Hydrophobicity and drag reduction properties of surfaces coated with silica aerogels and xerogels

Superhydrophobic surfaces have application in self-cleaning, anti-fouling and drag reduction. Most superhydrophobic surfaces are constructed using complex fabrication methods. An alternative method is to use sol–gel methods to make hydrophobic aerogel and xerogel surfaces. In this work, hydrophobic silica aerogels and xerogels were made from the silica precursors tetramethoxysilane (TMOS) and methyltrimethoxysilane (MTMS) in volume ratios MTMS/TMOS of 0–75 % using a base-catalyzed recipe. Overall hydrophobicity was assessed using contact angle measurements on surfaces prepared from crushed aerogel and xerogel powders. The surfaces made from aerogels were super-hydrophobic (with contact angles of 167°–170°) for all levels of MTMS (10–75 %). Of the xerogel-coated surfaces, those made with 50 % MTMS were hydrophobic and with 75 % MTMS were superhydrophobic. Chemical hydrophobicity was assessed using Fourier transform infrared spectroscopy, which showed evidence of Si–CH₃ and Si–C bonds in the aerogels and xerogels made with MTMS. Morphological hydrophobicity was assessed using SEM imaging and gas adsorption. The drag characteristics of the aerogel- and xerogel-coated surfaces were measured using a rotational viscometer. Under laminar flow conditions all of the hydrophobic aerogel-coated surfaces (10–75 % MTMS) were capable of capturing an air bubble, thereby reducing the drag on a horizontal rotating surface by 20–30 %. Of the xerogel-coated surfaces, only the one made from 75 % MTMS could capture a bubble, which led to 27 % drag reduction. These results imply that morphological differences between silica aerogels and xerogels, rather than any differences in their chemical hydrophobicity, give rise to the observed differences in hydrophobicity and drag reduction for the sol–gel-coated surfaces.     

A Highly Convergent Synthesis of 2‐Phenyl Quinoline as Dual Antagonists for NK2 and NK3 Receptors

A novel and highly convergent synthesis leading to 2‐phenyl‐quinolines has been developed. As demonstrated in the preparation of 6‐fluoro‐3‐(3‐oxo‐piperazin‐1‐ylmethyl)‐2‐phenyl‐quinoline‐4‐carboxylic acid [(S)‐1‐cyclohexyl‐ethyl]‐amide (8), the method provides fascile access to this class of analogues via the common intermediate 7.     

Crotofolane‐ and Casbane‐Type Diterpenes from Croton argyrophyllus

Phytochemical analysis of Croton argyrophyllus led to the isolation of five new diterpenes named (5β,6β)‐5,6 : 13,16‐diepoxycrotofola‐4(9),10(18),13,15‐tetraen‐1‐one ( 1 ), (5β,6β)‐5,6 : 13,16‐diepoxy‐2‐epicrotofola‐4(9),10(18),13,15‐tetraen‐1‐one ( 2 ), (5β,6β)‐5,6 : 13,16‐diepoxy‐16‐hydroxy‐2‐epicrotofola‐4(9),10(18),13,15‐tetraen‐1‐one ( 3 ), (5β,6β)‐5,6 : 13,16‐diepoxy‐16‐hydroxy‐2‐epicrotofola‐4(9), 10(18),13,15‐tetraen‐1‐one ( 4 ) and (2E,5β,6E,12E)‐5‐hydroxycasba‐2,6,12‐trien‐4‐one ( 5 ), in addition to the known diterpenes crotonepetin and depressin, and acetylaleuritolic acid and spinasterol. The structures of the isolated compounds were established by a combination of spectroscopic methods, including HR‐ESI‐MS, 2D‐NMR, and X‐ray crystallography.     

Access to Indoles via Diels–Alder Reactions of 5‐Methylthio‐2‐vinylpyrroles with Maleimides

Diels–Alder reactions of 5‐methylthio‐2‐vinyl‐1H‐pyrroles with maleimides followed by isomerization gave tetrahydroindoles in moderate to good yield. Aromatization using activated MnO₂ in refluxing toluene gave the corresponding 2‐methylthioindoles in good yields, and demethylthioation using Raney nickel gave the 2‐H indoles in excellent yields. The protection of the adducts produced aromatization in improved yield, demonstrating the effectiveness of the methylthio group as a protecting group for pyrroles; however, 5‐methylthio‐2‐vinylpyrrole was shown to perform with slightly less efficiency than 2‐vinylpyrrole in Diels–Alder reactions, indicating the protective group was more deactivating than desired. This route toward indoles offers high convergency and conveniently available starting materials that are easily purified. Bis‐methylthioated vinylpyrroles were shown to have potential as highly activated Diels–Alder dienes.     

A Remarkable Synthesis of the Bicyclo[4.2.1]Nonenedione System

Allylation of the C-2 enolate of the bicyclo[3.3.1]nonenedione 1 proceeds with an unusual acyl migration to yield the C-allyl ester 5 of the rearranged bicyclo[4.2.1]nonenedione system.     

Hydrodynamic Models and Confinement Effects by Horizontal Boundaries

Confinement effects by rigid boundaries in the dynamics of ideal fluids are considered from the perspective of long-wave models and their parent Euler systems, with the focus on the consequences of establishing contacts of material surfaces with the confining boundaries. When contact happens, we show that the model evolution can lead to the dependent variables developing singularities in finite time. The conditions and the nature of these singularities are illustrated in several cases, progressing from a single-layer homogeneous fluid with a constant-pressure free surface and flat bottom, to the case of a two-fluid system contained between two horizontal rigid plates, and finally, through numerical simulations, to the full Euler stratified system. These demonstrate the qualitative and quantitative predictions of the models within a set of examples chosen to illustrate the theoretical results.

     

1,3‐Dimethyl­isoguanine

The structure of 1,3‐dimethyl­isoguanine [or 6‐amino‐1,3‐dimethyl‐1H‐purin‐2(3H)‐one], C₇H₉N₅O, has been redetermined and the correct assignment of H atoms on the heterocycle is now reported. Inter­molecular hydrogen‐bonding inter­actions confirm that this form is the correct mol­ecular structure; this form is also in agreement with an earlier reported structure of the trihydrate form.     

Muonium and micelles

A pseudo first-order term has been added to the kinetic analysis of micelle-mediated muonium reactions. It is discussed with respect to enhancements of several orders of magnitude for reactions such as that of 2-propanol. It covers the possibility of ‘trapping’ of muonium followed by tunneling.