The (n, 2n) cross sections of 85Rb, 87Rb and 144Sm

The (n, 2n) cross sections at neutron energies between 14.9 and 17.0 MeV have been measured for ⁸⁵Rb, ⁸⁷Rb and ¹⁴⁴Sm by the mixed-powder method and γ-ray detection by a Ge(Li) spectrometer. Using the ²⁷Al(n, α)²⁴Na reaction for monitoring, the measured cross sections were (in mb): ${}^{85}\text{Rb}\text{(}\text{n}\text{, 2}\text{n}\text{)}{}^{\mathrm{<mtext>84(</mtext><mtext>m+g</mtext><mtext>)</mtext>}}\text{Rb}\text{, 1125±141, 1177±148}\text{and}\text{1235±162}\text{at}\text{15.0±0.4}\text{MeV}\text{, 16.2±0.7}\text{MeV and}\text{17.0±0.9}\text{MeV, respectively}\text{;}{}^{85}\text{Rb}\text{(}\text{n}\text{, 2}\text{n}\text{)}{}^{\mathrm{<mtext>84</mtext><mtext>m</mtext>}}\text{Rb}\text{, 662±83, 688±87}\text{and}\text{765±99}\text{at}\text{15.0±0.4}\text{MeV}\text{, 16.2±0.7}\text{MeV and}\text{17.0±0.9}\text{MeV}\text{,}\text{respectively}\text{;}{}^{87}\text{Rb}\text{(}\text{n}\text{, 2}\text{n}\text{)}{}^{\mathrm{<mtext>86(</mtext><mtext>m+g</mtext><mtext>)</mtext>}}\text{Rb}\text{, 1336±168}\text{and}\text{1301±162}\text{at}\text{15.0±0.4}\text{MeV and}\text{16.2±0.7}\text{MeV respectively}\text{;}{}^{144}\text{Sm}\text{(}\text{n}\text{, 2}\text{n}\text{)}{}^{\mathrm{<mtext>143(</mtext><mtext>m+g</mtext><mtext>)</mtext>}}\text{Sm}\text{, 1202±130, 1300±141, 1516±179}\text{and}\text{1514±179}\text{at}\text{14.9±0.3}\text{MeV}\text{, 15.5±0.3}\text{MeV}\text{, 16.4±0.5}\text{MeV and}\text{16.7±0.2}\text{MeV, respectively}$. The measured values are compared with the statistical model calculations of Pearlstein.     

Translational and rotational diffusion of SF6 in zeolite NaY

Temperature dependence of equilibrium as well as dynamical properties of SF(6) in zeolite NaY have been investigated by molecular dynamics simulation. By about 200 K, SF(6) begins to have increased mobility. Strong orientational preference is exhibited by SF(6) during its passage through the 12-ring window, the bottleneck for diffusion. The preference is for orientation with C(3) followed by C(2) and then C(4) molecular symmetry axis perpendicular to the window plane. Translational motion is diffusive with an activation energy of 5.5 kJ/mol. Rotational-diffusion coefficient has an activation energy of 2.83 kJ/mol. Rotational motion is facile within the alpha-cage. Translational motion is hindered during passage through the 12-ring window when C(4) is perpendicular to the window plane. Orientational correlation functions P(1) and P(2) around C(2), C(3) and C(4) are reported. Only the long time decay of C(4) shows oscillations. This is attributed to the hindered rotation during intercage migration while passing through the 12-ring window.     

Adsorption isotherm and other properties of methane in zeolite A from an intermolecular potential derived from ab initio calculations

A classical Lennard-Jones potential is derived from a fit to the ab initio energies obtained from an all-electron mixed-basis calculation for methane in zeolite LTA. The potential predicts the heat of adsorption, adsorption isotherm, and self-diffusivity of methane in excellent agreement with experiment. This study suggests, for the first time, that ab initio energies-in addition to experimental data-can form a good basis for derivation of accurate classical potentials between organic and inorganic elements.     

A tetrameric sugar-based azobenzene that gels water at various pH values and in the presence of salts

A novel low-molecular mass tetrameric sugar derivative containing azobenzene core, 1, showed pronounced hydrogelation at micromolar concentration. Based on this observation, four related azobenzene based tetrameric sugar derivatives, 4-7, and three tetrameric sugar derivatives with a bis-terephthalamide core, 9-11, were also synthesized. However, none of these closely related analogues of the compound 1 showed effective gelation. The gel formed from 1 was characterized extensively using melting temperature analysis, UV-vis, FT-IR, circular dichroism spectroscopy, and scanning electron microscopy. The resultant gel exhibited impressive tolerance to the pH variation of the aqueous phase and gelated water in the pH range of 4-10. While UV-vis and CD spectroscopy indicated that pronounced aggregation of the azobenzene chromophores in 1 was responsible for gelation, FT-IR studies showed that hydrogen bonding is also a contributing factor in the gelation process. The melting of gel was found to depend on the pH of the aqueous medium in which gel was formed. The gel showed considerable photostability to UV irradiation, indicating tight intermolecular packing inside the gelated state that rendered azobenzene groups in the resultant aggregate refractory to photoisomerization. The electron micrographs of the aqueous gels of 1 showed the existence of spongy globular aggregates in such gelated materials. Addition of salts to the aqueous medium led to a delay in the gelation process and also caused remarkable morphological changes in the microstructure of the gel.     

Organocatalytic,Enantioselective Synthesis of Cyclohexadienone Containing Hindered Spirocyclic Ethers through an Oxidative Dearomatization/Oxa‐Michael Addition Sequence

An unprecedented enantioselective oxa‐Michael reaction of α‐tertiary alcohols using cinchona‐alkaloid‐based chiral bifunctional squaramide catalysts is reported. An oxidative dearomatization of phenol followed by an enantioselective oxa‐Michael addition sequence provided a broad array of chiral sterically hindered tetrahydrofurans and tetrahydropyrans attached to a cyclohexadienone moiety in spiro fashion. In general, good yields and excellent enantioselectivities (up to 99 %) were observed. The chiral oxo‐cycles obtained have easily been transformed into chromans without disturbing the enantioselectivity.     

Diffusion in nanoporous phases: size dependence and levitation effect

Self-diffusivity, D, of diffusants in widely differing mediums such as liquids (e.g., solution), porous solids (e.g., guests in zeolites), or ions in polar solvents exhibit strong size dependence. We discuss the nature of the size dependence observed in these systems. Altogether, different theoretical approaches have been proposed to understand the nature of size dependence of D not only across these widely differing systems but even in just one medium or class of systems such as, for example, ions in polar solvents. But molecular dynamics investigations in the past decade have shown that the size dependence of self-diffusion in guest-porous solids could have origins in the mutual cancellation of forces that occurs when the size of the diffusant is comparable to the size of the void. The effect leading to the maximum in D is known as the levitation effect (LE). Such a cancellation is a consequence of symmetry. This effect exists in all porous solids irrespective of the geometrical and topological details of the pore network provided by the solid. Recent studies show that the levitation effect and size-dependent diffusivity maximum exists for uncharged solutes in solvents. One of the consequences of this is the breakdown in the Stokes-Einstein relationship over a certain range of solute-solvent size ratio. Experimental measurements of ionic conductivity over the past hundred years have found the existence of a size-dependent diffusivity maximum leading to violation of the Walden's rule for ions in polar solvents. Molecular dynamics simulations and experimental data suggest that even this maximum has its origin in LE. Simulation studies of impurity atom diffusion in close-packed solids as well as ions in superionic and other solids suggest the existence of a size-dependent diffusivity maximum in these materials as well. The levitation effect is a universal effect leading to a maximum in diffusivity of a diffusant in a variety of condensed matter phases. The only condition for its existence appears to be the presence of van der Waals or electrostatic interactions.     

Identification of molecular fingerprints of phenylindole derivatives as cytotoxic agents: a multi-QSAR approach

Phenylindole is reported to be an interesting scaffold having promising cytotoxic activities and can overcome the cancer drug resistance possibly via binding to the colchicine binding site of tubulin. In order to find out the molecular fingerprints for the better cytotoxic activity of phenylindole derivatives, multiple validated chemometric modeling approaches namely hologram QSAR (HQSAR), Bayesian classification model, and pharmacophore mapping analyses were applied into a dataset of 102 phenylindole derivatives. The final HQSAR model shows good statistical significance (Q²?=?0.760; R²_Train?=?0.868; R²_Test?=?0.660), and the best pharmacophore hypothesis has the highest regression coefficient value (r?=?0.975) and the lowest RMS value of 0.679. Moreover, the Bayesian model is also statistically validated and robust to discriminate the cytotoxic and non-cytotoxic phenylindoles. These studies suggest that the amine group should be unsubstituted for retaining higher cytotoxicity. The pharmacophore mapping and Bayesian classification study suggest the importance of 2-phenyl group as a ring aromatic feature conducive to cytotoxicity. The steric and hydrophobic effect of long chain linear alkyl group has a positive influence on cytotoxicity as evidenced by the multi-QSAR study. Therefore, this multi-QSAR modeling reported here is beneficial in designing potential phenylindole cytotoxic agents in future.     

Cinchonamine Squaramide Catalyzed Asymmetric aza‐Michael Reaction: Dihydroisoquinolines and Tetrahydropyridines

The first example of a chiral cinchona‐squaramide catalyzed enantioselective intramolecular aza‐Michael addition for the synthesis of dihydroisoquinolines and tetrahydropyridines has been developed. In general, good yields and excellent enantioselctivities were observed. Broad classes of Michael acceptors, such as enones, esters, thioesters, and Weinreb amides, were successful substrates. The possibility of recycling the catalysts has also been demonstrated. An oxidation of combined enamine and keto functionalities on chiral dihydroisoquinolines leads to a single diastereomer of an architecturally unprecedented tetracyclic core without loss in enantioselectivity.     

Organocatalytic,Enantioselective Synthesis of Cyclohexadienone Containing Hindered Spirocyclic Ethers through an Oxidative Dearomatization/Oxa‐Michael Addition Sequence

An unprecedented enantioselective oxa‐Michael reaction of α‐tertiary alcohols using cinchona‐alkaloid‐based chiral bifunctional squaramide catalysts is reported. An oxidative dearomatization of phenol followed by an enantioselective oxa‐Michael addition sequence provided a broad array of chiral sterically hindered tetrahydrofurans and tetrahydropyrans attached to a cyclohexadienone moiety in spiro fashion. In general, good yields and excellent enantioselectivities (up to 99 %) were observed. The chiral oxo‐cycles obtained have easily been transformed into chromans without disturbing the enantioselectivity.