Optical studies of dynamic director configurations in ferroelectric liquid crystal devices

An investigation into the transmission spectrum of a ferroelectric liquid crystal device is undertaken. This is done both for an initial static state and during a switching process. Comparisons are made between experimental data and theoretical predictions. The dynamic internal director configurations in the device is shown to be consistent with a simple model during both monopolar and bipolar addressing pulses.     

Trapped in Misbelief for Almost 40 Years: Selective Synthesis of the Four Stereoisomers of Mefloquine

Here we report the synthesis of all four stereoisomers of mefloquine. Mefloquine (Lariam) is an important anti‐malaria drug that is applied as a racemate of the erythro form. However, the (?)‐isomer induces psychosis, while the (+)‐enantiomer does not have this undesired side effect. There are six syntheses of which five lead to the wrong enantiomer without the authors of these syntheses noting that they had synthesized the wrong compound. At the same time physical chemistry investigations had assigned the absolute configuration correctly and the last enantioselective synthesis that took these results into account delivered the correct absolute configuration. Since various synthetic approaches failed to provide the correct stereoisomers in previous syntheses, we submit here a synthetic approach with a domino Sonogashira‐6π‐electrocyclisation as key step that confirmed synthetically the correct absolute configuration of all four isomers.     

钒钼协同作用下杂多酸催化阻聚甲基丙烯酸甲酯

利用一锅法制备了Dawson型钨磷酸和钼钒磷酸,并用红外光谱和X-射线衍射表征了其结构.采用沸腾法研究了合成的杂多酸对甲基丙烯酸甲酯(MMA)的催化阻聚性能,考察了杂多酸结构、杂多酸用量和反应温度等因素对MMA本体聚合反应的影响.结果表明:钒钼元素在杂多酸催化阻聚MMA的反应中具有明显的协同作用,而且,杂多酸对MMA的催化阻聚作用随钒原子数的增加而增强,杂多酸的用量和反应温度对MMA自聚反应的速率影响较大.在过氧化苯甲酰(BPO)为0.04 g,MMA为10 mL,H9P2Mo15V3O62质量为MMA的0.06%,反应温度为101.2℃或H9P2Mo15V3O62质量为MMA的0.03%,反应温度为89.4℃时,MMA自聚反应被抑制.与传统和常用酚阻聚剂相比,Dawson型钼钒磷酸具有阻聚效果好、后处理简单、无腐蚀和污染问题等优点,能够作为MMA的阻聚剂使用.     

Divergent synthesis of 6H-isoindolo[2,1-a]indol-6-ones and indenoindolones: an investigation of Pd-catalyzed isocyanide insertion

A novel Pd-catalyzed intramolecular cyclization via tert-butyl isocyanide insertion from 2-(2-bromophenyl)-1H-indoles has been developed, which demonstrates the utility of isocyanides in C–N or C–C bond construction. Treatment of 2-(2-bromophenyl)-1H-indoles with tert-butyl isocyanide affords 6H-isoindolo[2,1-a]indol-6-ones with high efficiency. However, N-methyl or N-Boc protected 2-(2-bromophenyl)-1H-indoles gives indenoindolones in excellent yields under the same condition, which reveals that under the described situation, isocyanides insertion for the formation of C–N bonds is prior to that of C–C bonds.     

FRET based selective and ratiometric ‘naked-eye’ detection of CN in aqueous solution on fluorescein–Zn–naphthalene ensemble platform

We have developed a FRET-based ratiometric fluorescent probe for the detection of CN⁻ using a fluorescein–Zn–naphthalene ensemble (NFH·Zn²⁺). The sensing mechanism was ascribed by displacement approach. The chemosensor exhibits high selectivity and sensibility for CN⁻. The speculation was supported by fluorescence emission spectra, UV–vis spectrum, ¹H NMR titration experiments, and mass spectra. The interconversion of probe NFH and NFH·Zn²⁺ via the complexation/decomplexation by the modulation of Zn²⁺/CN⁻ mimics INHIBIT gate. In addition, it also shows an excellent performance in ‘dip stick’ method.     

Quality by design: A systematic and rapid liquid chromatography and mass spectrometry method for eprosartan mesylate and its related impurities using a superficially porous particle column

The present work describes the systematic development of a robust, precise, and rapid reversed‐phase liquid chromatography method for the simultaneous determination of eprosartan mesylate and its six impurities using quality‐by‐design principles. The method was developed in two phases, screening and optimization. During the screening phase, the most suitable stationary phase, organic modifier, and pH were identified. The optimization was performed for secondary influential parameters—column temperature, gradient time, and flow rate using eight experiments—to examine multifactorial effects of parameters on the critical resolution and generated design space representing the robust region. A verification experiment was performed within the working design space and the model was found to be accurate. This study also describes other operating features of the column packed with superficially porous particles that allow very fast separations at pressures available in most liquid chromatography instruments. Successful chromatographic separation was achieved in less than 7 min using a fused‐core C₁₈ (100 mm × 2.1 mm, 2.6 μm) column with linear gradient elution of 10 mM ammonium formate (pH 3.0) and acetonitrile as the mobile phase. The method was validated for specificity, linearity, accuracy, precision, and robustness in compliance with the International Conference on Harmonization Q2 (R1) guidelines. The impurities were identified by liquid chromatography with mass spectrometry.     

Model-based equipment-design for plant-based extraction processes – considering botanic and thermodynamic aspects

The growing demand for plant-based products in the food, cosmetics and pharmaceutical industry leads to the need for a systematic process and equipment-design for the potentially applicable extraction techniques. Therefore, in this article, the classification of plant-based raw materials according to their characteristics is discussed. Furthermore, physicochemical modelling via distributed plug flow approach is applied and its possible fields of application are examined. Here, especially the extraction of water from the plant-based raw material as well as the entailed effects on the equilibrium and the mass transport kinetics are concerned. In addition to that, an evaluation method for the examined and generally available equipment through spider diagram is proposed. The relation to the initially argued botanic systems is discussed in particular. The extraction of vanillin from vanilla beans serves as exemplary system for this.     

Coordination mechanism based on mobile actuator design for wireless sensor and actuator networks

Wireless sensor and actuator networks combine a large number of sensors and a lower number of actuators that are connected with wireless medium, providing distributed sensing and executing appropriate tasks in a special region of interest. To accomplish effective sensing and acting tasks, efficient coordination mechanism among the nodes is required. As an attempt in this direction, this paper develops a collaborative control and estimation mechanism, which addresses the nodes coordination in a distributed manner. First, we propose a regional controllability‐based virtual force algorithm as an actuator deployment strategy to enhance area coverage after an initial random placement of actuators. During this process, a dynamic coordination mechanism is adopted to control nodes. This mechanism incorporates two components, namely, proportional‐integral‐derivative neural network and recursive least squares‐based Kalman filter algorithms. Taking advantage of feedback control and online learning technology, the proposed coordination mechanism schedules the corresponding nodes on the basis of the characteristics of current events, utilizes proportional‐integral‐derivative neural network controller inside each actuator to improve system transient and steady‐state responses, and deals with system state/parameter estimation problems according to the recursive least squares‐based Kalman filter algorithm, so as to achieve better control accuracy. Simulations demonstrate the effectiveness of our proposed methods. Copyright © 2013 John Wiley & Sons, Ltd.     

Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.     

N-CF3 Imidazolidin-2-one Derivatives via Photocatalytic and Silver-Catalyzed Cyclizations

While the N-trifluoromethylation of cyclic ureas is of interest for the potential to fundamentally change the properties of these biologically relevant moieties, the single synthetic procedure known to date describing their access only gives 4,4-disubstituted or fused aromatic cyclic N-CF₃ urea derivatives. We herein report an alternative approach to unleash access to the 4-monosubstituted imidazolidinone motif. The strategy relies on straightforward cyclization of readily accessible acyclic ureas, enabled by Ag-catalysis or light-assisted proton coupled electron transfer. The cyclic core is shown to be highly robust and amenable to various derivatizations, such as tandem Ni-catalysis, C−B, C−N, C−C cross couplings or C−H functionalizations, tolerating basic, nucleophilic and/or oxidizing conditions.