Cationic complexes of chelated bis(η-cyclopentadienyl)titanium(IV) with halometallates of gallium(III), indium(III) and thallium(III)

Summary Eight complexes of the chelated bis(-cyclopenta-dienyl)titanium(IV) cation. [-Cp₂TiL][MX₄] (L = acetyl-acetone, M = Ga^III, In^III or Ti^III: X = Cl, Br or I) have been isolated from aqueous solution and characterised by elemental analyses and i.r. data. Their ionic nature has been confirmed by conductance measurements.     

Physicochemical characterization and adsorption behavior of calcined Zn/Al hydrotalcite-like compound (HTlc) towards removal of fluoride from aqueous solution

A Zn/Al hydrotalcite-like compound (HTlc) was prepared by co-precipitation (at constant pH) method and was characterized by XRD, TG/DTA, FTIR, and BET surface area. The ability of Zn/Al oxide to remove F- from aqueous solution was investigated. All the adsorption experiments were carried out as a function of time, pH, concentration of adsorbate, adsorbent dose, temperature etc. It was found that the maximum adsorption takes place within 4 h at pH 6.0. The percentage of adsorption increases with increase in the adsorbent dose, but decreases with increase in the adsorbate concentration. From the temperature variation it was found that the percentage of adsorption decreases with increase in temperature, which shows that the adsorption process is exothermic in nature. The adsorption data fitted well into the linearly transformed Langmuir equation. Sulfate and phosphate were found to have profound effects on fluoride removal. Thermodynamic parameters such as DeltaG0, DeltaH0, and DeltaS0 were calculated. The negative value of DeltaH0 indicates that the adsorption process is exothermic. The apparent equilibrium constants (Ka) are also calculated and found to decrease with increase in temperature. With 0.01 M NaOH the adsorbed F- could be completely desorbed from Zn/Al oxide in 6 h.     

Synthesis of cross linked platinum metal containing polyyne polymers

Reaction of Pt(PⁿBu₃)₂Cl₂ (1) or Pt(AsⁿBu₃₂Cl₂ (2) with stoichiometric amounts of 1,3,5-triethynylbenzene, [1,3,5-(H? C?C? )₃C₆H₃] (3)yields monomeric, [1,3,5-Cl(PⁿBu₃)₂(Pt? C? C? )₃C₆H₃] (4), [1,3,5-(C1)(AsⁿBu₃)₂Pt? C? C? ₃C₆H₃] (5) or polymeric, {1,3,5-[(PⁿBu₃)₂Pt? C?C? ]₃C₆H₃? )ⁿ (6), {1,3,5-[(AsⁿBu₃)₂Pt? C? C? ]₃C₆H₃? }ⁿ (7) complexes. Treatment of (1) with (3) and 2,5-diethynyl-p-xylene,H? C? C? C₆H₂(CH₃)₂? C? C? H (8) in varying molar ratios yields a series of high molecular weight cross linked platinum metal containing polyyne copolymers.     

Inherently gain flattened L band TDFA based on W-fiber design

We present here a detailed theoretical analysis for realizing an inherently gain flattened L⁺ band thulium doped fiber amplifier (TDFA), based on a depressed inner-clad (W-fiber) design, wherein the inherent gain flattening is achieved by an optimized bend induced leakage loss. The leakage loss characteristics of W-fiber have been used to suppress higher wavelength amplified stimulated emission (ASE) in the designed TDFA, which otherwise depletes the population inversion in the amplifier, making it almost impossible to obtain high gain for wavelengths in and close to the conventional L-band. It has been shown through simulations that 20 dB net gain (±0.3 dB ripple) is achievable over 32 nm bandwidth (1604-1636 nm), using this design pumped with 160 mW of power. We also show that inherent gain flattening leads to redistribution of power among signal wavelengths, and hence an inherently gain-flattened TDFA is much more efficient as compared to a configuration that uses discrete filters for gain flattening. The net gain value and gain flattening of the designed TDFA module have been tested against tolerance with respect to fiber parameters as well as bend radius. This is for the first time to the authors knowledge that inherently gain flattened L⁺ band operation has been shown using TDFAs.     

Enhancing photocatalytic activity of zinc oxide by coating with some natural pigments

An attempt has been made to enhance the photocatalytic activity of zinc oxide semiconductor by coating it with extracts of natural pigments, chlorophyll and anthocyanin. Coated photocatalyst has been used for the photobleaching of rose bengal dye. Progress of the reaction has been monitored spectrophotometrically by measuring absorbance of the reaction mixture at definite time intervals. The effect of variation of different parameters such as pH, concentration of dye, amount of semiconductor and light intensity on the rate of photobleaching was also observed. A tentative mechanism for the reaction has been proposed.     

Proline‐based polymeric monoliths: Synthesis,characterization, and applications as organocatalysts in aldol reaction

Proline‐based polymer monoliths were synthesized via green protocol using lipase‐catalyzed esterification of methacrylic acid and 4‐hydroxyproline. Prolinyl methacrylate thus prepared was polymerized in situ as crosslinked monolith. The monolith was characterized by various techniques such as Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and nitrogen analysis and used as catalyst in aldol reactions. The swelling behavior of the monolith was also studied as function of various external parameters like pH and temperature. The monoliths synthesized with 1% crosslinker was selected as candidate monolith for use as catalyst in aldol reaction, which was studied as a function of time, temperature, substrate structure, and amount of water:EtOH. The catalysts exhibited high efficiency in the cross aldol reaction, especially with the aromatic substrates having electron withdrawing substituent, and also good activity retention was observed when recycleability was studied up to five cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1007–1015, 2010     

Non-isothermal kinetics of melting and nematic to isotropic phase transitions of 5CB liquid crystal

This work reports a non-isothermal kinetics of the melting and the nematic to isotropic (N–I) phase transitions of the pentylcyanobiphenyl (5CB) liquid crystal compared with octylcyanobiphenyl (8CB) liquid crystal using calorimetric technique. Temperature scans and heating rate scans were performed for 5CB and 8CB from 280 to 333 K at various rates using differential scanning calorimetry from 0.5 to 20 K min⁻¹. Double activation was observed for 5CB for two heating rate regimes whereas 8CB indicated single activation only. The 5CB has smaller enthalpy and entropy of the transitions and needs larger activation than 8CB. This kinetic change can be explained in terms of the length scale and mobility of the liquid crystal molecules.     

Spectrophotometric determination of zirconium with 5,7-dibromo-8-hydroxyquinoline in presence of thiocyanate

The characteristics of the ternary complex formed between zirconium(IV) and 5,7-dibromo-8-hydroxyquinoline in presence of thiocyanate have been studied with an analytical point of view. The resulting colored species is extractable into chloroform with absorption maximum at 416 nm, which leads to the determination of the trace amounts of the metal ion. The method obeys Beer’s law in the range 0.2–9.0 μg Zr/mL having molar absorbitivity and Sandell’s sensitivity values of 1.05 × 10⁴ L/mol cm and 0.0087 μg Zr/cm², respectively. The ratio of zirconium(IV), 5,7-dibromo-8-hydroxyquinoline and thiocyanate in the extracted species is found to be 1: 2: 2. A large number of foreign ions do not interfere in the proposed method. The applicability of the procedure is tested by carrying out satisfactorily the analysis of a wide variety of samples.     

A DFT study of the structures of pyruvic acid isomers and their decarboxylation

Pyruvic acid and its isomers, including the enol tautomers and enantiomeric lactone structures, have been investigated at the B3LYP/6-311 + + G(3df,3pd) level, and it is found that a keto form with trans C(methyl)C(keto)C(acid)O(hydroxyl) and cis C(keto)C(acid)OH, and with one methyl hydrogen in a synperiplanar position with respect to the keto oxygen, is the most stable. This agrees with previous theoretical and experimental determinations. However, no minimum corresponding to protonated pyruvate could be located, although previous semiempirical calculations had found such structures. Decarboxylation by different possible routes was then studied. It was found that the direct formation of acetaldehyde, the most stable of the resulting C2H4O isomers, via a four-center-like transition state is the most feasible, although there is a high activation barrier of 70 kcal mol(-1). In contrast to semiempirical calculations, it is found that no hydroxyethylidene-carbon dioxide complex exists as a product, and no transition state leading to the dissociation to hydroxethylidene could be located.     

Spectrophotometric determination of palladium with 4-(2-pyridylazo)resorcinol

Summary A simple photometric method for the determination of palladium has been worked out, employing pyridylazo-resorcinol (PAR) as a complexing ligand for the metal ion. The coloured species is extractable into chloroform in the presence of diethylamine, the absorbance of which is measured at 535 nm. The method is free from the interference of a large number of elements particularly the other platinum metals. It obeys Beer's law in the range of 0–3 g Pd/ml with Sandell's sensitivity of 0.0034 g Pd cm^–2. The ratio of metal to ligand in the complex is found to be 1:1. Analysis of various samples has been carried out with satisfactory and reproducible results (standard deviation ±0.002).