Incorporation of an allene unit into 1,4-dihydronaphthalene: generation of 1,2-benzo-1,4,5-cycloheptatriene and its dimerization

1-Bromo-1-fluoro-[1a,2,7,7a]-tetrahydro-1H-cyclopropa[b]naphthalene (19) has been prepared by the addition of bromofluorocarbene to 1,4-dihydronaphthalene (18). Treatment of a solution of 19 in dry ether with MeLi afforded the tricyclic hydrocarbon 17, resulting from the intramolecular C-H insertion of carbene 16, and two dimerization products, the head-to-head 20 and head-to-tail 21 allene dimers, confirming the formation of title cycloallene 15 as a reactive intermediate. B3LYP/6-31G(d) calculation predicts the activation barriers for insertion product 17 and allene product 15 as 3.70 and 9.52 kcal/mol, respectively. This prediction was in good agreement with our experimental results.     

Structural and rate studies of the 1,2-additions of lithium phenylacetylide to lithiated quinazolinones: influence of mixed aggregates on the reaction mechanism

The 1,2-addition of lithium phenylacetylide (PhCCLi) to quinazolinones was investigated using a combination of structural and rate studies. (6)Li, (13)C, and (19)F NMR spectroscopies show that deprotonation of quinazolinones and phenylacetylene in THF/pentane solutions with lithium hexamethyldisilazide affords a mixture of lithium quinazolinide/PhCCLi mixed dimer and mixed tetramer along with PhCCLi dimer. Although the mixed tetramer dominates at high mixed aggregate concentrations and low temperatures used for the structural studies, the mixed dimer is the dominant form at the low total mixed aggregate concentrations, high THF concentrations, and ambient temperatures used to investigate the 1,2-addition. Monitoring the reaction rates using (19)F NMR spectroscopy revealed a first-order dependence on mixed dimer, a zeroth-order dependence on THF, and a half-order dependence on the PhCCLi concentration. The rate law is consistent with the addition of a disolvated PhCCLi monomer to the mixed dimer. Investigation of the 1,2-addition of PhCCLi to an O-protected quinazolinone implicates reaction via trisolvated PhCCLi monomers.     

Adhesion of biologically inspired vertical and angled polymer microfiber arrays

This paper proposes an approximate adhesion model for fibrillar adhesives for developing a fibrillar adhesive design methodology and compares numerical simulation adhesion results with macroscale adhesion data from polymer microfiber array experiments. A technique for fabricating microfibers with a controlled angle is described for the first time. Polyurethane microfibers with different hardnesses, angles, and aspect ratios are fabricated using optical lithography and polymer micromolding techniques and tested with a custom tensile adhesion measurement setup. Macroscale adhesion and overall work of adhesion of the microfiber arrays are measured and compared with the models to observe the effect of fiber geometry and preload. The adhesion strength and work of adhesion behavior of short and long vertical and long angled fiber arrays have similar trends with the numerical simulations. A scheme is also proposed to aid in optimized fiber adhesive design.     

Infrared multiphoton excitation of small molecules

The collisionless infrared excitation by short CO₂ laser pulses of the molecules SO₂, OCS, NO₂, NH₃ and DN₃ is compared with that of larger molecules. The average number of photons absorbed per molecule and the fraction of molecules dissociated depends predominantly on the laser intensity, while for larger molecules with higher densities of vibrational states the excitation is primarily determined by the laser fluence.     

Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Optimization of Microwave-Assisted Extraction (MAE) for the Isolation of Antioxidants from Basil (Ocimum basilicum L.) by Response Surface Methodology (RSM)

Abstract

The recovery of antioxidants from basil (Ocimum basilicum L.) was modeled with the aid of response surface methodology (RSM) using microwave-assisted extraction (MAE). Face-centered central design (FCCD) was employed to optimize the MAE operational parameters including the extraction time (1 to 7?min), extraction temperature (30 to 120?°C), solid-to-solvent ratio (0.1 to 0.4), and solvent concentration (20 to 80% ethanol, v/v), and to obtain the best possible combinations of these parameters for a high antioxidant yield from basil. The total antioxidant capacity (TAC) was expressed in trolox (TR) equivalents per gram of dried sample (DS). Three of the operational parameters (temperature, extraction time and solvent concentration) were shown to have significant effect on the extraction efficiency of antioxidants in basil extracts (p?<?0.05). The solvent concentration was shown to be the most significant factor on antioxidant yield obtained by MAE. There was a close relationship between experimental and predicted values using the proposed method. This optimized MAE method shows an application potential for the efficient extraction of antioxidants from basil in the food and pharmaceutical industries.     

Segmental dynamics in poly(methyl acrylate) on silica: molecular-mass effects

The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the polymer-air interface and the less-mobile species near the polymer-silica interface. The mobility of the adsorbed 77 kDa PMA sample was the lowest among the four different molecular-mass samples studied. Samples studied with masses both larger and smaller than 77 kDa had larger mobile-component fractions in the adsorbed polymer. The additional mobility was attributed to the presence of either longer tail and loop conformations in the higher molecular-mass samples or the inherent mobility of the tails in the lower molecular-mass samples on the surface.     

Superelastic percolation network of polyacrylamide (PAAm)–kappa carrageenan (κC) composite

The elasticity of the polyacrylamide (PAAm)-kappa carrageenan (κC) composite was determined as a function of (w/v-%) κC content at 40 °C. The gel composites studied contained various percentages (w/v-%) of κC. The elasticity of the swollen PAAm-κC composite was characterized by using the tensile testing technique. This study investigated the elasticity and the percolation threshold of PAAm-κC composite as a function of κC content. It is understood that the compressive elastic modulus decreases up to 1 (w/v-%) of κC and then increases at contents above 1(w/v-%) of κC. The critical exponent of elasticity y was determined between 1 and 1.6 (w/v-%) of κC and found to be 0.68. The observed elastic percolation threshold is consistent with the suggested values of the superelastic percolation network.     

Infinitely many singular interactions on noncompact manifolds

We show that the ground state energy is bounded from below when there are infinitely many attractive delta function potentials placed in arbitrary locations, while all being separated at least by a minimum distance, on two dimensional non-compact manifold. To facilitate the reading of the paper, we first present the arguments in the setting of Cartan–Hadamard manifolds and then subsequently discuss the general case. For this purpose, we employ the heat kernel techniques as well as some comparison theorems of Riemannian geometry, thus generalizing the arguments in the flat case following the approach presented in Albeverio et al. (2004).