic resolution of tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate is presented. Enzyme, solvent and temperature optimization resulted in a new resolution method with E = 40 enantioselectivity. The acetate derivative of the (+)-(3S,4R) enantiomer formed while the (?)-(3R,4S) isomer remained intact. Very good enantioselectivities (E > 200) were achieved in the enzyme-catalyzed alcoholysis of the racemic acetate in i-propanol and t-butanol where the (+)-(3S,4R) enantiomer was prepared in pure form (ee > 99.7%). Absolute configuration of the (?)-(3R,4S)-enantiomer was determined by single crystal X-ray diffraction method.      

A TLC Study of the lipophilicity of thirty-two acetylcholinesterase inhibitors — 1,2,3,4-tetrahydroacridine and 2,3-dihydro-1H-cyclopenta[b]quinoline derivatives

The lipophilicity of thirty-two novel acetylcholinesterase (AChE) inhibitors — 1,2,3,4-tetrahydroacridine and 2,3-dihydro-1H-cyclopenta[b]quinoline derivatives was studied by thin layer chromatography. The analyzed compounds were chromatographed on RP-18, RP-8, RP-2, CN and NH₂ stationary phases with dioxane — citric buffer pH 3.0 binary mobile phases containing different proportions of dioxane. R_M values for pure water were extrapolated from the linear Soczewiński-Wachtmeister equation and six compounds with known literature log P values were used as reference calibration data set for computation of experimental log P values. The obtained results were compared with computationally calculated partition coefficients values (AlogPs, AClogP, AlogP, MlogP, KOWWIN, XlogP2, XlogP3) by PCA and significant differences between them were observed.     

Spectral properties and photophysical behaviour of water soluble cationic Mg(II) and Al(III) phthalocyanines

Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (F_T) and the triplet lifetimes (t_T) were found to be higher in DMSO with Φ_T ranging from 0.32 to 0.51, while t_T ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where Φ_T ranged from 0.15 to 0.19 and t_T from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA).      

Salutaridine and its derivatives as thebaine-equivalents in the synthesis of aporphines

Here we report the transformation of tetracyclic morphinan salutaridine (1) into 2,3,10,11-tetrasubstituted (R)-aporphines. This method serves as another chemical proof of the previously verified biosynthetic connection with pentacyclic morphinan-6,8-diene-type thebaine. In the presence of nucleophiles, this procedure could lead to pharmacologically interesting new tetrasubstituted aporphinoids. The enantioselective synthesis of 7S-salutaridinol (2) has been also achieved in order to investigate the acid-catalyzed reactions of this natural morphinan.      

Synthesis and antiproliferative activity in vitro of new 2-aminobenzimidazole derivatives. Reaction of 2-arylideneaminobenzimidazole with selected nitriles containing active methylene group

A series of pyrimido[1,2-a]benzimidazole and α-cyanocinnamic acid derivatives have been synthesized in the reactions of Schiff bases 2–7 with selected nitriles containing an active methylene group: malononitrile 8–12, cyanoacetamide 13–16, benzyl cyanide 17–21, benzoylacetonitrile 22–24, cyanoacetate methyl ester 25–28 and benzylacetamide 29. The structures 8–29 were confirmed by the results of elementary analysis and their IR, ¹H-, ¹³C-NMR and MS spectra. The products 8–29 of various chemical structure pyrimido[1,2-a] benzimidazole 8–12, 14–16, 17–21, 23–24, 26 and α-cyanocinnamic acid derivatives 13, 22, 25, 27, 28 were obtained, which are of interest for biological studies or which can be substrates for further synthesis. The selected compounds 10, 13, 14, 17, 19, 21, 23–25 and 28 were screened for their antiproliferative activity in vitro against neoplastic and normal cell lines. The most active two compounds were: 2-(o-bromophenylene)-3-cyano-4-phenyl-1,2-dihydropyrimido[1,2-a]benzimidazole (24) and 3-cyano-4-phenyl-2-(2,4-dimethoxyphenyl)-1,2-dihydropyrimido[1,2-a]benzimidazole (23). However, similarly like cisplatin used as the control, they showed no selectivity towards cancer cells, by inhibiting proliferation of normal mouse fibroblasts in similar manner.      

The crystal structure of Sm4Ni11In20 and its relation to other indium-rich compounds

Polycrystalline Sm₄Ni₁₁In₂₀ was obtained by arc-melting of metal ingots. A subsequent high temperature treatment was used for single crystal growth. The Sm₄Ni₁₁In₂₀ crystal structure (U₄Ni₁₁Ga₂₀ type; C2/m, a = 22.5457(3) Å, b = 4.34929(5) Å, c = 16.5479(2) Å, β = 124.592(2)°, R1 = 0.0358, wR2 = 0.0934) was determined by single crystal synchrotron radiation X-ray diffraction from 2014 independent reflections with I > 2σ(I). Sm₄Ni₁₁In₂₀ extends the R ₄Ni₁₁In₂₀ (R = Y, Gd, Tb, Dy, Ho) series of phases. The R ₄Ni₁₁In₂₀ and RNi₃In₆ (LaNi₃In₆ type; R = La, Ce, Pr, Nd, Eu) series have similar compositions. Their structures share similar fragments; in particular the rare earth atom coordination polyhedra are pentagonal prisms with additional atoms.      

Synthesis of new (arylcarbonyloxy)aminopropanol derivatives and the determination of their physico-chemical properties

Eight hydrochlorides of 3-{2-[(2/4-fluorophenoxy)-ethylamino]}-2-hydroxypropyl-4-alkoxybenzoates and four hydrochlorides of 3-tert-butylamino-2-hydroxypropyl-4-butoxybenzoates were prepared as potential antagonists of the β₁-adrenergic receptor (beta-blockers). A multistep synthesis of these compounds is described as well as their detailed analytical characterization. The pharmacokinetic properties of these weak base compounds are significantly influenced by their acid-base dissociation constant, pK _a. The knowledge of this value is crucial for new drug development. This paper is aimed at developing a methodology that utilizes pH-dependent ¹H NMR spectroscopy for its routine analysis. The selected predicted physico-chemical parameters of the new (arylcarbonyloxy)aminopropanols (i.e., aryloxyaminopropanol derivatives) were compared with the model drugs esmolol and flestolol.      

Synthesis and reactivity of(\mu - H)(\mu _3 - \eta ^2 - H_2 )_4 )Os_3 (CO)_9 : An unusually reactive triosmium cluster

The synthesis of $(\mu - H)(\mu - \eta ^2 - H_2 )_4 )Os_3 (CO)_{10} $ (4) from piperidine and Os₃(CO)₁₀(CH₃CN)₂ and its solid state structure are reported. The room temperature reactions of the decarbonylation product of4, $(\mu - H)(\mu _3 - \eta ^2 - H_2 )_4 )Os_3 (CO)_9 $ (3), with P(C₆H₅)₃, CNCH₃, HCl and H₂ are reported. Overall, the products obtained closely resemble those obtained from the analogous, $(\mu - H)(\mu _3 - \eta ^2 - H_2 )_3 )Os_3 (CO)_9 $ (1). The isomerizations of the phosphine addition products $(\mu - H)(\mu - \eta ^2 - H_2 )_n )Os_3 (CO)_9 P(C_6 H_5 )_3 $ (n = 3,6a;n = 4,5a) have been studied by¹H-NMR techniques and the initial rearrangement was shown to be an intramolecular process. Slower conversion to the complex $(\mu - H)(\mu _3 - \eta ^2 - H_2 )_4 )Os_3 (CO)_8 P(C_6 H_5 )_3 $ (8) was observed and the solid state structure of this product is reported and compared with a related compound containing an ethyl,n-propylμ ₃-imidoyl ligand. Compound4 crystallizes in the triclinic space group Pl (#2) withZ= 2, and unit cell parametersa = 9.294(3) Å,b = 15.758(5) Å,c = 7.406(2) Å,a = 81.10(2)°,β=76.47(2)°,y =74.88(2)°, andV =1013(l) ų. Least-squares refinement of 2677 reflections gave a final discrepancy factor ofR = 0.054 (R _w = 0.066). Compound8 crystallizes in the space group C2/c with unit cell parametersa = 24.818(3) Å,b = 16.389(3) Å,c = 18.111(3) Å,β= 120.94(2)°,V = 6318(4) ų, andZ = 8. Least squares refinement of 3439 reflections gave a final discrepancy factor ofR = 0.039 (R _w =0.047).     

Investigation of electrical properties of PANI/chalcogenide junctions

Pure Polyaniline (EB) and Polyaniline doped with different protonic acids (ESs) were chemically synthesized using ammonium peroxydisulphate (APS) as an oxidant. Junctions have been prepared by evaporating chalcogenide materials (ZnSe, CdSe) on conducting polyaniline (EB & ESs) pellets using a vacuum evaporation technique. I–V characteristics of junctions have been studied at room temperature using the Keithley electrometer 6517A. I–V measurements show the rectification effect. A junction of ES[PO₄ ^3?] may be preferred over the other junctions due to its low ideality factor and maximum rectification ratio.      

Copper-cobalt ferrites as catalysts for methanol decomposition

Copper-cobalt ferrites with composition Cu_1?xCo_xFe₂O₄, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.      

A multi-property fluorescent probe for the investigation of polymer dynamics near the glass transition

In addition to the commonly observed single molecule fluorescence intensity fluctuations due to molecular reorientation dynamics, a perylene bisimide-calixarene compound (1) shows additional on-off fluctuations due to its ability to undergo intramolecular excited state electron transfer (PET). This quenching process is turned on rather sharply when a film of poly(vinylacetate) containing 1 is heated above its glass transition temperature (T _g), which indicates that the electron transfer process depends on the availability of sufficient free volume. Spatial heterogeneities cause different individual molecules to reach the electron transfer regime at different temperatures, but these heterogeneities also fluctuate in time: in the matrix above T _g molecules that are mostly nonfluorescent due to PET can become fluorescent again on timescales of seconds to minutes.The two different mechanisms for intensity fluctuation, rotation and PET, thus far only observed in compound 1, make it a unique probe for the dynamics of supercooled liquids.

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Preparation and conductivities of polyacrylic acid/polyvinylimidazole grafted and ungrafted iron oxide nanocomposite polymer electrolytes

Nanocomposites of Polyacrylic acid/polyvinylimidazole (PAA/PVI) with grafted and ungrafted iron oxide nanoparticles were prepared by a Reflux method. The Fe₃O₄ nanoparticles with 10 nm average diameter were synthesized by controlled co-precipitation and silanization of Si-PVI on Fe₃O₄ was used to obtain the grafted ones. Grafting becomes important at composites of less PVI that cause drastic decreases in AC conductivity. The content of PVI has important effects on the conductivity mechanism of these composites. The effect of grafting and Polyacrylic acid/polyvinylimidazole molar ratio on the conduction mechanism were studied. The conduction mechanism of iron oxide nanocomposites can be adjusted by changing molar ratio of Polyacrylic acid/polyvinylimidazole and grafting of Fe₃O₄ NPs.      

Silver particles growth by pulse electrolysis in acetonitrile solutions

The morphology of silver particles deposited on ITO-glass surface by pulse electrolysis in acetonitrile solutions of AgNO₃ has been analyzed. The influences of potential value (E) as well pulse duration (τ_on) and pause (τ_off) on the size and geometry of the particles has been discussed. It has been shown that in the range of 0.0 ≤ E ≤ ?1.5 V at τ_on = 6 ms and 90 ≤ τ_off ≤ 490 ms formation of silver particles (～20–50 nm) and their agglomeration (～0.2–2 µm) take place. The tendency to increase size of the particles in 3D has been observed with the increase of cathode potential. Decreasing of duty cycle leads to more discrete deposited particles.      

Obtaining and characterizing modified tannins by physical-chemical methods

After oxidation of tannins (Tannins 1–3) extracted from grape seeds, Tanoxil compounds with increased solubility and enhanced antioxidant activities were synthesized. In this research, ABTS^+· assay and a chemiluminescence method were used for antioxidant measurement of hydrophilic compounds (Tanoxils 1–3).

It was observed that the antioxidant activity (AA, %) is very similar for the three samples, while at the same time AA is quite high (93.16%–96.48%). The percentage of inhibition by ABTS^+· is higher for Tanoxil 2 (96.4%) as compared to Tannin 2 compound (14.34%). Moreover, the total content (T_CF) of carboxyl and phenolic groups was investigated. T_CF values, determined for Tanoxil products, revealed a double (Tanoxil 1) or triple (Tanoxil 2) increase as compared to the value of the T_CF of Tannin 1. Tanoxil products represent an interest for future research as they have a high AA (96.4%) and the content of acidic groups is significant (T_CF, 0.191 meq g^?1).

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Thermodynamic protonation constants of vardenafil by the nonlinear regression of multiwavelength pH-spectrophotometric titration data

pH-spectrophotometric titration data were used to determine protonation constants of vardenafil at different ionic strengths I and temperatures of 25°C and 37°C. The use of two different multiwavelength and the multivariate treatment of spectral data, SPECFIT32 and SQUAD(84) nonlinear regression analyses and INDICES factor analysis is presented. The reliability of the protonation constants of the drug was proven with goodness-of-fit tests of the pH-spectra. The thermodynamic protonation constants log K _T ⁱ were estimated by a nonlinear regression of (log K, I) data using the Debye-Hückel equation, yielding log K ₄ ^T = 3.59(1) and 3.26(1), log K ₃ ^T = 5.64(1) and 5.81(1), log K ₂ ^T = 9.41(1) and 8.59(2), log K ₁ ^T = 10.92(2) and 10.05(1) at 25°C and 37°C, where the figure in brackets is the standard deviation in last significant digit. Concurrently, the experimental determination of four thermodynamic protonation constants was combined with the computational prediction of the MARVIN program based on knowledge of the chemical structures of the drug and was in good agreement with its experimental value. The factor analysis of spectra in the INDICES program predicts the correct number of light-absorbing components when the instrument error is known and when the signal-to-error ratio SER is higher than 10.