Effect of lentil and bean flours on rheological and baking properties of wheat dough

The potential of legume flours (lentil and bean) in bakery applications was investigated. The study indicated that legume flours were characterised by high protein (27.30–27.35 mass %) and total dietary fibre (14.91–21.52 mass %), relatively high water holding capacity (4.71–5.42 g g^?1), and good emulsifying properties (emulsifying capacity: 32.73–46.96 cm³ per 100 cm³ and emulsion stability: 60.52–90.90 cm³ per 100 cm³). Fine wheat flour was partially substituted with 10 mass %, 20 mass %, and 30 mass % levels of lentil and bean flours in order to study their farinographic characteristics and baking behaviour. The addition of legume flours increased water absorption capacity (from 58.50 mass % to 74.90 mass %) and dough development time (from 3.50 min to 5.50 min), whereas dough stability was reduced (from 6.67 min to 2.30 min). The presence of legume flours in dough negatively affected the physical parameters of baked rolls and resulted in the reduction in volume, specific volume, and cambering. Sensory evaluation showed that the most acceptable baked rolls were obtained when the wheat-legume blend flour containing 10 mass % of legume flour was applied. Higher levels of legume flours in the products adversely affected the shape, crust colour, crumb elasticity, and hardness of the final products.     

New liquid crystal based on 2-phenylthiophene central core

Six series of bent-shaped liquid crystals based on phenylthiophene central unit and differing in lateral substitution, the number and orientation of ester linkages and character of the terminal chain have been synthesised and studied. In comparison with the previously investigated biphenyl-based analogues, the presence of the thiophene unit results in a strong increase of transition temperatures and appearance of calamitic phases, the character of which depended on the structural changes of mesogens.     

(1,3-Dimethyluracil-5-yl)mercury(II): Preparative, Structural, and NMR Spectroscopic Studies of an Analog of CH(3)Hg(II)

The solution behavior of (1,3-DimeU-C5)Hg(CH(3)COO) (1a) (1,3-DimeU = 1,3-dimethyluracil) with regard to acetate replacement by anions X (Cl(-), Br(-), I(-), NO(3)(-), SCN(-), CN(-)) and by other model nucleobases (1-methylcytosine, 1-MeC, 1-methyluracil, 1-MeUH, 1-methylthymine, 1-MeTH, 9-ethylguanine, 9-EtGH, and 2-thiouracil, 2-ThioUH) has been studied, primarily by means of (1)H and (199)Hg NMR spectroscopy. Moreover, the bis(1,3-DimeU-C5) complex of Hg has been crystallized and studied by X-ray crystallography. 7a: orthorhombic system, space group Fdd2, a = 14.185(4) ?, b = 25.275(7) ?, c = 7.924(2) ?, V = 2840(2) ?(3), Z = 8. The acetato ligand of 1a is readily displaced by anions X, frequently followed by disproportionation reactions leading to HgX(2) and 7a. The donor atom X trans to C(5) has an effect on (3)J coupling between (199)Hg and H(6) of the 1,3-DimeU ligand according to NO(3)(-) > OAc(-) > Cl(-) approximately Br(-) > I(-) > SCN(-) > CN(-) > 1,3-DimeU-C5 with extremes being 222 (X = NO(3)(-)) and 107 Hz (7a). In the presence of excess metal ions (Ag(+), Hg(2+)), 1a forms hetero- and homonuclear derivatives with the second metal ion probably sitting at O(4). The mixed nucleobase complexes have the second base bound to Hg via N(3) (1-MeU (2a), 1-MeT (3a)), N(4) (1-MeC(-) (4a), 1-MeC (4b)), N(1) (9-EtG (5a)), N(7) (9-EtGH (5b)), and N(1), N(7) (9-EtG (5c)), as well as S(2) (2-ThioU (6a)). With the exception of the 9-ethylguanine complexes 5b and 5c, all the other complexes are inert on the (1)H time scale. In several cases, e.g. 2a, 3a, 4a, and 5a, formation of dinuclear Hg or heteronuclear Ag and Pt derivatives has been established by multinuclear NMR spectroscopy.     

Enantiomeric separation of R,S‐tolterodine and R,S‐methoxytolterodine with negatively charged cyclodextrins by capillary electrophoresis

The methods for separation of R,S‐tolterodine and R,S‐methoxytolterodine enantiomers using sulfated α‐, β‐CD and phosphated‐γ‐CD by CE in acidic BGE based on Tris/phosphate pH 2.5 buffer were developed. Sulfated α‐ and β‐CD allow anodic detection while phosphated‐γ‐CD allows only cathodic detection of the separated enantiomers. The influence of chiral selector (CS)'s concentration as well as the influence of composition and concentration of BGE on resolutions were studied. Reversal migration order of tolterodine and methoxytolterodine enantiomers was observed, when sulfated‐α‐ and sulfated‐β‐CD were used. The developed methods with all three studied CSs, were validated and compared. All proposed methods enable determination of 0.2% of S‐tolterodine as an optical impurity in pills, however the method with phosphated‐γ‐CD provided lower detection limit, better repeatability of peak areas and migration times, and also lower consumption of CS. Developed method employing phosphated‐γ‐CD that was applied for the determination of optical purity of R‐tolterodine in commercial pills.     

Liquid chromatographic method for enantiopurity control of alaptide using polysaccharide stationary phases

Separation of veterinary drug alaptide ((S)-8-methyl-6,9-diazaspiro(4,5)decane-7,10-dione) from a chiral impurity (R-enantiomer) was developed. Five chiral columns (three amylose and two cellulose type) were evaluated in a reversed-phase system. Three of them offered satisfactory enantiomeric resolution. Finally, three methods were validated and proved to be applicable for the determination of a chiral impurity content below 0.1% (method A: 3-AmyCoat column, tris-[3,5-dimethylphenyl]carbamoyl amylose; mobile phase: water/methanol/propan-2-ol/butan-2-ol=75:20:3.5:1.5 v/v, flow rate: 0.40 mL/min; column temperature: 30 °C; method B: Chiralpak AS-3R, tris-[1-phenylethyl]carbamoyl amylose; water/acetonitrile=80:20 v/v, 0.40 mL/min; 40 °C; method C: Chiralcel OZ-3R, tris-[3-chloro-4-methylphenyl] carbamoyl cellulose; water/acetonitrile=80:20 v/v, 0.40 mL/min; 40 °C). Some decrease in efficiency with repeated sample injections was observed for the 3-AmyCoat column. The resistance to mass transfer in the stationary phase increased probably due to the change in chiral selector conformation. This effect was considerably suppressed by propan-2-ol or to a greater extent by butan-2-ol added to a mobile phase. Simple regeneration was also suggested to recover efficiency of the column.     

Complexation between the fungicide tebuconazole and copper(II) probed by electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the complex formation between tebuconazole (1) and copper(II) salts, which both are commonly used fungicides in agriculture. Experiments with model solutions containing 1 and CuCl(2) reveal the initial formation of the copper(II) species [(1)CuCl](+) and [(1)(2)CuCl](+) which undergo reduction to the corresponding copper(I) ions [(1)Cu](+) and [(1)(2)Cu](+) under more drastic ionization conditions in the ESI source. In additional experiments, copper/tebuconazole complexes were also detected in samples made from soil solutions of various origin and different amount of mineralization. The direct sampling of such solutions via ESI-MS is thus potentially useful for understanding of the interactions between copper(II) salts and tebuconazole in environmental samples.     

A novel amido–pyrophosphate MnII chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O

The title complex, trans‐bis(dimethylformamide‐κO)bis{N,N′‐N′′,N′′′‐tetra‐tert‐butyl[oxybis(phosphonic diamide‐κO)]}manganese(II) dichloride dihydrate, [Mn(C₁₆H₄₀N₄O₃P₂)₂(C₃H₇NO)₂]Cl₂·2H₂O, is the first example of a bis‐chelate amido–pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)₂]₂ fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn^II atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six‐membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)₂ and P(O)] and O[P(O)(N)₂]₂. This analysis shows that the six‐membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N—H...O and N—H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O—H...Cl hydrogen bonds.     

Bis(di‐2‐pyridylamine‐κ2N2,N2′)(nitrato‐κ2O,O′)nickel(II) nitrate

<!?tpct=26.8pt>In the ionic title compound, [Ni(NO₃)(C₁₀H₉N₃)₂]NO₃, the central Ni^II atom exhibits cis‐NiN₄O₂ octahedral coordination with three chelating ligands, viz. one nitrate anion and two di‐2‐pyridylamine (dpya) molecules. A second nitrate group acts as a counter‐ion. The complex cations and the nitrate anions are also linked by N—H...O hydrogen bonds. The compound was prepared in two different reproducible ways: direct synthesis from Ni(NO₃)₂ and dpya yielded systematically twinned crystals (the twinning law is discussed), while single crystals were obtained unexpectedly from the Ni(NO₃)₂/dpya/maleic acid/NaOH system.     

Exponential repulsion improves structural predictability of molecular docking

Molecular docking is a powerful tool for theoretical prediction of the preferred conformation and orientation of small molecules within protein active sites. The obtained poses can be used for estimation of binding energies, which indicate the inhibition effect of designed inhibitors, and therefore might be used for in silico drug design. However, the evaluation of ligand binding affinity critically depends on successful prediction of the native binding mode. Contemporary docking methods are often based on scoring functions derived from molecular mechanical potentials. In such potentials, nonbonded interactions are typically represented by electrostatic interactions between atom‐centered partial charges and standard 6–12 Lennard–Jones potential. Here, we present implementation and testing of a scoring function based on more physically justified exponential repulsion instead of the standard Lennard–Jones potential. We found that this scoring function significantly improved prediction of the native binding modes in proteins bearing narrow active sites such as serine proteases and kinases. © 2016 Wiley Periodicals, Inc.     

PEG‐Modified Macroporous Poly(Glycidyl Methacrylate) and Poly(2‐Hydroxyethyl Methacrylate) Microspheres to Reduce Non‐Specific Protein Adsorption

To minimize non‐specific protein adsorption on macroporous poly(glycidyl methacrylate) and poly(2‐hydroxyethyl methacrylate) microspheres containing amino and/or carboxyl groups, the microspheres are coated with α,ω‐bis‐carboxy poly(ethylene glycol) and amino‐terminated poly(ethylene glycol‐co‐propylene glycol) or α‐methoxy‐ω‐amino poly(ethylene glycol). Adsorption of bovine serum albumin (BSA), γ‐globulin, ¹²⁵I‐BSA, pepsin, and chymotrypsin on neat and PEGylated microspheres is determined by UV–VIS spectroscopy of supernatants and eluates or by measurement of radioactivity in an ionization chamber. Neat and PEGylated microspheres adsorb 0.8–70% and 0.02–44% of protein, respectively.