Synthesis and catalytic activity of binuclear titanium imido complexes

Treatment of the N-P ligand ArPN(SiMe3)2 with TiCl4 affords the imido-bridged binuclear titanium complex [TiCl2(THF)(micro-NArP)]2 (ArP = m-C6H4PR2) which reacts with Ni(0) or Pd(ii) to give heterotrinuclear compounds, while activation with methylaluminoxane generates a new type of imido-based ethene polymerisation catalyst that is tolerant of -PR2 functional groups.     

Effect of pH and α-, β- and γ-cyclodextrin on the spectral properties of etoricoxib: spectroscopic and molecular dynamics study

The spectral properties of etoricoxib (ETR) at pH 2.0, 6.0 and 10.0 in the presence of cyclodextrins (CDs) were investigated. The absorption spectrum of ETR in acidic medium exhibited two bands centered at 236 and 273 nm, while in basic medium it exhibited two bands centered at 236 and 285 nm. No change in the spectrum was observed in the presence of CDs. The fluorescence emission spectra of ETR in acidic and basic media exhibited one band at 380 nm and another one at 484 nm. The emission band at 484 nm was enhanced when ETR was complexed with β-CD and γ-CD at pH 2.0, 6.0 and 10.0, while the band at 380 nm was enhanced selectively when ETR was complexed with α-CD at pH 2.0. Molecular dynamics simulations computations revealed that at pH 2.0, the sulfonyl moiety of H₂ETR²⁺ is preferentially included within the α-CD cavity, which is believed to cause the enhancement of the band at 380 nm. Moreover, at pH 6.0 and 10.0, the enhancement of the band at 484 nm was related to the inclusion of the chloropyridinyl and methylpyridinyl groups of the bipyridine moiety of HETR⁺ and ETR within β-CD and γ-CD cavities. Benesi–Hildebrand analysis showed that the ETR/β-CD complex adopts a 1:1 stoichiometry with association constant of K ₁₁?=?64.8 at pH 2.0, K ₁₁?=?105.4 at pH 6.0 and K ₁₁?=?520.5 at pH 10.0.     

Iron(III) complexes with a biologically relevant aroylhydrazone: crystallographic evidence for coordination versatility

Complexation of iron(III) with the heterodonor chelating agent 3,5-di-tert-butylsalicylidene benzoylhydrazine, H2(3,5-tBu2)salbh, in the absence or presence of a base affords the complex cation [Fe{H(3,5-tBu2)salbh}2]+ or the neutral compound [Fe{H(3,5-tBu2)salbh}{(3,5-tBu2)salbh}], respectively, as revealed by single-crystal X-ray analyses. Such a synthetic and crystallographic demonstration of the coordination versatility of an aroylhydrazone toward iron is uncommon. The oxidation and spin states of the iron have been verified with magnetic and spectroscopic measurements.     

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.     

New possible mode of ligand-metal cooperation in PC(sp3)P pincer complexes

Ligand-metal cooperation in iridium and platinum complexes bearing tricyclic dibenzobarrelene-based PC(sp(3))P pincer ligands is discussed. We demonstrated that the carbon-metal bond in these complexes may be efficiently cleaved and regenerated via 1,2-addition/elimination reactions.     

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.     

Modeling of Swelling Behaviors of Acrylamide-Based Polymeric Hydrogels by Intelligent System

Hydrogels based on acrylamide (AAm) were synthesized by free radical polymerization in an aqueous solution using N,N’-methylenebisacrylamide (MBAAm) as crosslinker. To obtain anionic hydrogels, 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) and acrylic acid (AAc) were used as comonomers. The swelling behaviors of all hydrogel systems were modeled using an artificial neural network (ANN) and compared with a multivariable least squares regression (MLSR) model and phenomenal model. The predictions from the ANN model, which associated input parameters, including the amounts of crosslinker (MBA) and comonomer, and swelling values with time, produce results that show excellent correlation with experimental data. The parameters of swelling kinetics and water diffusion mechanisms of the hydrogels were calculated using the obtained experimental data. Model analysis indicated that the ANN models could accurately describe complex swelling behaviors of highly swellable hydrogels.     

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.