Solid-supported solution-phase synthesis of 4-amino-1,2,4,5-tetrahydro-2-benzazepine-3-ones

Starting from Boc-o-aminomethylphenylalanine, a solution-phase parallel synthesis of 2,4-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepine-3-ones is described. This heterocycle has two nitrogen functions, which are differentiated and can be selectively substituted. The sources of diversity are aldehydes for the R(1) position and carboxylic acids, sulfonyl chlorides, or isocyanates for the R(2) position. High-throughput synthesis and purification of this multistep synthetic sequence was accomplished using polymer-bound reagents and scavengers and liquid-liquid extraction protocols, and a small library of compounds was prepared. Polymer-bound cyanoborohydride was found to work well for the reductive amination. Scavenging of excess of amine was performed by polymer-bound benzaldehyde, and cyclization was performed in the presence of polymer-bound coupling reagent 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC). After Boc-deprotection, the second nitrogen can be acylated using carboxylic acids, sulfonylated or converted to a urea. The acylation is again performed by polymer-bound EDC. Excellent yields and purities were obtained.     

Synthesis gas reactions on Pd-catalysts

Reactions of synthesis gas (CO/H₂) have been followed on a number of Pd-metal and Pd-alloy catalysts. Formation of methanol is sensitive to the choice of the carrier, but as the literature (and some of the data presented) is indicating, it is not proportional to the Pd-metal surface area. Alloying with Ag does not suppress methane formation substantially. It has been inferred from these results that methane is formed, at least partially, from an oxygen containing intermediate and that Pd ions play a role in the formation of these intermediates.

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Surface characterization of a cross‐linked cytochrome c film on cysteamine‐modified gold electrodes

The aim of the present paper is to characterize a cross‐linked horse heart cytochrome c (HHC) film on cysteamine‐modified gold electrodes. The HHC film was deposited using 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide (EDC) as a coupling agent. Attenuated total reflection infrared (ATR‐IR) spectroscopic analyses were performed to characterize the newly formed surface on a qualitative and conformational level. The film thickness was measured using a noncontact optical surface profiler, while quantitative data and information on the heterogeneity of the film were obtained by means of synchrotron radiation X‐ray micro fluorescence (SR micro‐XRF). Results indicate that, in addition to electrochemical studies, spectroscopic analysis methods are essential to gain insight in the effect of immobilization strategies on protein conformations. The latter is of relevance in the development and optimization of biosensors. Copyright © 2009 John Wiley & Sons, Ltd.     

Fourier transform laser microprobe mass spectrometry for the molecular identification of inorganic compounds

This study attempted to determine the molecular composition of inorganic analytes at the surface of solids by Fourier transform laser microprobe mass spectrometry (FT LMMS) with an external ion source. A database was established from the analysis of pure compounds. FT LMMS uses a similar ionization as the older LMMS instruments with time-of-flight (TOF) mass analyzer. However, apart from the mass resolution, the mass spectral patterns can be significantly different in FT LMMS compared to TOF LMMS. FT LMMS yields detailed information on the analyte by means of structural fragments, enabling us to specify the main building blocks, as well as adduct ions, consisting of the analyte molecule and a stable ion. Hence, deductive reasoning allows tentative characterization of the analogs without reference spectra, except for compounds with the same elements in different stoichiometries. In that case comparative data are needed.     

Block order restrictions in combinatorial electric energy auctions

In Europe, the auctions organized by “power exchanges” one day ahead of delivery are multi-unit, double-sided, uniformly priced combinatorial auctions. Generators, retailers, large consumers and traders participate at the demand as well as at the supply side, depending or whether they are short or long in electric energy. Because generators face nonconvex costs, in particular startup costs and minimum run levels, the exchanges allow “block orders” that are all-or-nothing orders of a given amount of electric energy in multiple consecutive hours, while the standard order consists of an amount for a single hour that can be curtailed. All exchanges restrict the size (MWh/h), the type (span in terms of hours) or the number (per participant per day) of blocks that can be introduced. This paper discusses the rationale of block order restrictions. Based on simulations with representative scenarios, it is argued that the restrictions could be relaxed, which some exchanges have already started doing.     

Vapor Phase Growth of Functional Pentacene Films at Atmospheric Pressure

Compared to traditional vacuum evaporation techniques for small organic molecules, organic vapor phase deposition (OVPD) possesses a extra processing parameter: the pressure of process gas P_ch. Here, the influence of large P_ch variations (from 0.1 mbar to atmospheric pressure) on pentacene thin film growth is explored. OVPD operation at higher P_ch is characterized by lower carrier gas velocities and lower organic diffusivities. These result in an invariance of the material utilization efficiency over the entire pressure span and in an advantageous equilibrium evaporation regime in the source. An increase in P_ch yields rough pentacene layers. Classical nucleation theory is applied to demonstrate how the pressure rise triggers homogeneous nucleation in the gas phase, causing the observed roughening. The use of lower deposition rates, higher dilution flow rates, and higher substrate temperatures result in the suppression of gas phase nucleation and the growth of smooth pentacene films at atmospheric pressure. Using these optimized conditions, state‐of‐the‐art pentacene thin film transistors with saturation mobilities above 0.9 cm²/Vs are reproducibly fabricated. p‐Type circuits are also made and a 19‐stage ring oscillator with a stage delay of 51 μs at a supply voltage of 15 V is demonstrated.     

Consistency of the preoperative and intraoperative diagnosis of benign vocal fold lesions

The purpose of this retrospective study was to compare the preoperative and intraoperative diagnosis of benign vocal fold lesions for consistency. The diagnosis was made in 221 consecutive patients with benign vocal fold lesions for which a microlaryngoscopy was carried out in a general ENT-clinic. The preoperative diagnosis was obtained by both white halogen and stroboscopic light. The intraoperative diagnosis was obtained by direct microscopic visualization and palpation of the vocal folds. In 36% of the patients, the preoperative diagnosis was changed intraoperatively. In 31% of the patients, a lesion was missed at the preoperative examination and a lesion was diagnosed only during microlaryngoscopy. Bilateral lesions were found in 53% of the patients preoperatively, and in 82% of the patients intraoperatively. Specially intracordal lesions constituted a diagnostic pitfall. Because the preoperative and intraoperative diagnosis often differed, both the patients and the ENT-surgeon must keep an open mind about what may need to be done at surgery.     

Wearable Self-Powered Electrochemical Devices for Continuous Health Management

The wearable revolution is already present in society through numerous gadgets. However, the contest remains in fully deployable wearable (bio)chemical sensing. Its use is constrained by the energy consumption which is provided by miniaturized batteries, limiting the autonomy of the device. Hence, the combination of materials and engineering efforts to develop sustainable energy management is paramount in the next generation of wearable self-powered electrochemical devices (WeSPEDs). In this direction, this review highlights for the first time the incorporation of innovative energy harvesting technologies with top-notch wearable self-powered sensors and low-powered electrochemical sensors toward battery-free and self-sustainable devices for health and wellbeing management. First, current elements such as wearable designs, electrochemical sensors, energy harvesters and storage, and user interfaces that conform WeSPEDs are depicted. Importantly, the bottlenecks in the development of WeSPEDs from an analytical perspective, product side, and power needs are carefully addressed. Subsequently, energy harvesting opportunities to power wearable electrochemical sensors are discussed. Finally, key findings that will enable the next generation of wearable devices are proposed. Overall, this review aims to bring new strategies for an energy-balanced deployment of WeSPEDs for successful monitoring of (bio)chemical parameters of the body toward personalized, predictive, and importantly, preventive healthcare.     

Potentiometric detection of organic acids in liquid chromatography using polymeric liquid membrane electrodes incorporating macrocyclic hexaamines

Potentiometric detection employing coated-wire electrodes was applied to the determination of organic acids in liquid chromatography (LC). Poly(vinyl chloride)-based liquid membranes, incorporating lipophilic macrocyclic hexaamines as neutral ionophores were used as electrode coatings. The selectivity and sensitivity of the macrocycle-based electrodes were found to be superior to an electrode based on a lipophilic anion exchanger (a quaternary ammonium salt). Sensitive detection was obtained for the di- and tricarboxylic acids tartaric, malonic, malic, citric, fumaric, succinic, pyruvic, 2-oxoglutaric and maleic acids after separation in reversed-phase LC. Detection limits (signal/4sigmanoise=3) of 6 pmol for malonic acid and 2 pmol for maleic acid were attained. The detection was explained using a molecular recognition model. The hexaamine-based potentiometric electrodes had a 1-s response time at 1 ml min(-1) flow-rates. They were stable for at least 4 months, with an intra-electrode variation of 3.2% (n=5).     

An experimental study on the effect of ad placement,product involvement and motives on Facebook ad avoidance

Facebook users do not visit the social networking site to see advertising. They are either just surfing the platform or searching for information. Therefore, advertising content is vulnerable to ad avoidance. In this study, the effect of two Facebook ad placements, sidebar ads and message stream ads, on ad avoidance intention was investigated through an online experiment. Sidebar placements are put next to the content stream, while message stream advertising is interwoven with the original Facebook content. 253 Respondents (M_age?=?39.4, SD?=?8.7, 50.2% female) were given either a searching or surfing task. The intention of respondents to avoid ads placed in the message stream was significantly higher than to avoid ads placed in the sidebar. Through multiple moderation analysis, we found that Facebook motivations and product involvement were significant moderators of the effect of ad placement on ad avoidance intent. Our results point to the crucial role of the degree of product involvement when targeting Facebook ads to the right audience and choosing the appropriate ad placement. We discussed implications for research and the professional field.