Monitoring of liquid flow through microtubes using a micropressure sensor

The pressure-driven liquid flow through microtubes was studied in a range of very low Reynolds numbers (<0.15) by monitoring the pressure change in situ. Cylindrical microtubes with diameters ranging from 50 ?m to 500 ?m were examined and two types of tube material, namely PEEK polymer and fused silica were compared. A good linear relation for the pressure drop versus flow rate was obtained. Apparent deviations between the measured slopes with those calculated using conventional theory were attributed to uncertainties in the calculated values which are dominated by the uncertainties in the microtube diameters. It was found that a period of stabilisation time was required for reaching a steady flow after the syringe pump was switched on/off or to a different flow rate. The stabilisation time was likely due to the compressibility of the fluid. Insignificant difference between PEEK polymer and fused silica microtubes in terms of flow resistance was observed. The in-situ measurement of pressure drops provides a convenient approach for monitoring fluid flow through microtubes and detecting dimensional changes within microchannels in Lab-on-a-Chip and microreactor systems

Chelation enables selectivity control in enantioconvergent Suzuki–Miyaura cross-couplings on acyclic allylic systems

Asymmetric Suzuki–Miyaura cross-couplings with aryl boronic acids and allylic electrophiles are a powerful method to convert racemic mixtures into enantioenriched products. Currently, enantioconvergent allylic arylations are limited to substrates that are symmetrical about the allylic unit, and the absence of strategies to control regio-, E/Z- and enantioselectivity in acyclic allylic systems is a major restriction. Here, using a system capable of either conjugate addition or allylic arylation, we have discovered the structural features and experimental conditions that allow an acyclic system to undergo chemo- and regioselective, enantioconvergent allylic Suzuki–Miyaura-type arylation. A wide variety of boronic acid coupling partners can be used, and both alkyl and aromatic substituents are tolerated on the allylic unit so that a wide variety of structures can be obtained. Preliminary mechanistic studies reveal that the chelating ability of the ester group is crucial to obtaining high regio- and enantioselectivity. Using this method, we were able to synthesize the natural products (S)-curcumene and (S)-4,7-dimethyl-1-tetralone and the clinically used antidepressant sertraline (Zoloft)

Poly(bisphenol) polymers as passivating agents for carbon electrodes in ionic liquids

Poly(bisphenol) polymers are identified as a new class of passivating agents for carbon electrodes in ionic liquids. They are inert and can readily be deposited as thin, conformal films by electropolymerization. Unlike conventional poly(monophenol) polymers, a single voltammetric scan is sufficient to accomplish their deposition. This is seen, for example, in the cases of poly(bisphenol A) and poly(bisphenol P). In each case, the thickness of the electropolymerized films is determined by the quantum tunneling distance of the faradaic electrons. Thus, film growth terminates when the faradaic electrons can no longer transit the film at a measurable rate. At that point, all the faradaic reactions cease, while the capacitive charging processes continue unabated. Experimentally, film thicknesses are observed in the range 4–30 nm. A challenging test for the poly(bisphenol) polymers is to coat them onto arrays of microelectrodes (RAM electrodes). Normally, microelectrodes are difficult to coat by electropolymerization due to the intense flux of soluble intermediates away from their surfaces. In the present work, however, coating is facile due to the extreme insolubility of the intermediates. This same property makes the films strongly adherent. Such remarkable behavior suggest that poly(bisphenol) films may have an important role to play as passivating agents in supercapacitors. They may also find application in other areas of technology that require thin-film passivity, such as nanostructural engineering and device physics

Supercatalysis by superexchange

In modern transition state theory, the rate constant for an electron transfer reaction is expressed as the product of four factors: an exponential factor, a pre-exponential factor, an electronic transmission coefficient, and a nuclear transmission coefficient. The activation energy of the reaction manifests inside the exponential factor, and on the conventional view, catalysis occurs by decreasing this activation energy below its catalyst-free value. In the present work we report the discovery of an unusual counter-example in which catalysis occurs by increasing the electron transmission coefficient far above its catalyst-free value. The mechanism involves the formation of a superexchange bridge between an electron donor (a graphite cathode) and an electron acceptor (a pentasulfide ion). The bridge consists of a dz2 orbital inside a cobalt phthalocyanine molecule. The dramatic result is the acceleration of the reduction of pentasulfide ions by more than 5 orders of magnitude compared with the catalyst-free case

A universal equivalent circuit for carbon-based supercapacitors

A universal equivalent circuit is proposed for carbon-based supercapacitors. The circuit, which actually applies to all porous electrodes having non-branching pores, consists of a single vertical ladder network in series with an RC parallel network. This elegant arrangement explains the three most important shortcomings of present-day supercapacitors, namely open circuit voltage decay, capacitance loss at high frequency, and voltammetric distortion at high scan rate. It also explains the shape of the complex plane impedance plots of commercial devices and reveals why the equivalent series capacitance increases with temperature. Finally, the construction of a solid-state supercapacitor simulator is described. This device is based on a truncated version of the universal equivalent circuit, and it allows experimenters to explore the responses of different supercapacitor designs without having to modify real supercapacitors

Are short-term variations in solar oscillation frequencies the signature of a second solar dynamo?

In addition to the well-known 11-year solar cycle, the Sun's magnetic activity also shows significant variation on shorter time scales, e.g. between one and two years. We observe a quasi-biennial (2-year) signal in the solar p-mode oscillation frequencies, which are sensitive probes of the solar interior. The signal is visible in Sun-as-a-star data observed by different instruments and here we describe the results obtained using BiSON, GOLF, and VIRGO data. Our results imply that the 2-year signal is susceptible to the influence of the main 11-year solar cycle. However, the source of the signal appears to be separate from that of the 11-year cycle. We speculate as to whether it might be the signature of a second dynamo, located in the region of near-surface rotational shear.Comment: 6 pages, 2 figures, proceedings for SOHO-24/GONG 2010 conference, to be published in JPC