Effect of nanoclay and macroinitiator on the kinetics of atom transfer radical homo- and copolymerization of styrene and methyl methacrylate initiated with CCl3-terminated poly (vinyl acetate) macroinitiator

Effect of nanoclay on the kinetics of atom transfer radical bulk homo- and copolymerization of styrene (St) and methyl methacrylate (MMA) initiated with CCl₃-terminated poly (vinyl acetate) macroinitiator at 90 °C was investigated. CuCl/PMDETA was used as a catalyst system. Results showed that nanoclay significantly enhances the homopolymerization rate of MMA. It was attributed to the activated conjugated CC bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (AlOH) of nanoclay as well as to the effect of nanoclay on the dynamic equilibrium between the active (macro)radicals and dormant species. Homopolymerization rate of St (a noncoordinative monomer with nanoclay) decreased slightly in the presence of nanoclay. It could be explained by inserting of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. Controlled/living characteristic of all the reactions were confirmed by GPC results. More reliable reactivity ratios of the St and MMA in the presence of nanoclay were calculated by using the cumulative average copolymer composition at the moderate to high conversion to be r_St = 0.290 ± 0.082, r_MMA = 0.443 ± 0.093 (extended Kelen-Tudos method) and r_St = 0.293 ± 0.071, r_MMA = 0.447 ± 0.080 (Mao-Huglin method). Results indicated that the rate of incorporation of MMA comonomer into the copolymer increases in the presence of nanoclay, verifying the existence of interaction between the carbonyl group of MMA comonomer and the hydroxyl moiety of nanoclay. It was found that in the presence of nanoclay, tendency of the random copolymerization of St and MMA toward an alternating copolymerization increases.     

Multivariate optimization of hydrodistillation-headspace solvent microextraction of thymol and carvacrol from Thymus transcaspicus

In this paper multivariate response surface methodology (RSM) has been used for the optimization of hydrodistillation-headspace solvent microextraction (HD-HSME) of thymol and carvacrol in Thymus transcaspicus. Quantitative determination of compounds of interest was performed simultaneously using gas chromatography coupled with flame ionization detector (GC-FID). Parameters affecting the extraction efficiency were assessed and the optimized values were 5 min, 2 μL and 3 min for the extraction time, micro-drop volume and cooling time after extraction, respectively. The amounts of analyte extracted increased with plant weight. The calibration curves were linear in the ranges of 6.25-81.25 and 1.25-87.50 mg L⁻¹ for thymol and carvacrol, respectively. Limit of detection (LOD) for thymol and carvacrol was 1.87 and 0.23 mg L⁻¹, respectively. Within-day and between-day precisions for both analytes were calculated in three different concentrations and recoveries obtained were in the range of 89-101% and 95-116% for thymol and carvacrol, respectively.     

Roots of C*-algebra elements under numerical range condition

Let be a C*-algebra with unit 1. For each a ∈ , the C*-algebra numerical range is defined by V(a) = {φ(a): φ ∈ , φ ≥ 0,φ(1) = 1}. In a 2003 paper Li, Rodman and Spitkovsky have found the ω-th roots of elements in C*-algebra under a numerical range condition, when ω ∈ [1,∞). In this paper, we will give a short proof of the above result in the case of ω is a positive integer number. We also give a simple proof for ω-th root of an element a ∈ , when ω ∈ [1,∞) and V(a)∩ {z ∈ ℂ: z ≤ 0} = . The first author was supported by the Shiraz university Research Council Grant No. 86-GRSC-32.     

H-point standard addition method for simultaneous determination of Fe(II), Co(II) and Cu(II) in micellar media with simultaneous addition of three analytes

H-point standard addition method, HPSAM, with simultaneous addition of three analytes is proposed for the resolution of ternary mixtures. It is a modification of the previously described H-point standard addition method that permits the resolution of three species from a unique calibration set by making the simultaneous addition of the three analytes. The method calculates the analyte concentration from spectral data at two wavelengths where the two species selected as interferents present the same absorbance relationship. These wavelength pairs are easily found, and can be selected to give the most precise results. Diethyldithiocarbomate (DDC) in a cationic micellar solution of cetyltrimethylammonium bromide (CTAB) was used for determination of Fe(II), Co(II) and Cu(II) at pH 5.50. The results showed that simultaneous determination of Fe(II), Co(II) and Cu(II) could be preformed in the range of 0.0–6.0, 0.0–8.0 and 0.0–12.0 μg ml⁻¹, respectively. The proposed method was successfully applied to the simultaneous determination of Fe(II), Co(II) and Cu(II) in several synthetic mixtures containing different concentration of Fe(II), Co(II) and Cu(II).     

Synthesis,Characterization, and Crystal Structure of a Chromium(III)‐Complex Containing 2,6‐Pyridinedicarboxylic Acid and 1,10‐Phenanthroline

The reaction of solution 2,6‐pyridinedicarboxylic acid and 1,10‐phenanthroline ( 1 ) with CrCl₃·6H₂O led to the complex [Cr(phen)(pydc)(H₂O)][Cr(pydc)₂]·4H₂O ( 2 ) (phen is 1,10‐phenanthroline and pydcH₂ is 2,6‐pyridinedicarboxylic acid). 2 was characterized by elemental analysis, IR spectroscopy and single‐crystal structure determination. Crystal data for 2 at ?80 °C: triclinic, space group , a = 818.5(1), b = 1492.2(1), c = 1533.6(2) pm, α = 76.45(1)°, β = 84.22(1)°, γ = 77.99(1)°, Z = 2, R₁ = 0.0416.     

CeCl3·7H2O‐catalyzed one‐pot Kabachnik–Fields reaction: A green protocol for three‐component synthesis of α‐aminophosphonates

CeCl₃·7H₂O has been utilized as an efficient Lewis acid catalyst for the three‐component coupling of aldehydes, aromatic amines, and diethylphosphite to produce α‐aminophosphonates under solvent‐free conditions. The advantages of this protocol are high yield, mild reaction conditions, less environmental pollution, and simple work‐up procedure. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:397–403, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20635     

A novel robust proportional-integral （PI） adaptive observer design for chaos synchronization

In this paper, chaos synchronization in the presence of parameter uncertainty, observer gain perturbation and exogenous input disturbance is considered. A nonlinear non-fragile proportional-integral (PI) adaptive observer is designed for the synchronization of chaotic systems; its stability conditions based on the Lyapunov technique are derived. The observer proportional and integral gains, by converting the conditions into linear matrix inequality (LMI), are optimally selected from solutions that satisfy the observer stability conditions such that the effect of disturbance on the synchronization error becomes minimized. To show the effectiveness of the proposed method, simulation results for the synchronization of a Lorenz chaotic system with unknown parameters in the presence of an exogenous input disturbance and abrupt gain perturbation are reported.     

A green non-acid-catalyzed process for direct N=N–C group formation: comprehensive study,modeling, and optimization

The aim of this work is to introduce, model, and optimize a new non-acid-catalyzed system for a direct N\(=\)N–C bond formation. By reacting naphthols or phenol with anilines in the presence of the sodium nitrite as nitrosonium (\(\hbox {NO}^{+})\) source and triethylammonium acetate (TEAA), a N\(=\)N–C group can be formed in non-acid media. Modeling and optimization of the reaction conditions were investigated by response surface method. Sodium nitrite, TEAA, and water were chosen as variables, and reaction yield was also monitored. Analysis of variance indicates that a second-order polynomial model with F value of 35.7, a P value of 0.0001, and regression coefficient of 0.93 is able to predict the response. Based on the model, the optimum process conditions were introduced as 2.2 mmol sodium nitrite, 2.2 mL of TEAA, and 0.5 mL \(\hbox {H}_{2}\hbox {O}\) at room temperature. A quadratic (second-order) polynomial model, by analysis of variance, was able to predict the response for a direct N=N–C group formation. Predicted response values were in good agreement with the experimental values. Electrochemistry studies were done to introduce new Michael acceptor moieties. Broad scope, high yields, short reaction time, and mild conditions are some advantages of the presented method.     

Perfect quantum excitation energy transport via single edge perturbation in a complete network

We consider quantum excitation energy transport (EET) in a network of two-state nodes in the Markovian approximation by employing the Lindblad formulation. We find that EET from an initial site, where the excitation is inserted to the sink, is generally inefficient due to the inhibition of transport by localization of the excitation wave packet in a symmetric, fully-connected network. We demonstrate that the EET efficiency can be significantly increased up to ≈100% by perturbing hopping transport between the initial node and the one connected directly to the sink, while the rate of energy transport is highest at a finite value of the hopping parameter. We also show that prohibiting hopping between the other nodes which are not directly linked to the sink does not improve the efficiency. We show that external dephasing noise in the network plays a constructive role for EET in the presence of localization in the network, while in the absence of localization it reduces the efficiency of EET. We also consider the influence of off-diagonal disorder in the hopping parameters of the network.     

Evaluation of essential oils for maintaining postharvest quality of Thompson seedless table grape

The effects of postharvest spraying of essential oils from sweet basil (Ocimum basilicum), fennel (Foeniculum vulgare), summer savory (Satureja hortensis) and thyme (Thymus vulgaris) on fungal decay and quality parameters of the 'Thompson seedless' table grape stored at 0?±?1°C for 60 days were evaluated. Results showed that the essential oils, especially of thyme and fennel, have a good inhibitory effect on the development of fungal decay in Thompson table grapes. In addition, essential oils reduced weight loss, berry and rachis browning and had no considerable adverse effect on the flavour of the fruits. GC-MS analysis showed that the main compounds identified in sweet basil, fennel, summer savory and thyme oils are linalool (65.25%), trans-anethole (64.72%), carvacrol (54.14%) and β-ocimene (12.62%), respectively. Therefore, these essential oils have good potential for use as an alternative to synthetic fungicides for the preservation and storage of table grapes.