An efficient method for the preparation of benzyl γ-ketohexanoates

Twenty acid chlorides, 4-(mono/di-benzyloxy)-4-ketobutanoyl chlorides (Ia–XXa) were synthesised by the reaction of monoesters of succinic acid with thionyl chloride. The product thus obtained (4-benzyloxy-4-ketobutanoyl chlorides) was treated with diethylcadmium to convert it into the corresponding keto-esters (Ib–XXb), the mono/di-benzyl-γ-ketohexanoates, with a good yield. All the compounds thus prepared were characterised by physical, spectroscopic (UV-VIS, IR, ¹H NMR, ¹³C NMR), and mass measurements techniques.     

The Newtonian Viscosity of Polymer Solutions

Viscosity measurements of cellulose acetate and polyisobutylene over a wide range of concentrations and molecular weights have been made. The data so obtained and the data taken from the literature for schizophyllan show that the viscosity varies smoothly with concentration of the polymer for the whole range of concentrations and molecular weights investigated. The characteristic concentrations, C_ch , of the polymers are calculated by the following equations: C_ch = 0.77/[η] or C_ch = 1.08/[η]. The relationship between molecular weight and intrinsic viscosity is obtained by fitting the data by the method of least squares. By plotting the reduced viscosity versus the reduced concentration, superposition curves are obtained for both cellulose acetate and polyisobutylene. It is not possible to obtain superposition curves for schizophyllan, which is a more rigid polymer.     

A hybrid wrapper–filter approach to detect the source(s) of out-of-control signals in multivariate manufacturing process

With modern data-acquisition equipment and on-line computers used during production, it is now common to monitor several correlated quality characteristics simultaneously in multivariate processes. Multivariate control charts (MCC) are important tools for monitoring multivariate processes. One difficulty encountered with multivariate control charts is the identification of the variable or group of variables that cause an out-of-control signal. Expert knowledge either in combination with wrapper-based supervised classifier or a pre-filter with wrapper are the standard approaches to detect the sources of out-of-control signal. However gathering expert knowledge in source identification is costly and may introduce human error. Individual univariate control charts (UCC) and decomposition of T²$T^2$ statistics are also used in many cases simultaneously to identify the sources, but these either ignore the correlations between the sources or may take more time with the increase of dimensions. The aim of this paper is to develop a source identification approach that does not need any expert-knowledge and can detect out-of-control signal in less computational complexity. We propose, a hybrid wrapper–filter based source identification approach that hybridizes a Mutual Information (MI) based Maximum Relevance (MR) filter ranking heuristic with an Artificial Neural Network (ANN) based wrapper. The Artificial Neural Network Input Gain Measurement Approximation (ANNIGMA) has been combined with MR (MR-ANNIGMA) to utilize the knowledge about the intrinsic pattern of the quality characteristics computed by the filter for directing the wrapper search process. To compute optimal ANNIGMA score, we also propose a Global MR-ANNIGMA using non-functional relationship between variables which is independent of the derivative of the objective function and has a potential to overcome the local optimization problem of ANN training. The novelty of the proposed approaches is that they combine the advantages of both filter and wrapper approaches and do not require any expert knowledge about the sources of the out-of-control signals. Heuristic score based subset generation process also reduces the search space into polynomial growth which in turns reduces computational time. The proposed approaches were tested by exhaustive experiments using both simulated and real manufacturing data and compared to existing methods including independent filter, wrapper and Multivariate EWMA (MEWMA) methods. The results indicate that the proposed approaches can identify the sources of out-of-control signals more accurately than existing approaches.     

Two-step numerical procedure for complex permittivity retrieval of dielectric materials from reflection measurements

A two-step measurement procedure has been proposed for measurement of complex permittivity of dielectric materials using one-port reflection measurements. In the procedure, as a first step, a graphical method is applied to analyze on the complex reflection-coefficient plane the general pattern of dielectric behavior of the sample. Then, as a second step, optimization algorithms are utilized for retrieving electrical properties of samples. The procedure requires measurement of complex reflection scattering parameters of at least two samples with different lengths. It has been validated by X-band measurements of three polyvinyl chloride samples with lengths 5, 10, and 20 mm.     

Tuning a Single Ligand System to Stabilize Multiple Spin States of Manganese: A First Example of a Hydrazone‐Based Manganese(III) Spin‐Crossover Complex

A series of bis‐chelate pseudo‐octahedral mononuclear coordination complexes of manganese with the chromophore [MnN₄O₂]ⁿ⁺ (n=0, 1) have been generated in all three principal oxidation states of this transition‐metal center under ambient conditions by utilizing a readily tunable, versatile phenolic pyridylhydrazone ligand system (i.e., H₂(3,5‐R¹,R²)‐L; L=ligand). Strategic combinations of the nature and position of a variety of substituent groups afforded selective, spontaneous stabilization of multiple spin states of the manganese center, which, upon close crystallographic scrutiny, appears to be in part due to the occurrence or absence of hydrogen‐bonding interactions that involve the phenolate/phenolic oxygen atom. The divalent complexes are isolable in two forms, namely, molecular [Mn^II{H(3,5‐R¹,R²)‐L}₂] and ionic [Mn^II{H₂(3,5‐R¹,R²)‐L}{H(3,5‐R¹,R²)‐L}]ClO₄, with the latter complex converting easily into the former complex on deprotonation. Accessibility of the higher‐valent states is achievable only when the phenolate oxygen atom is sterically hindered from participation in hydrogen bonding. The [Mn^III{H(3,5‐tBu₂)‐L}₂]ClO₄ complex is the first example of a hydrazone‐based Mn^III complex to exhibit spin crossover. Formation of the tetravalent complexes [Mn^IV{(3,5‐R¹,R²)‐L}₂] (R¹=tBu, R²=H; R¹=R²=tBu) necessitates base‐assisted abstraction of the hydrazinic proton.     

Development of a flow-through optosensor for determination of Co(II)

A flow-through optical fibre chemical sensor for the determination of Co(II) at trace level using immobilised 2-(4-pyridylazo)resorcinol (PAR) as the reagent phase is proposed. PAR is physically adsorbed onto XAD-7. This method provided a great sensitivity and simplicity with wide linear response range from 1x10(-2) to 1x10(3)ppm and detection limit of 20ppb. This method also showed a reproducible result with relative standard deviation (R.S.D.) of 1.78% and response time of approximately 5min. The response towards Co(II) was also reversible using acidified KCl as the regenerating solution. Interference studies showed that Cr(III) significantly interfered during the determination. Excellent agreement with reference to inductively coupled plasma optical emission spectroscopy (ICPOES) method was achieved when the developed sensor was applied for determination of Co(II) in aqueous samples.     

Crystallization behavior of Mg–Cu–Y amorphous alloy

Amorphous Mg₆₁Cu₂₄Y₁₅ ribbons were manufactured by melt-spinning at wheel speeds in the range 5?C20?ms^?1. The crystallization behavior of amorphous ribbons was investigated by a combination of differential scanning calorimetry (DSC) and X-ray diffractometry. DSC measurements showed that the amorphous ribbons exhibit distinct glass transition temperature and wide supercooled liquid region before crystallization. During continuous heating three exothermic peaks and two endothermic peaks were observed. The characteristic thermodynamic parameters such as T _g, T _x , ??T _x , and T _rg are around 432?C439, 478?C485, 46?C54?K, and 0.55?C0.56, respectively. Isothermal annealing DSC traces for this amorphous alloy, the first crystallization peak showed a clear incubation period and Avrami exponent was found to be 2.30?C2.74, which indicate that the transformation reaction involved nucleation and three-dimensional diffusion controlled growth. Mechanical properties of the as-quenched and subsequently annealed ribbons were examined by Vickers microhardness (HV) measurements. Results showed that microhardness of the as-quenched ribbons were about 309?HV. However, the results also showed that microhardness of the rapidly solidified ribbons increases with the increasing temperature.     

Solubility of LIDOCAINE in Ionic, Nonionic and Zwitterionic Surfactants

The solubility of an anesthetic drug, LIDOCAINE, in water was investigated in the presence of ionic, nonionic and zwitterionic surfactants at 25 °C, and the solubility was found to increase linearly with the surfactant concentration. The molar solubilization ratio, R _m,s, and Gibbs free energy, DG_s^o\Delta G_{\mathrm{s}}^{\mathrm{o}} values for nonionic surfactants fall in the order DDAO > Brij 35 > Brij 30, whereas for ionic and zwitterionic surfactants the order is DDAPS > DTAB > SDS. The high negative values of the Gibbs energies in the cases of DDAO and DDAPS prove them to be better surfactants for solubilizing this drug as compared to the other surfactants.     

Intelligent active force control of a 3-RRR parallel manipulator incorporating fuzzy resolved acceleration control

This paper introduces a novel intelligent control scheme for robust and precise positioning and orientation of a class of highly non-linear 3-RRR (revolute-revolute-revolute) planar parallel manipulator. The primary objective is to force the manipulator to track accurately a prescribed Cartesian trajectory when the system is subjected to different types of disturbances in the forms of forced harmonic excitations. A two level fuzzy tuning resolved acceleration control (FLRAC) is first designed and implemented to the system to demonstrate the stable response of the manipulator in performing trajectory tracking tasks in the absence of the disturbances. In this scheme, the first level of fuzzy tuning is used to acquire the proportional-derivative (PD) gains linearly while the second level considers non-linear tuning for determining the other parameters of the fuzzy controller to increase its performance. Then, the controller is added in series with an active force controller (AFC) to create a novel two degree-of-freedom (DOF) controller known as FLRAC-AFC which is subsequently and rigorously tested for system robustness and accuracy in tracking the prescribed trajectory. The simulation study provides further insight into the potentials of the proposed robotic system in rejecting the disturbances for the given operating conditions. The results clearly show that the FLRAC-AFC scheme provides a much superior trajectory tracking capability compared to the conventional linear RAC alone.     

Stacked films immobilization of MBTH in nafion/sol-gel silicate and horseradish peroxidase in chitosan for the determination of phenolic compounds

The stacked-film immobilization of 3-methyl-2-benzothiazolinone hydrazone (MBTH) in hybrid nafion/sol-gel silicate film and horseradish peroxidase (HRP) in chitosan, performed in order to allow the determination of phenolic compounds, was investigated via an optical method. The stacked films were deposited onto a microscope glass slide by a spin-coating technique. The quinone or free radical product formed by the enzymatic reactions of phenolic compounds interacts with MBTH to form azo-dye products, which can be measured spectrophotometrically at a wavelength of 500 nm. The color intensity of the product was found to increase in proportion to the phenolic concentration after 5 min of exposure. The response of the biosensor was linear over concentration ranges of 0.025–0.500, 0.010–0.070 and 0.050–0.300 mM for guaiacol, resorcinol and o-cresol, respectively, and gave detection limits of 0.010, 0.005 and 0.012 mM. The sensor exhibited good sensitivity and stability for at least two months.