Orientational ordering of a nematic liquid crystal and its mixture with its chain-perfluorinated analogue

The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using ¹³C NMR. The method of proton-encoded local field (PELF) spectroscopy in combination with off-magic-angle spinning (OMAS) of the sample was used. High resolution 2D spectra were obtained, from which the order parameters were calculated. Linear relations between the obtained order parameters and anisotropic chemical shifts determined by 1D ¹³C NMR were established and semi-empirical parameters were achieved. A 1:2 mixture of 7CPB and its chain-perfluorinated analogue (7PFCPB) showed interesting phase behaviour with the change of temperature. It was studied by the use of ¹³C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained from the 2D NMR method.     

System identification of a pick-and-place mechanism driven by a permanent magnet synchronous motor

The main objective of this study is to utilize two dynamic models: a mathematical model and a simple model, to identify a pick-and-place mechanism (PPM) which is driven by a permanent magnet synchronous motor (PMSM). In this paper, Hamilton’s principle is employed to derive the mathematical model, which is a nonlinear differential equation, while Newton’s second law is utilized to derive the simple linear model. In system identification, we adopt the real-coded genetic algorithm (RGA) to find not only the parameters of the PPM, but also the PMSM simultaneously. From the identification simulations and experimental results, it is demonstrated that the identification results of the mathematical model present the better matching with the experimental results of the system.     

Dynamic analysis of a non-conservative band–wheel system with a moving boundary part 2: Numerical results

The dynamic formulations of a non-conservative band/wheel system with a moving boundary are derived in the companion paper by use of Hamilton’s principle and calculus of variation. In this paper, numerical simulations for the system are obtained in transient amplitudes of the string and positions of the moving boundary by a modified finite difference method (FDM). Since the moving boundary position may not locate exactly at a grid point for any computational time, a special technique of the FDM is proposed to approximate both the transversality condition of a moving boundary and the partial differential equation of the neighboring grid points. The effects of parameters such as radius of the wheel, tension of the string, propagation speeds of the longitudinal and transverse wave and various initial conditions on the transient responses are investigated and compared with those of the fixed boundary problem.     

A rational approach in the design of selective mesoporous adsorbents

Two MCM-41 derived adsorbents have been tailor-made for the separation of silver and copper ions using the hard-soft, acid-base (HSAB) principle as the design guideline. NH2-MCM-41 containing "hard" Lewis base adsorption sites (i.e., RNH2) was prepared for the adsorption of the "hard" Lewis acid, Cu2+, and SH-MCM-41 with a grafted "soft" thiolpropyl base was prepared for the selective removal of Ag+, a "soft" Lewis acid. Single- and binary-component adsorption studies were conducted at different metal concentrations, solution compositions, and pH values. The experimental results showed that SH-MCM-41 has excellent affinity and capacity for silver adsorption and adsorbed only the silver ions with copper remaining in the solution. The selectivity was not affected by the metal concentration and composition, anion, and pH. Under similar experimental conditions, NH2-MCM-41 selectively adsorbed copper from the binary solution. The selectivity of NH2-MCM-41 remained for the copper at different pH values, although the adsorption capacity diminished at lower pH values. The type of anions used affected copper adsorption on NH2-MCM-41 with an increased copper uptake in the presence of the sulfate ions. A simple Freundlich adsorption model was sufficient to describe metal adsorption on SH-MCM-41 and NH2-MCM-41, and the LeVan and Vermeulen model was successfully used to predict the adsorption capacity and selectivity for binary-component adsorptions.     

Variable selection for discriminating herbal medicines with chromatographic fingerprints

When discriminating herbal medicines with pattern recognition based on chromatographic fingerprints, typically, the majority of variables/data points contain no discrimination information. In this paper, chemometric approaches concerning forward selection and key set factor analysis using principal component analysis (PCA), unweighted and weighted methods based on the inner- and outer-variances, Fisher coefficient from the between- and within-class variations were investigated to extract representative variables. The number of variables retained was determined based on the cumulative variance percent of principal components, the ratio of observations to variables and the factor indicative function (IND). In order to assess the methods for variable selection and criteria levels to determine the number of variables retained, the original and reduced datasets were compared with Procrustes analysis and a weighted measure of similarity. Moreover, the tri-variate plots of the first three PCA scores were used to visually examine the reduced datasets in low dimensional space. Herbal samples were finally discriminated by use of Bayes discrimination analysis with the reduced subsets. The case study for 79 herbal samples showed that, the methods of forward selection associating the variables with the loadings closest to 0 and key set factor analysis were preferable to determine the representative variables. Procrustes analysis and the weighted measure were not indicative to extract representative variables. High matching between the original and reduced datasets did not suggest high prediction accuracy. Visually examining the PC1-PC2-PC3 scores projection plots with the reduced subsets, not all the herb samples could be separated due to the complexity of chromatographic fingerprints.     

Dynamic analysis and system identification of an LCD glass-handling robot driven by a PMSM

In this paper, Hamilton’s principle is employed to derive Lagrange’s equations of an liquid crystal display (LCD) glass-handling robot driven by a permanent magnet synchronous motor (PMSM). The robot has three arms driven by two timing belts. The dynamic formulations can be expressed by one and four independent variables, which are named as the rigid and flexible models, respectively. In order to verify the dynamic formulation is correct, we reduce the flexible model to the rigid one under some assumptions. In this paper, we adopt the real-coded genetic algorithm (RGA) to identify all the parameters of the robot and PMSM simultaneously. It is found that the RGA can identify system parameters which are difficult to be measured in practical problems, for examples, the inductance, stator resistance, motor torque constant, damping coefficient of the motor and timing belts. In numerical simulations, vibrations due to flexibility of the timing belts are investigated for the angular displacements, speeds, accelerations of arms, and the horizontal and vertical displacements of the robot. The angular displacements of the robot arm and the translational positions of the robot end are obtained in the numerical simulations and experimental results. From their comparisons, it is demonstrated that identification results of the dynamic model with four independent variables present the better matching with experimental results of the system.     

‘One-flask’ transformation of isocyanates and isothiocyanates to guanidines hydrochloride by using sodium bis(trimethylsilyl)amide

A ‘one-flask’ synthesis of guanidines was developed by reacting isocyanates and isothiocyanates with sodium bis(trimethylsilyl)amide followed by addition of primary or secondary amines with a catalytic amount of AlCl₃. The desired guanidines were obtained in good yields and the reaction was applicable to aliphatic and aromatic substrates. A plausible mechanism was proposed through the generation of cyanamide anion from isocyanates or isothiocyanates with sodium bis(trimethylsilyl)amide. Addition of amines and catalytic amount of AlCl₃ smoothly converted the cyanamides to the desired guanidines.     

Homoleptic Platinum(II) and Palladium(II) Organothiolates and Phenylselenolates: Solvothermal Synthesis,Structural Determination,Optical Properties,and Single‐Source Precursors for PdSe and PdS Nanocrystals

Homoleptic d⁸‐metal organothiolates and phenylselenolates [M(EC₆H₅)₂]_∞ (E=S, M=Pt 1 , M=Pd 2 , M=Ni 5 ; E=Se, M=Pt 3 , M=Pd 4 ) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X‐ray diffraction data. In each case, the EC₆H₅ (E=S, Se) ligand binds to two metal ions (M=Pt, Pd, and Ni) to form chain‐like structures with planar (in 1 ) or zig‐zag (in 2 , 3 , 4 , 5 ) conformations. The [M(SR)₂]_∞ complexes (M=Pt, R=4‐tert‐butylphenyl 6 ; R=2‐naphthyl 8 ; R=4‐nitrophenyl 10 and M=Pd, R=4‐tert‐butylphenyl 7 ; R=2‐naphthyl 9 ; R=4‐nitrophenyl 11 ) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6 , 7 , 8 , 9 , 10 , 11 have the same [M(SR)₂]_∞ formulation as 1 and 2 . The cyclic complex [Pd₆(SCH₃)₁₂] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain‐like polymer structure is proposed for both [Pd(SC₁₂H₂₅)₂]_∞ 13 and [Pd(SC₁₆H₃₃)₂]_∞ 14 ; these polymeric chains self‐assemble to give layer‐like structures. Solid‐state diffuse reflectance spectra reveal that the optical band gap E_g (eV) of complexes 1 , 6 , 8 , 10 and of 2 , 7 , 9 , 11 are in the range of 2.10–3.00 eV and 2.10–2.63 eV, respectively, and 5 has the lowest E_g value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase‐pure Pd₁₇Se₁₅ and PdS nanocrystals, respectively. Field‐effect transistors fabricated with a drop‐cast thin film made from Pd₁₇Se₁₅ nanocrystals prior treated with an ethanolic solution of 1‐hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7×10^?2 cm² V^?1 s^?1 and 6×10^?2 cm² V^?1 s^?1, respectively.     

One-pot ethynylation and catalytic desilylation in synthesis of mestranol and levonorgestrel

A one-pot ethylnylation and catalytic desilylation reaction was developed for the synthesis of mestranol and levonorgestrel. Addition of trimethylsilylacetylide to the carbonyl group at C-17 of the steroids yielded the C-17α-trimethylsilylacetylenyl adducts, which were desilylated with a catalytic amount of TBAF (0.050 equiv) in one pot to provide the corresponding mestranol and levonorgestrel both in 90% yields. A plausible mechanism was proposed for the catalytic desilylation through the regeneration of the fluoride ion from the reaction of alkoxide on the steroid with Me₃SiF. The one-pot ethynylation and catalytic desilylation methodology provided an alternative route and avoided the traditional use of flammable and explosive acetylene gas toward the synthesis of mestranol and levonorgestrel.