An Accelerated Coordinate Gradient Descent Algorithm for Non-separable Composite Optimization

Journal of Optimization Theory and Applications - Coordinate descent algorithms are popular in machine learning and large-scale data analysis problems due to their low computational cost iterative...     

A Convenient Synthesis of Vinyl Sulfides

tert-Alkyl sulfides, with an α-(1H-benzotriazol-1-yl) group 6 and 13 , are readily prepared from N-[(aryl-thio)methyl]-1H-benzotriazoles 3 and N-( 11 ), respectively, by reaction with BuLi and then with the appropriate electrophile. The tert-alkyl sulfides 6 and 13 are smoothly converted by BF₃. OEt₂ into vinyl sulfides 5, 7 or 12 , respectively, in satisfactory yields.     

Olefins turned alkylating agents: diastereoselective intramolecular Zr-catalyzed olefin alkylations

The first examples of intramolecular Zr-catalyzed electrophilic alkylation of aryl olefins are disclosed. Substituted carbo- and heterocycles are prepared efficiently and diastereoselectively.     

Anion-receptor molecules: Macrocyclic and macrobicyclic effects on anion binding by polyammonium receptor molecules

The stability constants for anion binding by the acyclic hexaamine 1 , its macrocyclic analogue 2 , and the bicyclic compound 3 in their protonated forms are reported. Compound 3 forms stable and selective complexes with halide ions, the stability sequence being I^? > Br^? > Cl^?. Compound 2 forms more stable complexes with sulfate, oxalate, and malonate dianions than its acyclic analogue 1 and shows a better selectivity pattern. Compound 3 forms stronger complexes with oxalate^2? than 2 and shows a remarkably high binding selectivity between oxalate^2? and malonate^2?. The comparison of the ability of 1–3 to complex anions demonstrates the macrocyclic and macrobicyclic effects on anion binding stability and selectivity.     

Mutual Separation and Determination of Th(IV) and U(VI) Using Arsenazo III as a Dye Collector Reagent by Flotation‐Spectrophotometric Method

This paper reports a simple and highly selective method for the separation, preconcentration, and determination of trace amounts of thorium and uranium in some complex samples via staircase flotation. The method is based on the initial flotation of the Th(IV)‐arsenazo III complex in the presence of U(VI) from a solution of 5 mol dm^?3 HCl, then reduction of U(VI) to U(IV) and repetition of the flotation step. In both steps, the floated complex was dissolved in a 5‐mL portion of methanol and its absorbance was measured at 655 nm, spectrophotometrically. For a 30‐mL portion of the sample, Beer's law was obeyed over the concentration ranges of 3.40 × 10^?7to 3.06 × 10^?6 mol dm^?3 for Th(IV) and3.40 × 10^?7 to 3.40 × 10^?6 mol dm^?3 for U(IV) with the apparent molar absorptivity of 4.20 × 10⁵ dm³ mol^?1 cm^?1 and 3.59 × 10⁵ dm³ mol^?1 cm^?1, respectively. The RSDs (n = 7) corresponding to 1.7 × 10^?6 mol dm^?3 of Th(IV) and U(IV) were obtained as 1.7% and 1.87%. The detection limits (7 blanks) for both the metal ions were found to be 1.7 × 10^?7 mol dm^?3. The important benefit of the method is that the determinations are free from the interference of almost all cations and anions found in the complex matrixes, such as seawater samples. The proposed method was also applied to reference materials, and the determinations were shown to have good agreement with the certified values.     

Copolyesterification between poly(butylene terephthalate), terephthalic acid and hydroquinone diacetate: a kinetic analysis

The kinetics of liquid crystalline copolyester synthesis via melt transesterification between poly(butylene terephthalate) (PBT), terephthalic acid (TA) and hydroquinone diacetate (HQDA) is examined. Two different copolyester compositions PBT30/(HQDA+TA) 70 and PBT 50/(HQDA+TA) 50 mol% ratio were synthesized. The ratio of HQDA to TA was kept constant for all the reactions.The copolyesters were synthesized via melt polycondensation route at 265°C, 275°C and 285°C using two different transesterification catalysts, zinc acetate and dibutyl tin oxide. A key postulation assumed in this work is that the reaction originates between TA and HQDA to form a dimer which slices PBT chain. The copolyesterification rate constant for a system containing butylene glycol a more nonpolar moiety compared to ethylene glycol in poly(ethylene terephthalate) has been determined. The activation energy values for the different copolymer systems has also been determined. The rate constants for the uncatalyzed and catalyzed copolyesterification reaction and the activation energy values for the reaction have been determined.     

Synthesis and characterization of [Cu(Phca2en)(PPh3)X] (X=Cl, Br, I, NCS, N3) complexes: crystal structures of [Cu(Phca2en)(PPh3)Br] and [Cu(Phca2en)(PPh3)I]

New mixed-ligand copper(I) complexes, [Cu(Phca₂en)(PPh₃)X], [Phca₂en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N₃ (5)] have been synthesized and characterized by various techniques. ¹H and ¹³C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca₂en)(PPh₃)Br] (2) and [Cu(Phca₂en)(PPh₃)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh₃ moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.     

Ketoconazol‐Triiodide Ion Pair Complex as a Suitable Carrier in an Iodide Selective Membrane Electrode

A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10^?2 to 1.0 × 10^?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions.     

Crystalline molecular alloys

The dicationic tecton 1-2H(+) leads in the presence of anionic M(CN)(6)(3-) complexes to two almost identical crystalline systems A (M = Fe) and B (M = Co) composed of 2-D H-bonded networks and water molecules. The epitaxial growth of B on A used as seed or A on B generates crystalline molecular alloys.     

A simple colorimetric method for the assay of penicillin G salt and penicillamine by oxidation with iodate

A simple colorimetric procedure is described for determination of penicillin G salt and penicillamine. It is based on oxidation with potassium iodate at room temperature and measurement of the liberated iodine at 520 nm after extraction with carbon tetrachloride. Compared with other procedures, this method proved to be more rapid, highly reproducible and reasonably accurate. The relative standard deviation did not exceed 0.9% and 0.4% for penicillin and penicillamine, respectively. The procedure has been successfully applied to pharmaceutical preparations containing either of the two compounds.