Chromatography-Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.     

A soluble and multichromic conducting polythiophene derivative

A new soluble polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1-4-nitrophenyl-2,5-di(2-thienyl)-1H-pyrrole (SNSNO₂). Chemical method produces a polymer which is completely soluble in organic solvents. The structures of both the monomer and the soluble polymer were elucidated by ¹H and ¹³C-NMR and FTIR. The average molecular weight has been determined by GPC to be Mn = 6.3 × 10³ for the chemically synthesized polymer. P(SNSNO₂) was also synthesized via potentiostatic electrochemical polymerization. Characterizations of the resulting polymer were performed by cyclic voltammetry CV, FTIR and UV-Vis spectroscopy. Four-probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. In addition, dual type polymer electrochromic devices ECDs based on P(SNSNO₂) with poly3,4-ethylenedioxythiophene (PEDOT) were constructed. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts and optical memories.     

Synthesis of vinca alkaloids and related compounds. 100. Stereoselective oxidation reactions of compounds with the aspidospermane and quebrachamine ring system. First synthesis of some alkaloids containing the epoxy ring

The first syntheses of the alkaloids (-)-mehranine (3), (+)-voaphylline/conoflorine (4), (+)-N(a)-methylvoaphylline/hecubine (5), and (-)-lochnericine (2) were achieved by stereoselective epoxidation starting from (-)-tabersonine (1), through intermediates with the aspidospermane and quebrachamine skeleton.     

Nitro Derivatives of Parabanic Acid as Potential Explosives: A Theoretical Study

This work deals with certain parabanic acid (PA) derivatives because they possess great calculated density (>1.8 g · cm^–3) and high content of nitrogen (26 %). Computed ballistic properties of eight different parabanic acid derivatives are presented. The structures were optimized at the B3LYP/6‐31G(d, p) level. The calculated data for PA are found to be compatible with the experimental X‐ray data. The detonation performance analyses were done using empirical Kamlet‐Jacobs equations. Additionally, detonation products were assigned and power index were calculated. All the compounds considered are powerful candidates for high energy materials.     

High-throughput prediction of blood-brain partitioning: a thermodynamic approach

A high-throughput in silico screening tool for potentially CNS active compounds was developed on the basis of the correlation of solvation free energies and blood-brain partitioning (log(cbrain/cblood) = log BB) data available from experimental sources. Utilizing a thermodynamic approach, solvation free energies were calculated by the fast and efficient generalized Born/surface area continuum solvation model, which enabled us to evaluate more than 10 compounds/min. Our training set involved a structurally diverse set of 55 compounds and yielded a function of log BB = 0.035Gsolv + 0.2592 (r = 0.85, standard error 0.37). Calculation of solvation free energies for 8700 CNS active compounds (CIPSLINE database) revealed that Gsolv is higher than -50 kJ/mol for the 96% of these compounds which can be used as suitable criteria for the identification of compounds preferable for CNS penetration.     

Efficient algorithms for robust and stable principal component pursuit problems

The problem of recovering a low-rank matrix from a set of observations corrupted with gross sparse error is known as the robust principal component analysis (RPCA) and has many applications in computer vision, image processing and web data ranking. It has been shown that under certain conditions, the solution to the NP-hard RPCA problem can be obtained by solving a convex optimization problem, namely the robust principal component pursuit (RPCP). Moreover, if the observed data matrix has also been corrupted by a dense noise matrix in addition to gross sparse error, then the stable principal component pursuit (SPCP) problem is solved to recover the low-rank matrix. In this paper, we develop efficient algorithms with provable iteration complexity bounds for solving RPCP and SPCP. Numerical results on problems with millions of variables and constraints such as foreground extraction from surveillance video, shadow and specularity removal from face images and video denoising from heavily corrupted data show that our algorithms are competitive to current state-of-the-art solvers for RPCP and SPCP in terms of accuracy and speed.     

Time-Dependent Shape Factors for Uniform and Non-Uniform Pressure Boundary Conditions

Matrix–fracture transfer functions are the backbone of any dual-porosity or dual-permeability formulation. The chief feature within them is the accurate definition of shape factors. To date, there is no completely accepted formulation of a matrix–fracture transfer function. Many formulations of shape factors for instantly-filled fractures with uniform pressure distribution have been presented and used; however, they differ by up to five times in magnitude. Based on a recently presented transfer function, time-dependent shape factors for water imbibing from fracture to matrix under pressure driven flow are proposed. Also new matrix–fracture transfer pressure-based shape factors for instantly-filled fractures with non-uniform pressure distribution are presented in this article. These are the boundary conditions for a case for porous media with clusters of parallel and disconnected fractures, for instance. These new pressure-based shape factors were obtained by solving the pressure diffusivity equation for a single phase using non-uniform boundary conditions. This leads to time-dependent shape factors because of the transient part of the solution for pressure. However, approximating the solution with an exponential function, one obtains constant shape factors that can be easily implemented in current dual-porosity reservoir simulators. The approximate shape factors provide good results for systems where the transient behavior of pressure is short (a case commonly encountered in fractured reservoirs).     

Surface Characterization of a Novel D-��-D Type Ligand by IGC at Infinite Dilution

The adsorption properties and acid?Cbase contributions to the surface energy of (E)-N-((E)-3-(4-(dimethylamino)phenyl)allylidene)-4-(4-((E)-((E))-3-(4(dimethylamino)phenyl)allylidene)amino)-3-methylnaphthalen-1-yl)-2-ethylnaphthalen-1-amine which is a new D-??-D Type Schiff base ligand (L) were determined by inverse gas chromatography (IGC) at infinite dilution. The retentions of several organic solvents on L were measured in the temperature range from 40 to 100 °C by IGC. The dispersive component of the surface energy, $ \gamma_{S}^{D} $ of studied adsorbent surface was estimated using retention times of different nonpolar organics in the infinite dilution region. Thermodynamic parameters of adsorption (free energy, $ \Updelta G_{A}^{S} , $ enthalpy, $ \Updelta H_{A}^{S} $ and entrophy, $ \Updelta S_{A}^{S} $ ), dispersive components of the surface energies, $ \gamma_{S}^{D} $ and the acid, K _A and base, K _D constants for the L were calculated. The obtained results proved that IGC is an efficient and successful technique for the characterization of adsorption properties and acid?Cbase quantity of these kinds of materials.     

Bioactive Abietane-Type Diterpenoid Glycosides from Leaves of Clerodendrum infortunatum (Lamiaceae)

In this study, two previously undescribed diterpenoids, (5R,10S,16R)-11,16,19-trihydroxy-12-O-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl-17(15→16),18(4→3)-diabeo-3,8,11,13-abietatetraene-7-one (1) and (5R,10S,16R)-11,16-dihydroxy-12-O-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl-17(15→16),18(4→3)-diabeo-4-carboxy-3,8,11,13-abietatetraene-7-one (2), and one known compound, the C₁₃-nor-isoprenoid glycoside byzantionoside B (3), were isolated from the leaves of Clerodendrum infortunatum L. (Lamiaceae). Structures were established based on spectroscopic and spectrometric data and by comparison with literature data. The three terpenoids, along with five phenylpropanoids: 6′-O-caffeoyl-12-glucopyranosyloxyjasmonic acid (4), jionoside C (5), jionoside D (6), brachynoside (7), and incanoside C (8), previously isolated from the same source, were tested for their in vitro antidiabetic (α-amylase and α-glucosidase), anticancer (Hs578T and MDA-MB-231), and anticholinesterase activities. In an in vitro test against carbohydrate digestion enzymes, compound 6 showed the most potent effect against mammalian α-amylase (IC₅₀ 3.4 ± 0.2 μM) compared to the reference standard acarbose (IC₅₀ 5.9 ± 0.1 μM). As yeast α-glucosidase inhibitors, compounds 1, 2, 5, and 6 displayed moderate inhibitory activities, ranging from 24.6 to 96.0 μM, compared to acarbose (IC₅₀ 665 ± 42 μM). All of the tested compounds demonstrated negligible anticholinesterase effects. In an anticancer test, compounds 3 and 5 exhibited moderate antiproliferative properties with IC₅₀ of 94.7 ± 1.3 and 85.3 ± 2.4 μM, respectively, against Hs578T cell, while the rest of the compounds did not show significant activity (IC₅₀ > 100 μM).     

Naked Eye Detection of Carbonate,Hydroxide, and Cyanide Ions with 1,4′‐Diazaflavonium Bromides: A Simple Spectrophotometric Method for Cyanide Determination

Anion sensor properties of N‐alkyl‐substituted 1,4′‐diazaflavonium bromides in methanol–water were evaluated by UV–vis spectrometry. Pronounced changes were observed in the absorption spectra of all compounds for only OH^?, CO₃^2?, and CN^? among F^?, Cl^?, Br^?, I^?, OH^?, CO₃^2?, NO₃^?, PO₄^3?, CN^?, SO₄^2?, HSO₄^?, HCO₃^?, SCN^?, NO₂^?, and P₂O₇^2? ions. Two new absorption bands at 385 and 685 nm accompanying the distinct color change for OH^?, CO₃^2?, and CN^? ions were observed in case of all compounds. The color changes were from pink to blue for CO₃^2? and OH^? ions and from pink to purple for CN^? ion. Thanks to the distinct color change, the compounds can be used as selective colorimetric anion sensors. Linear changes of absorbance of N‐heptyl‐substituted compound at 385 nm as a function of the ion concentration were used to determine CN^? ion in water samples. Detection and quantification limits of the proposed method were 0.94 and 2.82 mg/L, respectively.