Nano palladium supported on high‐surface‐area metal–organic framework MIL‐101: an efficient catalyst for Sonogashira coupling of aryl and heteroaryl bromides with alkynes

Palladium nanoparticle‐incorporated metal–organic framework MIL‐101 (Pd/MIL‐101) was successfully synthesized and characterized using X‐ray diffraction, nitrogen physisorption, X‐ray photoelectron, UV–visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL‐101 and high stability of nano‐size palladium particles. Pd/MIL‐101 nanocomposite was investigated for the Sonogashira cross‐coupling reaction of aryl and heteroaryl bromides with various alkynes under copper‐free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Spherically symmetric static inhomogeneous cosmological models

Spherically symmetric static cosmological models filled with black-body radiation are considered. The models are isotropic about a central observer but inhomogeneous. It is suggested that the energy density of the free gravitational field, which is coupled to the isotropic radiation energy density, might play an important role in generating sufficient field (vacuum) energy (when converted into thermal energy) and initiate processes like inflation. On the central world line the energy density of the free gravitational field vanishes whereas the proper pressure and density of the isotropic black-body radiation are constants. Further, it is shown that the cosmological constant is no more arbitrary but given in terms of the central pressure and density. Also, at its maximum value the energy density of the free gravitational field is proved to be equal to one third of the combined value of radiation pressure and density.     

Heck cross-coupling of vinyl heteroaromatic compounds with aryl and heteroaryl halides using Pd(II) complex under phosphine-free conditions

The palladium-catalyzed cross-coupling reaction of vinyl heteroaromatic compounds with aryl bromides and heteroaryl bromides is described using air and moisture stable N,N′,N″,O-tetrafunctional Pd catalyst under phosphine-free conditions. As a result a variety of trans-1,2-disubstituted vinyl heterocycles were obtained in high to good yields.     

Optical and dielectric properties of isothermally crystallized nano-KNbO3 in Er3+-doped K2O–Nb2O5–SiO2 glasses

Precursor glass of composition 25K₂O–25Nb₂O₅–50SiO₂ (mol%) doped with Er₂O₃ (0.5 wt% in excess) was isothermally crystallized at 800 °C for 0–100 h to obtain transparent KNbO₃ nanostructured glass–ceramics. XRD, FESEM, TEM, FTIRRS, dielectric constant, refractive index, absorption and fluorescence measurements were carried out to analyze the morphology, dielectric, structure and optical properties of the glass–ceramics. The crystallite size of KNbO₃ estimated from XRD and TEM is found to vary in the range 7–23 nm. A steep rise in the dielectric constant of glass–ceramics with heat-treatment time reveals the formation of ferroelectric nanocrystalline KNbO₃ phase. The measured visible photoluminescence spectra have exhibited green emission transitions of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 upon excitation at 377 nm (⁴I_15/2 → ⁴G_11/2) absorption band of Er³⁺ ions. The near infrared (NIR) emission transition ⁴I_13/2 → ⁴I_15/2 is detected around 1550 nm on excitation at 980 nm (⁴I_15/2 → ⁴I_11/2) of absorption bands of Er³⁺ ions. It is observed that photoluminescent intensity at 526 nm (²H_11/2 → ⁴I_15/2), 550 nm (⁴S_3/2 → ⁴I_15/2) and 1550 nm (⁴I_13/2 → ⁴I_15/2) initially decrease and then gradually increase with increase in heat-treatment time. The measured lifetime (τ_f) of the ⁴I_13/2 → ⁴I_15/2 transition also possesses a similar trend. The measured absorption and fluorescence spectra reveal that the Er³⁺ ions gradually enter into the KNbO₃ nanocrystals.     

Optical Analysis of Er3+:Boro-Fluoro-Phosphate Glasses

This paper deals with the preparation and optical analysis of Er³⁺ (0.2 mol%) boro-fluoro-phosphate glasses in the following glass compositions:

• Series A: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 AlF₃

• Series B: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 LiF

Measured Vis-NIR absorption spectra of Er³⁺:boro-fluoro-phosphate glasses have revealed nine absorption bands at 377 nm, 405 nm, 450 nm, 486 nm, 519 nm, 543 nm, 649 nm, 973 nm and 1529 nm, which correspond with the transitions of ⁴I_15/2 → ⁴G_11/2, (²G_9/2,⁴H_9/2), ⁴F_5/2, ⁴F_7/2, ²H_11/2, ⁴S_3/2, ⁴F_9/2, ⁴I_11/2, and ⁴I_13/2, respectively. With an excitation at λ _exci = 375 nm, a bright green emission (⁴S_3/2 → ⁴I_15/2) at 547 nm has been observed from these erbium glasses. Judd–Ofelt characteristic intensity Ω_λ (λ = 2, 4, 6) parameters are obtained from the absorption spectra, and these results were used to compute the radiative properties of Er³⁺:boro-fluoro-phosphate glasses. The NIR emission (⁴I_13/2 → ⁴I_15/2) at 1547 nm from these glasses was measured with an Ar⁺ laser (514.5 nm) as an excitation source.     

Spherical gravitational collapse with photon emission and a generalized Schwarzchild interior solution

The general dynamical equations for perfect fluid filled spheres with an outward flux of photons are derived. The vital role played by the energy density of the free gravitational field in accelerating photon production has been emphasized. It is pointed out that even when the material energy density is finite, the energy density of the free gravitational field can take infinitely large values resulting in vanishing surface area of the star. A generalized Schwarzschild interior solution with conformally flat geometry but with photon emission has been obtained. It is pointed out that the interior conformal coordinate system bears a strong resemblance to the exterior Krushkal coordinates. It is shown that for spherical star the invariant velocity of the fluid particles, falling towards the centre, is proportional to its radius suggesting that the outer envelopes collapse at a faster rate than the core part. It is shown that the interior radiating solution can be matched with generalized Schwarzchild exterior solution.     

Kinetics and mechanism of oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-cystine by manganese(III) in sulfuric acid medium

The kinetics of oxidation of l-cystine by Mn^III have been studied in sulfuric acid medium at 30 °C. The reaction was followed spectrophotometrically at λmax = 500 nm. The reaction shows first order dependence on both [Mn^III] and [cystine]. It was found that the rate of the reaction decreases with increase of [H⁺] up to a certain point and then remains unchanged. The oxidation product of the reaction was found to be cysteic acid. A plausible mechanism has been proposed to account for the experimental results.     

Time Resolved Fluorescence and Energy Transfer Analysis of Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>–Er<Superscript>3+</Superscript> Triply-Doped Ba–Al-Metaphosphate Glasses for an Eye Safe Emission (1.54 μm)

This paper reports on the preparation and systematic analysis of energy transfer mechanisms in Nd³⁺–Yb³⁺–Er³⁺ co-doped new series of barium-alumino-metaphosphate glasses. The time resolved fluorescence of Nd³⁺ in triply doped Ba–Al-metaphosphate glasses have revealed that, Yb³⁺ ions could function as quite efficient bridge for an energy transfer between Nd³⁺ and Er³⁺ ions. As a result, a fourfold emission enhancement at 1.54 μm of Er³⁺ ions has been achieved through an excitation of ⁴F_5/2 level of Nd³⁺ at 806 nm for the glass having 3 mol% Yb³⁺ with an energy transfer efficiency reaching up to 94%. Decay of donor (Nd³⁺) ion fluorescence has been analyzed based on theoretical models such as direct energy transfer model (Inokuti–Hirayama) and migration assisted energy transfer models (Burshtein’s hopping and Yokota–Tanimoto’s diffusion). The corresponding energy transfer parameters have been evaluated and discussed. Primarily, electrostatic dipole–dipole (s ~ 6) interactions are found to be responsible for the occurrence of energy transfer process in theses glasses.     

Concentration quenched luminescence and energy transfer analysis of Nd3+ ion doped Ba-Al-metaphosphate laser glasses

This paper reports the dopant ion (Nd³⁺) concentration effects on its luminescence properties in a new glass system based on barium-alumino-metaphosphates. Amongst the studied concentrations range of 0.276–13.31×10²⁰ ions/cm³, the glass with 2.879×10²⁰ ions/cm³ (1 mol%) Nd³⁺ concentration shows intense NIR emission from ⁴F_3/2 excited state, followed by a decrease in emission intensity for further increase in Nd³⁺ ion concentration. The observed luminescence quenching is ascribed to Nd³⁺ self-quenching through the donor-donor migration assisted cross-relaxation mechanism. The microscopic energy transfer parameters for donor-acceptor energy transfer, C _DA, and donor-donor energy migration, C _DD, have been obtained from the theoretical fittings to experimental decay curves and the spectral overlap model respectively. The C _DD parameters (×10^?39 cm⁶/sec) are found to be about three orders greater than that of C _DA (×10^?42 cm⁶/sec) for Nd³⁺ self-quenching in this host, demonstrating that the excitation energy migration among donors is due to the hopping mechanism. The energy transfer micoparameters obtained in the present study are comparable to the values reported for commercially available laser glasses LHG-8 and Q-98.     

Optimization of critical medium components for the maximal production of gentamicin by Micromonospora echinospora ATCC 15838 using response surface methodology

Optimization of the fermentation medium components for maximum gentamicin production by Micromonospora echinospora ATCC 15838 was carried out. Response surface methodology was applied to optimize the medium constituents. A 2⁴full-factorial central composite design was chosen to explain the combined effects of the four medium constituents, viz. starch, soyabean meal, K₂HPO₄, and CoCl₂ and to design a minimum number of experiments. A second order model was developed and fitted using least square method. The R ² value of the model was 0.9723, which shows that model is best fit for the present studies. The results of analysis of variance and regression of a second order model showed that the linear effects of starch (p<0.001697) and CoCl₂(p<7.99E-13), and cross product effects of starch and soyabean meal (p<0.029876) and soyabean meal and CoCl₂ (p<0.008909) were more significant, suggesting that these were critical variables having the greatest effect on the production of gentamicin in the production medium. The optimized medium consisting of 9 g/L starch, 3 g/L soyabean meal, 0.9 g/L K₂HPO₄, and 0.01 g/L CoCL₂ predicted 850 mg/L of gentamicin which was almost 110% higher than that of the unoptimized medium. The amounts of starch, soyabean meal, and K₂HPO₄ required were also reduced with RSM.