Supramolecular Arrangement and DFT analysis of Zinc(II) Schiff Bases: An Insight towards the Influence of Compartmental Ligands on Binding Interaction with Protein

We report, for the first time, a detailed crystallographic study of the supramolecular arrangement for a set of zinc(II) Schiff base complexes containing the ligand 2,6-bis((E)-((2-(dimethylamino)ethyl)imino)methyl)-4-R-phenol], where R=methyl/tert-butyl/chloro. The supramolecular study acts as a pre-screening tool for selecting the compartmental ligand R of the Schiff base for effective binding with a targeted protein, bovine serum albumin (BSA). The most stable hexagonal arrangement of the complex [Zn − Me] (R=Me) stabilises the ligand with the highest FMO energy gap (ΔE=4.22 eV) and lowest number of conformations during binding with BSA. In contrast, formation of unstable 3D columnar vertebra for [Zn − Cl] (R=Cl) tend to activate the system with lowest FMO gap (3.75 eV) with highest spontaneity factor in molecular docking. Molecular docking analyses reported in terms of 2D LigPlot+ identified site A, a cleft of domains IB, IIIA and IIIB, as the most probable protein binding site of BSA. Arg144, Glu424, Ser428, Ile455 and Lys114 form the most probable interactions irrespective of the type of compartmental ligands R of the Schiff base whereas Arg185, Glu519, His145, Ile522 act as the differentiating residues with ΔG=−7.3 kcal mol⁻¹.     

Scarlet Flax Linum grandiflorum (L.) In Vitro Cultures as a New Source of Antioxidant and Anti-Inflammatory Lignans

In vitro cultures of scarlet flax (Linum grandiflorum L.), an important ornamental flax, have been established as a new possible valuable resource of lignans and neolignans for antioxidant and anti-inflammatory applications. The callogenic potential at different concentrations of α-naphthalene acetic acid (NAA) and thidiazuron (TDZ), alone or in combinations, was evaluated using both L. grandiflorum hypocotyl and cotyledon explants. A higher callus induction frequency was observed on NAA than TDZ, especially for hypocotyl explants, with a maximum frequency (i.e., 95.2%) on 1.0 mg/L of NAA. The presence of NAA (1.0 mg/L) in conjunction with TDZ tended to increase the frequency of callogenesis relative to TDZ alone, but never reached the values observed with NAA alone, thereby indicating the lack of synergy between these two plant growth regulators (PGRs). Similarly, in terms of biomass, NAA was more effective than TDZ, with a maximum accumulation of biomass registered for medium supplemented with 1.0 mg/L of NAA using hypocotyls as initial explants (DW: 13.1 g). However, for biomass, a synergy between the two PGRs was observed, particularly for cotyledon-derived explants and for the lowest concentrations of TDZ. The influence of these two PGRs on callogenesis and biomass is discussed. The HPLC analysis confirmed the presence of lignans (secoisolariciresinol (SECO) and lariciresinol (LARI) and neolignan (dehydrodiconiferyl alcohol [DCA]) naturally accumulated in their glycoside forms. Furthermore, the antioxidant activities performed for both hypocotyl- and cotyledon-derived cultures were also found maximal (DPPH: 89.5%, FRAP 866: µM TEAC, ABTS: 456 µM TEAC) in hypocotyl-derived callus cultures as compared with callus obtained from cotyledon explants. Moreover, the anti-inflammatory activities revealed high inhibition (COX-1: 47.4% and COX-2: 51.1%) for extract of hypocotyl-derived callus cultures at 2.5 mg/L TDZ. The anti-inflammatory action against COX-1 and COX-2 was supported by the IC₅₀ values. This report provides a viable approach for enhanced biomass accumulation and efficient production of (neo)lignans in L. grandiflorum callus cultures.     

An eleven-vertex metallaborane with tetracapped pentagonal bipyramidal geometry

A metallaborane of novel structure, [(Cp*Mo)(2)B(3)H(3)Se(2){Fe(CO)(2)}(2){Fe(CO)(3)}(2)] (2; Cp* = η(5)-C(5)Me(5)), with tetracapped pentagonal bipyramidal geometry, isolated from the reaction of [(Cp*Mo)(2)B(4)H(4)Se(2)], 1 with [Fe(2)(CO)(9)]; the title compound exhibit an 11-vertex closo-cage geometry, having eight skeletal electron pairs (sep) and 98 valence electrons, appropriate for its geometric structure.     

31P and 1h NMR as probes of domain alignment in a rigid crystalline surfactant mesophase

A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform (31)P and (1)H NMR spectroscopy. Shear alignment was reflected through both (31)P NMR and (1)H NMR spectra. A complicated (31)P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. (31)P NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, (1)H NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of (31)P NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that (31)P and (1)H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis.     

Regeneration of Carbonyl Compounds from Oximes and Hydrazones Using Peroxymonosulfate on Silica gel under Solvent-free Conditions

In an environmentally benign solvent-free system, oximes and hydrazones are rapidly transformed into parent carbonyl compounds using peroxymonosulfate on silica gel under microwave irradiation in good to excellent yields.     

Broadband dielectric relaxation study on a diluted solution of a ferroelectric liquid crystal by time domain reflectometry

Abstract

In this work, complex permittivity measurements on a diluted solution of the ferroelectric liquid crystal, 4-[(S,S)-2,3-epoxyhexyloxy]-phenyl 4-(decyloxy)-benzoate, which shows ferroelectric smectic C phase (S*_C), have been performed. Using time domain reflectometry, at frequencies between 10 MHz and 10 GHz, in the temperature range from 50°C down to 10°C for every 10°C, at 5, 10 and 30 wt.% in benzene we observe two independent relaxation processes around 150 MHz and 2 GHz. It is shown that the high frequency process is due to the internal molecular reorientations while the low frequency one is due to molecular orientation around the long molecular axis. It is concluded that the reorientation around the long axis is hindered and leads to a resultant macroscopic polarization.     

Synthesis of oxacalothrixin B and its analogues involving iodine/TBHP-mediated electrocyclization

The total synthesis of oxacalothrixins, an isostere of biologically important carbazoloquinone alkaloid, calothrixin B was achieved from 2-acetyl-3-methylbenzofuran. An iodine/TBHP-mediated oxidative cyclization of benzofuranyl-enamine has been employed as a key step to synthesize, the crucial intermediate 1-hydroxy dibenzofurancarbaldehyde. The latter upon reductive cyclization followed by PIDA-mediated oxidation furnished oxacalothrixin B and its analogues.     

Mixing examples in the class of piecewise monotone and continuous maps of the unit interval

A process (T, P) is said to have the “ ” property if there is a uniform, positive lowerbound δ on the separation between theT-P names of (almost) every pair of pointsx≠y. A finite group rotation with partition into distinct points provides a trivial example. Given any process having the property we show that there exists a Bernoulli shiftB so thatT×B is measurably isomorphic to the natural extension of a piecewise monotone, continuous, and expanding map of the unit interval. This construction is applied to produce interval maps which are ergodic but not weak-mixing, weak-mixing but not mixing, and mixing but not exact with respect to their unique absolutely continuous invariant measures, in contrast with the results known for piecewiseC ^1+∈ expansive interval maps. In obtaining these examples we identify a number of nontrivial classes of automorphismsT which admit processes having the property. Supported by NSERC grant OGP0046586 90.     

Limiting Spectral Distribution of Random k-Circulants

Consider random k-circulants A _k,n with n????,k=k(n) and whose input sequence {a _l } _l??0 is independent with mean zero and variance one and $\sup_{n}n^{-1}\sum_{l=1}^{n}\mathbb{E}|a_{l}|^{2+\delta}<\infty$ for some ??>0. Under suitable restrictions on the sequence {k(n)} _n??1, we show that the limiting spectral distribution (LSD) of the empirical distribution of suitably scaled eigenvalues exists, and we identify the limits. In particular, we prove the following: Suppose g??1 is fixed and p ₁ is the smallest prime divisor of g. Suppose $P_{g}=\prod_{j=1}^{g}E_{j}$ where {E _j }_1??j??g are i.i.d. exponential random variables with mean one. (i) If k ^g =?1+sn where s=1 if g=1 and $s=o(n^{p_{1}-1})$ if g>1, then the empirical spectral distribution of n ^?1/2 A _k,n converges weakly in probability to $U_{1}P_{g}^{1/(2g)}$ where U ₁ is uniformly distributed over the (2g)th roots of unity, independent of P _g . (ii) If g??2 and k ^g =1+sn with $s=o(n^{p_{1}-1})$ , then the empirical spectral distribution of n ^?1/2 A _k,n converges weakly in probability to $U_{2}P_{g}^{1/(2g)}$ where U ₂ is uniformly distributed over the unit circle in ?², independent of P _g . On the other hand, if k??2, k=n ^o(1) with gcd?(n,k)=1, and the input is i.i.d. standard normal variables, then $F_{n^{-1/2}A_{k,n}}$ converges weakly in probability to the uniform distribution over the circle with center at (0,0) and radius $r=\exp(\mathbb{E}[\log\sqrt{E}_{1}])$ .