Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic clay for Friedel-Crafts type benzylation reactions

Fe-Mg-hydrotalcite (Mg/Fe = 3) anionic clay with or without calcination (at 200–800‡C) has been used for the benzylation of toluene and other aromatic compounds by benzyl chloride. Hydrotalcite before and after its calcination was characterized for surface area, crystalline phases and basicity. Both the hydrotalcite, particularly after its use in the benzylation reaction, and the catalyst derived from it by its calcination at 200–800‡C show high catalytic activity for the benzylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the chlorides and oxides of iron on the catalyst surface.     

Use of 2,4,6-trichloro-1,3,5-triazine (TCT) as organic catalyst in organic synthesis

Organic catalysts have found wide applications in organic synthesis. Many organic reactions, which originally do not occur under normal conditions or are difficult to operate normally, have been successfully conducted under mild conditions in the presence of catalysts. In recent years, 2,4,6-trichloro-1,3,5-triazine (TCT, cyanuric chloride) has been used as organic catalyst in many organic synthesis, because it is stable, nonvolatile, inexpensive, commercially available, and easy to handle. On account of these properties it has been used as a green catalyst and sometimes is a catalyst of choice in organic reactions.     

Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes

Reactions of nonheme Fe^III–superoxo and Mn^IV–peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)Fe^III(O₂)]^2? and [(TAML)Mn^IV(O₂)]^2?, with nitric oxide (NO) afford the Fe^III–NO₃ complex [(TAML)Fe^III(NO₃)]^2? and the Mn^V–oxo complex [(TAML)Mn^V(O)]^? plus NO₂^?, respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that M^III–peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)Fe^III(O₂)]^2? and [(TAML)Mn^IV(O₂)]^2? with NO, are converted into M^IV(O) and ^.NO₂ species through O?O bond homolysis of the peroxynitrite ligand. Then, a rebound of Fe^IV(O) with ^.NO₂ affords [(TAML)Fe^III(NO₃)]^2?, whereas electron transfer from Mn^IV(O) to ^.NO₂ yields [(TAML)Mn^V(O)]^? plus NO₂^?.     

Robust Shape Fitting via Peeling and Grating Coresets

Let P be a set of n points in ℝ ^d . A subset of P is called a (k,ε)-kernel if for every direction, the directional width of ε-approximates that of P, when k “outliers” can be ignored in that direction. We show that a (k,ε)-kernel of P of size O(k/ε ^(d−1)/2) can be computed in time O(n+k ²/ε ^d−1). The new algorithm works by repeatedly “peeling” away (0,ε)-kernels from the point set. We also present a simple ε-approximation algorithm for fitting various shapes through a set of points with at most k outliers. The algorithm is incremental and works by repeatedly “grating” critical points into a working set, till the working set provides the required approximation. We prove that the size of the working set is independent of n, and thus results in a simple and practical, near-linear ε-approximation algorithm for shape fitting with outliers in low dimensions. We demonstrate the practicality of our algorithms by showing their empirical performance on various inputs and problems. A preliminary version of this paper appeared in Proceedings of the 17th Annual ACM-SIAM Symposium on Discrete Algorithms, pp. 182–191. P.A. and H.Y. are supported by NSF under grants CCR-00-86013, EIA-01-31905, CCR-02-04118, and DEB-04-25465, by ARO grants W911NF-04-1-0278 and DAAD19-03-1-0352, and by a grant from the U.S.–Israel Binational Science Foundation. S.H.-P. is supported by a NSF CAREER award CCR-0132901.     

Morphological and electro-optical responses of dichroic polymer dispersed liquid crystal films

Dichroic polymer dispersed liquid crystal (DPDLC) films containing different concentration of dichroic dye have been prepared by polymerization induced phase separation technique using nematic liquid crystal material in UV curable polymer NOA 65 and anthraquinone dichroic dye. The effects of applied voltage and temperature on the LC droplet morphology and its optical characteristics were studied in detail. Liquid crystal droplets containing low concentration of dye (0.25%) in polymer matrix exhibit bipolar configuration at lower applied voltage (10 V) whereas at relatively higher voltage (15 V) maltese type liquid crystal droplets were seen. In addition, low concentration DPDLC film shows better optical transmission and higher contrast ratio.     

Validated LC Method for Simultaneous Analysis of Tramadol Hydrochloride and Aceclofenac in a Commercial Tablet

This paper describes development and validation of a high-performance liquid chromatographic method for simultaneous analysis of tramadol hydrochloride (TR) and aceclofenac (AC) in a tablet formulation. When the combination formulation was subjected to ICH-recommended stress conditions, adequate separation of TR, AC, and the degradation products formed was achieved on a C₁₈ column with 65:35 (v/v) 0.01 M ammonium acetate buffer, pH 6.5—acetonitrile as mobile phase at a flow rate of 1 mL min⁻¹. UV detection was performed at 270 nm. The method was validated for specificity, linearity, LOD and LOQ, precision, accuracy, and robustness. The method was specific against placebo interference and also during forced degradation. The linearity of the method was investigated in the concentration ranges 15–60 μg mL⁻¹ (r = 0.9999) for TR and 40–160 μg mL⁻¹ (r = 0.9999) for AC. Accuracy was between 98.87 and 99.32% for TR and between 98.81 and 99.49% for AC. Because degradation products were well separated from the parent compounds, the method was stability-indicating.

     

Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent

The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.     

Application of Vitamin E TPGS in ocular therapeutics – Attributes beyond excipient

Diseases affecting the anterior segment and the external surface of the eye are usually treated by drugs applied topically. The formulations designed for this purpose are developed to deliver active pharmaceutical agents to the eye optimally. These formulations are prepared by adding various agents (excipients) that help to maintain stability of the formulation, prevent microbial contamination, and allow easy administration with adequate drug bioavailability with the minimum ocular irritation and toxic effects at the administration site. The excipients do not have their own pharmacological actions, but Vitamin E TPGS (d-α-Tocopheryl polyethylene glycol 1000 succinate) seems to break this notion. Besides having drug formulation enhancement properties, it also possesses antioxidant properties, which have been found to have a beneficial effect on various ophthalmological diseases such as age-related macular degeneration, uveitis, glaucoma, and cataract. In this review, we primarily focus on the properties and applications of Vitamin E TPGS in ocular drug delivery and the benefits of Vitamin E (Vit E) in numerous sight-threatening ailments of the rear and front segment of the eye. Additionally, p-glycoprotein inhibition and the anti-cancer potential of vitamin E TPGS have also been summarized.     

Effect of degradation on electronic properties of polymer solar cells

We present here the effect of degradation on electronic properties of polymer solar cells. Investigations were performed on two types of solar cells based on the bulk‐heterojunction network of poly(3‐hexylthiophene) and phenyl [6,6] C₆₁ butyric acid methyl ester, one with slow degradation whereas other with faster degradation. Samples were prepared in identical conditions with controlled atmosphere, but for faster degradation, one of the samples was exposed to ambient air (rich in O₂ and H₂O molecules) before deposition of top metal electrode. The sample with slow degradation showed linear degradation in short circuit current density (J_sc), whereas the sample with faster degradation exhibited exponential degradation in J_sc. Linear degradation happens due to degradation in the active layer only whereas the exponential degradation is because of through degradation of the solar cell. The effect of degradation is investigated on different diode parameters. Because of different degradation processes in the two samples, the variations in diode parameters with time are different. Copyright © 2013 John Wiley & Sons, Ltd.