Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes

Reactions of LAl with ethyne, mono- and disubstituted alkynes, and diyne to aluminacyclopropene LAl[eta2-C2(R1)(R2)] ((L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3); R1 = R2 = H, (1); R1 = H, R2 = Ph, (2); R1 = R2 = Me, (3); R1 = SiMe3, R2 = C[triple bond]CSiMe3, (4)) are reported. Compounds 1 and 2 were obtained in equimolar quantities of the starting materials at low temperature. The amount of C2H2 was controlled by removing an excess of C2H2 in the range from -78 to -50 degrees C. Compound 4 can be alternatively prepared by the substitution reaction of LAl[eta2-C2(SiMe3)2] with Me3SiC[triple bond]CC[triple bond]CSiMe3 or by the reductive coupling reaction of LAlI2 with potassium in the presence of Me3SiC[triple bond]CC[triple bond]CSiMe3. The reaction of LAl with excess C2H2 and PhC[triple bond]CH (<1:2) afforded the respective alkenylalkynylaluminum compounds LAl(CH=CH2)(C[triple bond]CH) (5) and LAl(CH=CHPh)(C[triple bond]CPh) (6). The reaction of LAl(eta2-C2Ph2) with C2H2 and PhC[triple bond]CH yielded LAl(CPh=CHPh)(C[triple bond]CH) (7) and LAl(CPh=CHPh)(C[triple bond]CPh) (8), respectively. Rationally, the formation of 5 (or 6) may proceed through the corresponding precursor 1 (or 2). The theoretical studies based on DFT calculations show that an interaction between the Al(I) center and the C[triple bond]C unit needs almost no activation energy. Within the AlC2 ring the computational Al-C bond order of ca. 1 suggests an Al-C sigma bond and therefore less pi electron delocalization over the AlC2 ring. The computed Al-eta2-C2 bond dissociation energies (155-82.6 kJ/mol) indicate a remarkable reactivity of aluminacyclopropene species. Finally, the 1H NMR spectroscopy monitored reaction of LAl(eta2-C2Ph2) and PhC[triple bond]CH in toluene-d8 may reveal an acetylenic hydrogen migration process.     

Effect of counterions on the activity of lipase in cationic water-in-oil microemulsions

This paper delineates how the different counterions affect the physicochemical properties of the aqueous aggregates and thereby the lipase activities at the interface of cationic water-in-oil microemulsions. To this end, we have synthesized a series of cetyltrimethylammonium-based surfactants, 1-14, having aliphatic, aliphatic with aromatic substitution at the alpha position, and aromatic carboxylate anion as the counterion. The physicochemical characterizations of these aqueous aggregates were done by conductometric, tensiometric, fluorometric techniques to determine counterion binding (beta), critical micelle concentration (cmc), and micropolarity at the microenvironment. It has been found that the activity of lipase mainly increases with hydrophobicity (which is directly proportional to the counterion binding (beta) of the surfactant) of the counterion and reaches a maximum when the beta value is around 0.5. Increase in hydrophobicity as well as beta leads to the attachment of more counterions at interface resulting in enhancement of interfacial area. Consequently, the enzyme may attain flexible secondary conformation at the augmented surface area and also allow larger population of substrates and enzyme molecules at the interface leading to the enhancement in lipase activity. After an optimum value of beta, further increase probably produces a steric crowding at the interface, hindering the smooth occupancy of enzyme and the substrate in this region leading to decrease of enzyme activity, while molecular surface area of the counterion did not show any virtual influence on the lipase activity. Thus, the variation in the counterion structure and hydrophobicity plays a crucial role in modulating the lipase activity.     

Study of electrolyte induced aggregation of gold nanoparticles capped by amino acids

This work reports the electrolyte induced aggregation of gold nanoparticles directly conjugated to amino acid by chemical reduction in aqueous solution. The study was focused on three different classes of amino acids depending on the nature of alpha substituent, viz. l-cysteine, l-leucine, and l-asparagine. The band broadening and the red shift of surface plasmon band with increase in flocculation parameter showed the aggregation of gold nanoparticles with increase in electrolyte concentration and decrease in pH as monitored by UV-visible spectrophotometer. The (1)H NMR spectrum demonstrates that the sulfide bond of cysteine and alpha amino group of leucine and asparagine interact with nanoparticles surface. Furthermore, transmission electron microscope (TEM) and thermogravimetric analysis (TGA) were performed to characterize and to support the fate of stabilization of the gold nanoparticles by amino acid.     

Synthesis of the proposed structure of mucoxin via regio- and stereoselective tetrahydrofuran ring-forming strategies

An enantioselective total synthesis of the proposed structure of mucoxin (1) is described. Mucoxin, an annonaceous acetogenin isolated from bioactive leaf extracts of Rollinia mucosa, is the first acetogenin containing a hydroxylated trisubstituted tetrahydrofuran (THF) ring. This natural product is a highly potent and specific antitumor agent against MCF-7 (breast carcinoma) cell lines (ED50 = 3.7 x 10(-3) microg/mL compared to adriamycin, ED50 = 1.0 x 10(-2) microg/mL). The total synthesis described herein features two regio- and stereoselective THF ring-forming reactions. The 2,3,5-trisubstituted THF portion (C13-C17) was accessed using a highly regioselective cyclization of a methylene-interrupted epoxydiol, and the 2,5-disubstituted THF ring (C8-C12) was conveniently assembled via a 1,2-n-triol cyclization strategy. The spectral data of the synthetic material and two of its diastereomers did not match the reported data for the natural product. On the basis of detailed spectroscopic analysis of the synthesized molecule, we reason that the spectral discrepancies are due to stereochemical misassignment of the natural product.     

JKR adhesion in cylindrical contacts

Planar JKR adhesive solutions use the half-plane assumption and do not permit calculation of indenter approach or visualization of adhesive force–displacement curves unless the contact is periodic. By considering a conforming cylindrical contact and using an arc crack analogy, we obtain closed-form indenter approach and load–contact size relations for a planar adhesive problem. The contact pressure distribution is also obtained in closed-form. The solutions reduce to known cases in both the adhesion-free and small-contact solution (Barquins, 1988) limits. The cylindrical system shows two distinct regimes of adhesive behavior; in particular, contact sizes exceeding the critical (maximum) size seen in adhesionless contacts are possible. The effects of contact confinement on adhesive behavior are investigated. Some special cases are considered, including contact with an initial neat-fit and the detachment of a rubbery cylinder from a rigid cradle. A comparison of the cylindrical solution with the half-plane adhesive solution is carried out, and it indicates that the latter typically underestimates the adherence force. The cylindrical adhesive system is novel in that it possesses stable contact states that may not be attained even on applying an infinite load in the absence of adhesion.     

Conformally flat collapsing stars in <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>) gravity

The present work includes an analytical investigation of a collapsing spherical star in f(R) gravity. The interior of the collapsing star admits a conformal flatness. Information regarding the fate of the collapse is extracted from the matching conditions of the extrinsic curvature and the Ricci curvature scalar across the boundary hypersurface of the star. The radial distribution of the physical quantities such as density, anisotropic pressure and radial heat flux are studied. The inhomogeneity of the collapsing interior leads to a non-zero acceleration. The divergence of this acceleration and the loss of energy through a heat conduction forces the rate of the collapse to die down and the formation of a zero proper volume singularity is realized only asymptotically.     

A Total Measure of Multi-Particle Quantum Correlations in Atomic Schrödinger Cat States

We propose a total measure of multi-particle quantum correlation in a system of N two-level atoms (N qubits). We construct a parameter that encompasses all possible quantum correlations among N two-level atoms in arbitrary symmetric pure states and define its numerical value to be the total measure of the net atom-atom correlations. We use that parameter to quantify the total quantum correlations in atomic Schrödinger cat states, which are generated by the dispersive interaction in a cavity. We study the variation of the net amount of quantum correlation as we vary the number of atoms from N=2 to N=100 and obtain some interesting results. We also study the variation of the net correlation, for fixed interaction time, as we increase the number of atoms in the excited state of the initial system, and notice some interesting features. We also observe the behaviour of the net quantum correlation as we continuously increase the interaction time, for the general state of N two-level atoms in a dispersive cavity.     

QM/MM study of the interaction between zigzag SnC nanotube and small toxic gas molecules

Adsorptions of small toxic molecules such as CO, N₂, HCN, SO₂, H₂CO, and NH₃ on a single‐walled (6,0) SnC nanotube (SnCNT) are investigated using Quantum Mechanics/Molecular Mechanics (QM/MM) methodology. The calculations are carried out at the B3LYP/6‐311++G(d,p)//LANL2DZ:UFF level of theory. The high layer of the model consists of a pyrene‐type ring on the nanotube surface as the adsorption site, where one gas molecule is allowed to interact. Conversely, for the adsorption of the two molecules, a larger site like a coronene ring is used for the high layer. Adsorption energy, Gibbs free energy change, Mulliken charge transfer, and total electron‐density maps are computed in each case. The adsorption strength of the gas molecule on the SnCNT surface is also analyzed from the density of states projected to different atoms (PDOS) of the nanotube–adsorbate complexes. The adsorptions of CO and N₂ on the (6,0) SnCNT surface require to cross potential barriers, and the corresponding transition structures are identified by ONIOM‐IRC calculations. For the remaining four molecules, the processes of adsorption are predicted to be barrier‐less. The calculations for the adsorption of H₂CO on (5,0) and (7,0) SnCNT surfaces are extended to study the effect of the size of the nanotube. Results for the adsorption of a single molecule on (6,0) SnCNT using B3LYP functional are compared with those obtained from a dispersion corrected functional such as M06‐2X. © 2015 Wiley Periodicals, Inc.     

ortho‐Phenylenediamine: An Effective Spacer to Build Highly Magnetic Fe3O4/Au Nanocomposites

1,2‐Diaminobenzene, popularly known as ortho‐phenylenediamine (PDA), is found to be a prototype spacer for the deposition of gold nanoparticles on the surfaces of Fe₃O₄ microspheres. Upon carbonization with PDA, the morphology of the product changes significantly, and the resulting nanocomposites exhibit enhanced magnetism beyond the saturation value of Fe₃O₄. The Fe₃O₄/Au nanocomposites show good surface‐enhanced Raman spectroscopy activity with a detection limit of 10^?15 M .     

Spatial arrangement of carbon nanotubes in TiO2 photoelectrodes to enhance the efficiency of dye-sensitized solar cells

Three electrode structures with different spatial arrangements of carbon nanotubes (CNTs) in the mesoporous TiO(2) layer were employed in dye-sensitized solar cells to study the effect of surface states at the interface formed by the incorporation of CNTs. It was found that the decay of open circuit voltage (V(oc)) was significantly minimized by avoiding the direct contact of nanotubes to the conducting substrate by introducing a thin buffer layer of TiO(2) while maintaining the superior electron collection efficiency from the incorporation of nanotubes.