Synthesis and characterization of cholesterol-based nonsymmetric dimers terminated with ferrocenyl core

The molecular design, synthesis, and thermal behavior of cholesterol-based nonsymmetric dimers, which can also be regarded as metallomesogens, consisting of either two- or three-ring aromatic cores terminated with ferrocenyl unit are reported. The spacer length connecting the cholesterol and aromatic cores is held constant while the length of the spacer connecting ferrocene and aromatic cores has been varied. The occurrence of the enantiotropic mesomorphism in these compounds has been adjudged by optical, calorimetric, and X-ray diffraction studies. In particular these systems exhibit liquid crystal phases such as chiral nematic, twist grain boundary, and smectic A phases. Of these, the chiral nematic phase commonly occurs in all the synthesized compounds.     

A grid-based algorithm in conjunction with a gaussian-based model of atoms for describing molecular geometry

A novel grid-based method is presented, which in conjunction with a smooth Gaussian-based model of atoms, is used to compute molecular volume (MV) and surface area (MSA). The MV and MSA are essential for computing nonpolar component of free energies. The objective of our grid-based approach is to identify solute atom pairs that share overlapping volumes in space. Once completed, this information is used to construct a rooted tree using depth-first method to yield the final volume and SA by using the formulations of the Gaussian model described by Grant and Pickup (J. Phys Chem, 1995, 99 , 3503). The method is designed to function uninterruptedly with the grid-based finite-difference method implemented in Delphi, a popular and open-source package used for solving the Poisson–Boltzmann equation (PBE). We demonstrate the time efficacy of the method while also validating its performance in terms of the effect of grid-resolution, positioning of the solute within the grid-map and accuracy in identification of overlapping atom pairs. We also explore and discuss different aspects of the Gaussian model with key emphasis on its physical meaningfulness. This development and its future release with the Delphi package are intended to provide a physically meaningful, fast, robust and comprehensive tool for MM/PBSA based free energy calculations. © 2019 Wiley Periodicals, Inc.     

A triad of rhenium-mediated transformations

The title transformations are oxygen atom transfer, twin isomerization and regiospecific imine oxidation.Bispyridyldiazole ligands have furnished new oxygen atom transfer reagents of coordination type Re^VOCl₃(NN) which undergo a slower transfer to PPh₃ than the corresponding azole reagents. The rate of twin isomerization (linkage and geometrical) of meridional azole complexes of coordination type Re^III(OPnP)Cl₃(NN) to facial Re^III(PnPO)Cl₃(NN) decreases rapidly asn increases in the interval 1–4 (PnP is Ph₂P(CH₂)_nPPh₂). An α-diimine chelate of type Re^V(NPh)Cl₃(NN) is shown to undergo facile oxidation to the corresponding iminoamide complex Re_VI(NPh)Cl₃(NN) upon treating with dilute nitric acid. The reaction proceeds via regiospecific nucleophilic addition of waterto the more polarized imine function. Dedicated to Professor C N R Rao on his 70th birthday     

Using flow to switch the valency of bacterial capture on engineered surfaces containing immobilized nanoparticles

Toward an understanding of nanoparticle-bacterial interactions and the development of sensors and other substrates for controlled bacterial adhesion, this article describes the influence of flow on the initial stages of bacterial capture (Staphylococcus aureus) on surfaces containing cationic nanoparticles. A PEG (poly(ethylene glycol)) brush on the surface around the nanoparticles sterically repels the bacteria. Variations in ionic strength tune the Debye length from 1 to 4 nm, increasing the strength and range of the nanoparticle attractions toward the bacteria. At relatively high ionic strengths (physiological conditions), bacterial capture requires several nanoparticle-bacterial contacts, termed "multivalent capture". At low ionic strength and gentle wall shear rates (on the order of 10 s(-1)), individual bacteria can be captured and held by single surface-immobilized nanoparticles. Increasing the flow rate to 50 s(-1) causes a shift from monovalent to divalent capture. A comparison of experimental capture efficiencies with statistically determined capture probabilities reveals the initial area of bacteria-surface interaction, here about 50 nm in diameter for a Debye length κ(-1) of 4 nm. Additionally, for κ(-1) = 4 nm, the net per nanoparticle binding energies are strong but highly shear-sensitive, as is the case for biological ligand-receptor interactions. Although these results have been obtained for a specific system, they represent a regime of behavior that could be achieved with different bacteria and different materials, presenting an opportunity for further tuning of selective interactions. These finding suggest the use of surface elements to manipulate individual bacteria and nonfouling designs with precise but finite bacterial interactions.     

Rhenium chemistry of azooximes: oxygen atom transfer, azoimine chelation, and imine-oxime contrast

The concerned azooximes (L1OH, 1) are of type p-X-C6H4C(N2Ph)(NOH) (X = H, Me, Cl). The reaction of [Re(MeCN)Cl3(PPh3)2] with [Ag(L1OH)(L1O)] in cold dichloromethane-acetonitrile solvent has furnished the green colored ionized azoimine complex [ReV(O)Cl(PPh3)2(L1)](PF6), 2. In effect L1O- has undergone oxidative addition, the oxygen atom being transferred to the metal site. Upon treatment of [ReV(NPh)Cl3(PPh3)2] with L1OH in solution, the neutral azoimine complex [ReV(NPh)Cl3(L1H)], 3, resulted due to the spontaneous transfer of the oxime oxygen atom to a PPh3 ligand, which is eliminated as OPPh3. In contrast, the oxime of 2-acetylpyridine (L2OH, 4) did not undergo oxygen atom transfer and simply afforded the imine-oxime complex [ReV(NC6H4Y)Cl2(PPh3)(L2O)], 5, upon reacting with [ReV(NC6H4Y)Cl3(PPh3)2] (Y = H, Me, Cl). The spectral and electrochemical properties of 2, 3, and 5 and the structures of three representative compounds are reported. In the cation of 2 (X = H) the two PPh3 ligands lie trans to each other and the equatorial plane is defined by the five-membered azoimine chelate ring and the oxo and chloro ligands. The oxo ligand which forms a model triple bond (Re-O length 1.616(6) A) lies cis to the imine-N atom. In 3 (X = Cl) the ReCl3 fragment has meridional geometry and the imido nitrogen lies trans to the imine nitrogen of the planar azoimine chelate ring. In 5 x H2O (Y = Me), the Cl, oximato-N, and P atoms define an equatorial plane and the pyridine-N lies trans to the imido-N. The water of crystallization is hydrogen bonded to the oximato oxygen atom (O...O, 2.829(5) A). Reaction models in which chelation of the azooxime precedes oxygen atom transfer are proposed on the basis of oxophilicity of trivalent rhenium, Lewis acid activity of pentavalent rhenium, electron withdrawal by the azo group, and observed relative disposition of ligands in products.     

A test of the Hirshfeld definition of atomic charges and moments

Summary The Hirshfeld population analysis scheme which carves the molecular density into atomic density contributions is tested. This method does not require a reference to basis sets or their respective locations, but is based on a different physical and mathematical footing. The advantage of this method is that, when the molecular deformation density converges to the true solution, the computed net charges will necessarily converge. This method also allows a straightforward definition for local moments. About 36 molecules have been used to compute the conventional Mulliken and Löwdin population analyses with STO3G, 6311G** and Dunning-Hay split valence basis sets. These results have been compared to the estimates provided by the Hirshfeld model. The charges found in the Hirshfeld method are smaller than those from the other methods.     

Magnetic properties of hydrothermally synthesized BiFeO3 nanoparticles

BiFeO₃ nanoparticles with diameters in the range 65–90 nm were prepared using a hydrothermal technique. Low-temperature magnetic measurements showed ferromagnetic behavior of the samples below a certain temperature. The magnetization values were drastically reduced in the case of samples having larger diameters. This was explained as arising due to a reduction of the number of uncompensated spins associated with Fe³⁺ ions as particle diameter was increased. A surface spin disorder is believed to be responsible for this property.     

Bounding the number of stable homotopy types of a parametrized family of semi-algebraic sets defined by quadratic inequalities

We prove a nearly optimal bound on the number of stable homotopytypes occurring in a k-parameter semi-algebraic family of setsin R, each defined in terms of m quadratic inequalities. Ourbound is exponential in k and m, but polynomial in . More precisely,we prove the following. Let R be a real closed field and let = {P₁, ... , P_m} R[Y₁, ... ,Y,X₁, ... ,X_k], with deg_Y(P_i) 2, deg_X(P_i) d, 1 i m. Let S R^+k be a semi-algebraic set,defined by a Boolean formula without negations, with atoms ofthe form P 0, P 0, P . Let : R^+k R^k be the projection onthe last k coordinates. Then the number of stable homotopy typesamongst the fibers S_x = ^–1(x) S is bounded by (2^mkd)^O(mk).