A novel approach to the quantification of urinary aryl-propionamide-derived SARMs by UHPLC–MS/MS

A simple and sensitive procedure for the quantification of two commonly abused aryl-propionamide-derived selective androgen receptor modulators (SARMs), namely S-4 (GTx-007, andarine) and S-22 (GTx-024, MK-2866, ostarine, enobosarm), has been described. Urine samples were prepared for analysis by means of a dispersive liquid–liquid microextraction using methanol and chloroform as dispersive and extracting solvents, respectively. Factors that might influence the extraction process as well as their optimum conditions were evaluated by Box–Benken and central composite designs. After extraction, the analytes were quantified by UHPLC–MS/MS. The proposed procedure was validated on human urine samples. As a result, for both SARMs the detection limits were observed at 0.05 ng/mL and calibration curves were linear in the concentration range of 0.25–50 ng/mL with the coefficient of determination of 0.998.     

Synthesis of cyclic norspermidine derivative of protohemin IX

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Inhibition by polyphenols containing OH groups at different positions in the presence of lecithin

Russian Chemical Bulletin - An inhibition by the semisynthetic polyphenols bearing bicyclic isobornyl substituents and OH groups arranged variously relative to each other was investigated in the...     

Orthogonal and unitary tensor decomposition from an algebraic perspective

While every matrix admits a singular value decomposition, in which the terms are pairwise orthogonal in a strong sense, higher-order tensors typically do not admit such an orthogonal decomposition. Those that do have attracted attention from theoretical computer science and scientific computing. We complement this existing body of literature with an algebro-geometric analysis of the set of orthogonally decomposable tensors.More specifically, we prove that they form a real-algebraic variety defined by polynomials of degree at most four. The exact degrees, and the corresponding polynomials, are different in each of three times two scenarios: ordinary, symmetric, or alternating tensors; and real-orthogonal versus complex-unitary. A key feature of our approach is a surprising connection between orthogonally decomposable tensors and semisimple algebras—associative in the ordinary and symmetric settings and of compact Lie type in the alternating setting.     

Polymorphism of methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate: an experimental and theoretical study

Being a close analogue of amflutizole, methyl 4‐amino‐3‐phenylisothiazole‐5‐carboxylate (C₁₁H₁₀N₂O₂S) was assumed to be capable of forming polymorphic structures. Noncentrosymmetric and centrosymmetric polymorphs have been obtained by crystallization from a series of more volatile solvents and from denser tetrachloromethane, respectively. Identical conformations of the molecule are found in both structures. The two polymorphs differ mainly in the intermolecular interactions formed by the amino group and in the type of stacking interactions between the π‐systems. The most effective method for revealing packing motifs in structures with intermolecular interactions of different types (hydrogen bonding, stacking, dispersion, etc.) is to study the pairwise interaction energies using quantum chemical calculations. Molecules form a column as the primary basic structural motif due to stacking interactions in both polymorphic structures under study. The character of a column (straight or zigzag) is determined by the orientations of the stacked molecules (in a `head‐to‐head' or `head‐to‐tail' manner). Columns bound by intermolecular N—H…O and N—H…N hydrogen bonds form a double column as the main structural motif in the noncentrosymmetric structure. Double columns in the noncentrosymmetric structure and columns in the centrosymmetric structure interact strongly within the ab crystallographic plane, forming a layer as a secondary basic structural motif. The noncentrosymmetric structure has a lower density and a lower (by 0.59 kJ mol^?1) lattice energy, calculated using periodic calculations, compared to the centrosymmetric structure.     

Conformational polymorphs of 3‐cyclopropyl‐5‐(3‐methyl‐[1,2,4]triazolo[4,3‐a]pyridin‐7‐yl)‐1,2,4‐oxadiazole

The dipharmacophore compound 3‐cyclopropyl‐5‐(3‐methyl‐[1,2,4]triazolo[4,3‐a]pyridin‐7‐yl)‐1,2,4‐oxadiazole, C₁₂H₁₁N₅O, was studied on the assumption of its potential biological activity. Two polymorphic forms differ in both their molecular and crystal structures. The monoclinic polymorphic form was crystallized from more volatile solvents and contains a conformer with a higher relative energy. The basic molecule forms an abundance of interactions with relatively close energies. The orthorhombic polymorph was crystallized very slowly from isoamyl alcohol and contains a conformer with a much lower energy. The basic molecule forms two strong interactions and a large number of weak interactions. Stacking interactions of the `head‐to‐head' type in the monoclinic structure and of the `head‐to‐tail' type in the orthorhombic structure proved to be the strongest and form stacked columns in the two polymorphs. The main structural motif of the monoclinic structure is a double column where two stacked columns interact through weak C—H…N hydrogen bonds and dispersive interactions. In the orthorhombic structure, a single stacked column is the main structural motif. Periodic calculations confirmed that the orthorhombic structure obtained by slow evaporation has a lower lattice energy (0.97 kcal mol^?1) compared to the monoclinic structure.     

The Effect of the Side Chain on Gelation Properties of Bile Acid Alkyl Amides

Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all six compounds were studied for 36 solvents with varying polarities. Gelation was observed mainly in aromatic solvents, which is characteristic for bile-acid-based low molecular weight gelators. Out of 108 bile acid-solvent combinations, a total of 44 gel systems were formed, 28 of which from lithocholic acid derivatives, only two from deoxycholic acid derivatives, and 14 from cholic acid derivatives. The majority of the gel systems were formed from bile acids with hexyl side chains, contrary to the cyclohexyl group, which seems to be a poor gelation moiety. These results indicate that the spatial demand of the side chain is the key feature for the gelation properties of the bile acid amides.     

Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State

Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.     

Resonant generation of a solitary wave in a thermocline

The resonant generation of a second-mode internal solitary wave, resulting from a ship internal waves system damping in a thermocline, is studied experimentally. The source of the stationary internal waves was provided by an oblong ellipsoid of revolution towed horizontally and uniformly at the depth of the thermocline center. The ranges of the Reynolds and Froude numbers were 500Re=Ul/v 15000 and 0.3Fi=U/N _max D1.0, respectively. When the body's speed and the linear long-wave second-mode phase speed were equal, an internal solitary wave of the bulge type was observed. The shape of the wave satisfied the Korteweg-de Vries equation. The Urcell parameter was equal to 10.2.List of Symbols L, B, H towing tank length, breadth and height respectively - z vertical coordinate - D characteristic vertical dimension of the body - a minor semiaxis of an ellipsoid - b major semiaxis of an ellipsoid (maximum ellipsoid diameter D=2a) - l length of the body ( =2b) - U velocity of the body - t temperature - g acceleration due to gravity - i fresh water density at ith level - _4° fresh water density for temperature t=4°C - o water density at the center of the thermocline - _i density variation due to the temperature variation at the ith horizon - N Brunt-Väisälä frequency - N _max maximum value of Brunt-Väisälä frequency - Re Reynolds number - Fi internal Froude number - f _n eigenfunction of the boundary-value problem for the nth mode - _n nth mode frequency - k _{n n}th mode horizontal wavenumber - C _n limiting phase speed of a linear nth mode interval wave (= _n/k_n;k_n 0) - Ur Urcell parameter - v fresh water kinematic viscosity - conventional density - half-length of a solitary wave - ₀ solitary wave height - time This work was partially supported by the INTAS (grant no. 94-4057) and by the Russian Foundation of Basic Research under grant no. 94-05-17004-a.A version of this paper was presented at the Second International Conference on Experimental Fluid Mechanics, Torino, Italy, 4–8 July, 1994.