The synthesis, structure and photochromism of mercury(II)-iodide complexes of 1-CnH2n+1-2-(arylazo)imidazoles (n = 4, 6, 8)

The reaction of HgI₂ with 1-C_nH_2n+1-2-(arylazo)imidazole (Raai-C_nH_2n+1 where n = 4, 6, 8) has isolated iodide bridging dimeric complexes, [Hg(RaaiC_nH_2n+1)(μ-I)(I)]₂. The structures of the ligand and the complexes have been established by spectral (UV-Vis, IR, ¹H NMR) data. One of these complexes [Hg(1-hexyl-2-(p-tolylazo)imidazole)(μ-I)(I)]₂ has been structurally confirmed by single crystal X-ray diffraction study. The ligand, Raai-C_nH_2n+1 exists at ambient condition in trans geometry about azo (-NN-) group; the UV light irradiation in MeOH solution shows E-to-Z isomerisation. The reverse transformation, Z-to-E, is very slow with visible light irradiation while isomerises rapidly on heating. The coordinated ligand, Raai-C_nH_2n+1 in the complexes exhibit similar behaviour in DMF solution. Quantum yields (?_E→Z) of E-to-Z isomerisation are higher for free ligands than that of their metal complexes. The Z-to-E isomerisation is a thermally induced process. The activation energy (E_a) is calculated by controlled temperature experiment.     

Montamine, a unique dimeric indole alkaloid, from the seeds of Centaurea montana (Asteraceae), and its in vitro cytotoxic activity against the CaCo2 colon cancer cells

Reversed-phase HPLC analysis of the methanol extract of the seeds of Centaurea montana afforded a flavanone, montanoside (4), six epoxylignans, berchemol (7), berchemol 4′-O-β-d-glucoside (5), pinoresinol (10), pinoresinol 4-O-β-d-glucoside (8), pinoresinol 4,4′-di-O-β-d-glucoside (6), pinoresinol 4-O-apiose-(1→2)-β-d-glucoside (9), two quinic acid derivatives, trans-3-O-p-coumaroylquinic acid (1), cis-3-O-p-coumaroylquinic acid (2), and eight indole alkaloids, tryptamine (3), N-(4-hydroxycinnamoyl)-5-hydroxytryptamine (11), cis-N-(4-hydroxycinnamoyl)-5-hydroxytryptamine (12), centcyamine (16), cis-centcyamine (17), moschamine (13), cis-moschamine (14) and a dimeric indole alkaloid, montamine (15). While the structures of two new compounds, montanoside (4) and montamine (15), were established unequivocally by UV, IR, MS and a series of 1D and 2D NMR analyses, all known compounds were identified by comparison of their spectroscopic data with literature data. The antioxidant properties of these compounds were assessed by the DPPH assay, and their toxicity towards brine shrimps and cytotoxicity against CaCo-2 colon cancer cells were evaluated by the brine shrimp lethality and the MTT cytotoxicity assays, respectively. The novel dimer, montamine (15), showed significant in vitro anticolon cancer activity (IC₅₀=43.9 μM) while that of the monomer, moschamine (13), was of a moderate level (IC₅₀=81.0 μM).     

Recyclability of poly (N-isopropylacrylamide) microgel-based assemblies for organic dye removal from water

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgels and their aggregates have been shown to effectively remove organic dye molecules from aqueous solutions. Here, we investigate the reusability of these microgel-based systems by exposing them to the organic azo dye molecule, 4-(2-hydroxy-1-naphthylazo) benzenesulfonic acid sodium salt (Orange II). Following exposure, the microgels are isolated, and added to methanol to extract the trapped Orange II from the microgels, followed by a subsequent isolation. The isolated microgels were then exposed to Orange II once again, and the uptake efficiency of the recycled microgels determined. We found that the microgels and their aggregates could be reused to remove the organic dye with little loss in extraction efficiency with the number of recycling cycles.     

Rapid and Regiospecific Phenylthiolation of Some Organic Acids Catalyzed by AlCl3 in the Presence of Excess Anhydrous ZnCl2

Phenylthiolation of some carboxylic acids catalyzed by AlCl₃ in the presence of excess dehydrating agent (ZnCl₂) has been achieved. Moreover, regiospecificity was tested of some dioic acids and found to be specific at the aliphatic part of carboxylic functionality.     

Globrauneine A–F: six new triterpenoid esters from the leaves of Globimetula braunii

Abstract

Phytochemical study was conducted on the leaves of Globimetula braunii which is a hemi parasitic plant belonging to the family Loranthaceae. Extraction was carried out using cold extraction method with increasing polarity of solvents i.e n-hexane, CH₂Cl₂ and MeOH. The components were separated by chromatographic technique and the structures of the compounds were elucidated by extensive spectroscopic analyses including MS, FTIR, 1D and 2D NMR, HRMS and chemical methods. Six new pentacyclic triterpenoid esters named as globrauneine A (1), globrauneine B (2), globrauneine C (3), globrauneine D (4), globrauneine E (5), and globrauneine F (6), together with six known compounds (7 – 12) were successfully isolated from the leaves of G. braunii growing on Piliostigma thonningii. These results depict a substantial support to the chemotaxonomy of the genus Globimetula.     

Efficiency and Output Power Evaluation of a Wavelength Converter Based on FWM in a Single Mode Fiber

A frequency domain analysis is presented to determine the performance characteristics of a tunable alloptical wavelength converter using four-wave mixing (FWM) in a single mode fiber (SMF) around the zero dispersion wavelength using two pump lasers. The output converted signal power as well as efficiency evaluated at a bit rate of 10 Gb/s show that the signal power is substantially higher at lower values of wavelength separation.     

Swarnalin and cis-swarnalin, two new tetrahydrofuran derivatives with free radical scavenging activity, from the aerial parts of Cuscuta reflexa

The reversed-phase HPLC analysis of a methanol extract of the aerial parts of Cuscuta reflexa afforded a non-separable mixture (55 : 45) of two novel tetrahydrofuran derivatives, named swarnalin (1) and cis-swarnalin (2), and a known coumarin, 5,6,7-trimethoxycoumarin (3). The structures of the compounds were elucidated unequivocally by UV, HRFABMS and a series of 1D and 2D NMR analyses. The mixture of 1 and 2 showed significant free radical scavenging activity in the DPPH assay and the RC50 value was found to be 3.80 x 10(-4) mg mL(-1) for the mixture, compared to 2.88 x 10(-5) mg mL(-1) for the positive control, quercetin.     

Cadmium(II) complexes of (arylazo)imidazoles: synthesis, structure, photochromism, and density functional theory calculation

Reaction between CdX2 and 1-alkyl-2-(phenylazo)imidazole (RaaiR') has isolated complexes of composition Cd(RaaiR')2X2 in MeOH or MeCN. Crystallization of Cd(RaaiR')2I2 from N,N-dimethylformamide (DMF) has separated [Cd(RaaiR')I2.DMF], while Cd(RaaiR')2X2 (X = Cl and Br) remains unchanged in its composition upon crystallization under identical conditions. The structure has been established by spectral (UV-vis and 1H NMR) data and confirmation in the latter case by a single-crystal X-ray diffraction study of [Cd(TaiMe)I2.DMF] [where TaiMe = 1-methyl-2-(p-tolylazo)imidazole]. UV-light irradiation in a MeCN solution of Cd(RaaiR')2I2 and [Cd(RaaiR')I2.DMF] shows trans-to-cis isomerization of coordinated azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation. Quantum yields (phit-->c) of trans-to-cis isomerization are calculated, and the free ligand shows higher phi values than their cadmium(II) iodo complexes. The cis-to-trans isomerization is a thermally induced process. The activation energy (Ea) of cis-to-trans isomerization is calculated by a controlled-temperature experiment. The effects of the anions (Cl-, Br-, I-, and ClO4-) and the number of coordinated azoimidazoles (RaaiR') [Cd(RaaiR') or Cd(RaaiR')2] on the rate and quantum yields of photochromism are established in this work. A slow rate of photoisomerization of [Cd(RaaiR')4](ClO4)2 compared to Cd(RaaiR')I2 or Cd(RaaiR')2X2 may be associated with the increased mass and rotor volume of the complexes. The rate of isomerization is also dependent on the nature of X and follows the sequence Cd(RaaiR')2Cl2 < Cd(RaaiR')2Br2 < Cd(RaaiR')2I2. It may be related to the size and electronegativity of halide, which reduces the effective molar association in the order of I < Br < Cl and hence the rate. Gaussian 03 calculations of representative complexes and free ligands are used to explain the difference in the rates and quantum yields of photoisomerization.     

Optimal inventory policy for specialty chemical products in multiple packages

Many products are inventoried and sold in multiple outer packages, which causes the manufacturer or distributor to maintain a segmented inventory. Oftentimes, this scenario leads to shortages in some packages and over-stock in other package types. The shortages are usually linked to specific shortage costs, and the over-stock is always associated with some sort of unnecessary holding cost that either erodes profit margins or results in increased costs for the consumer. In this paper, the inventory policy for a specialty chemical manufacturer's cleaner, which is inventoried in four unique packages, is studied. A mathematical model is developed to account for the costs associated with initial procurement, holding and repackaging (shortage), which are the primary costs associated with the inventory system. Based upon this model, an optimal inventory policy is generated that reduces the need for repackaging, without requiring a prohibitive amount of safety stock. A specific historical case is summarized, and the results of this example are compared with the results that the new inventory policy would have produced, given the same circumstances.     

Methylcellulose-induced stability changes in protein-based emulsions

The emulsifying and oil-in-water stabilizing properties of methylcellulose (MeC) were investigated in bovine serum albumin (BSA)-based emulsions. The creaming stability, flocculation, surface concentration of BSA and MeC and droplet size were determined. Results obtained showed modifications of creaming rates that were related to MeC concentrations in the continuous and dispersed phases. Viscosity effects on creaming and changes in average droplet size (d₄₃) relating to droplet coverage were identified and delineated. Studies performed on macroscopic oil–water and air–water interfaces were used to identify interfacial structuring and composition. A good agreement was found between droplet surface composition and the resistance to coalescence of emulsion droplets. Emulsions that demonstrated a more rigid-like adsorbed interfacial layer were more stable with respect to coalescence. This study involving model emulsion systems provides a new insight into the stability of industrial preparations containing mixtures of proteins and polysaccharides.