Effect of electrolytes and surfactant concentration on the interfacial tension of o/w emulsion

Summary The adsorption studies of proteincationic, anionic and non-ionic surfactants and effect of electrolytes on the adsorption of triton 100 and protein mixture on kerosene oil/water interface have been studied. The lowering of interfacial tension is found to depend upon the emulsifier concentration and valency of the ions.     

Macroscopic recognition of iodide by polymer appended calix[4]amidocrown resin

ABSTRACT

The current study reveals the synthesis of polymer appended Calix[4]amidocrown-5 with specific binding affinity for iodide at ppm-level. The low detection limits are observed via UV-vis and fluorescence spectroscopy. The time-dependent solution and solid-state ¹²⁷I NMR studies with 18.8 and 19 ppm shifts, indicate a strong sensing nature of resin towards iodide ion. A significant reduction in surface area and pore volume with higher thermostability of resin after iodide uptake indicated iodide inclusion in the amidocrown cavity. The mechanism of iodide sensing may be governed by noncovalent interactions of NH and OH protons present in amidocrown and phenyl ring as observed in terms of emission enhancement in fluorescence spectroscopy. The binding affinity and stoichiometric determinations are determined by Benesi-Hildebrand and Jobs plots, respectively.     

A modified volumetric method for the estimation of streptomycin sulphate in pharmaceuticals

Summary A volumetric method for the estimation of streptomycin sulphate in pharmaceuticals is based on the quantitative discharge of the violet colour of the maltol-iron complex, produced when streptomycin is hydrolysed in alkaline medium and treated with ferric chloride, by potassium permanganate. It is simple, accurate and other antibiotics such as dihydrostreptomycin, sodium salt of benzyl penicillin, chloramphenicol do not interfere. Procain penicillin has to be separated by extractio with chloroform.

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Zusammenfassung Die beschriebene volumetrische Streptomycinbestimmung in Arzneimitteln beruht auf dem Abbau des Streptomycins in alkalischer Lösung zu Maltol, Bildung des Maltol-Eisen(III)-Komplexes und Titration mit Permanganat bis zur Entfärbung. Das Verfahren ist einfach auszuführen und gibt Werte von befriedigender Genauigkeit. Dihydrostreptomycin, Chloramphenicol sowie das Natriumsalz des Benzylpenicillins stören nicht. Procain-Penicillin muß vorher durch Extraktion mit Chloroform abgetrennt werden.

     

Low-lying levels in103Rh from Coulomb excitation

Five low-lying negative parity states of¹⁰³Rh up to 1277 keV excitation energy were observed to be Coulomb excited with 2·5–4·5 MeV protons. The de-excitation gamma rays from these levels were identified in the singles spectra recorded with a 57 cc Ge(Li) detector. The level energies, branching ratios, reduced transition probabilitiesB(E2) and the multipole mixing ratios () were obtained. The 880, 1106 and 1277 keV levels have been Coulomb excited with protons for the first time. The ambiguity in theJ values for 803 and 1106 keV levels have been resolved using ²-fits, the assigned spin values are 1/2^– and 5/2^–, respectively. The-values for 474·1 and 811·2 keV transitions were obtained for the first time. The results have been discussed in the light of previously reported results.The authors wish to thank Professor I. M. Govil for his active interest at various stages of this work. One of us (DCT) acknowledges the financial support from U.G.C., New Delhi, under Faculty Improvement Programme.     

Spontaneous translation of nanodroplet over a heterogeneous surface due to thermal cycles: role of solid–liquid interfacial fluctuations

ABSTRACT

We study the molecular-scale features of the solid surface that result in the spontaneous motion of a nanodroplet due to the periodic variation of temperature. We first employ a thermodynamic model to predict the variation of solid–fluid interfacial properties that can result in the above motion. The model identifies a composite (surface couple) made of two surfaces that are characterised by a large difference between the entropic parts of the solid–liquid interfacial free energies. In order to understand the molecular-scale features of the two surfaces that may form a surface couple, we performed grand canonical Monte Carlo simulations of Lennard Jones fluid and crystalline surfaces made of Lennard Jones-like atoms. We then used the cumulant expansions of the perturbation formulas to divide the interfacial entropy into two parts: The one that is directly affected by the solid–fluid attraction (direct part), and the other (indirect part) that is indirectly affected by the solid–fluid attraction via the alteration of interfacial fluctuations. Our results indicate that two surfaces form a surface couple if the differences between their chemical natures lead to large differences in the indirect part of the interfacial entropy, while the direct part remains relatively unaffected.     

Ultrafast spectroscopy and computational study of the photochemistry of diphenylphosphoryl azide: direct spectroscopic observation of a singlet phosphorylnitrene

The photochemistry of diphenylphosphoryl azide was studied by femtosecond transient absorption spectroscopy, by chemical analysis of light-induced reaction products, and by RI-CC2/TZVP and TD-B3LYP/TZVP computational methods. Theoretical methods predicted two possible mechanisms for singlet diphenylphosphorylnitrene formation from the photoexcited phosphoryl azide. (i) Energy transfer from the (π,π*) singlet excited state, localized on a phenyl ring, to the azide moiety, thereby leading to the formation of the singlet excited azide, which subsequently loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. (ii) Direct irradiation of the azide moiety to form an excited singlet state of the azide, which in turn loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. Two transient species were observed upon ultrafast photolysis (260 nm) of diphenylphosphoryl azide. The first transient absorption, centered at 430 nm (lifetime (τ) ～ 28 ps), was assigned to a (π,π*) singlet S(1) excited state localized on a phenyl ring, and the second transient observed at 525 nm (τ ～ 480 ps) was assigned to singlet diphenylphosphorylnitrene. Experimental and computational results obtained from the study of diphenyl phosphoramidate, along with the results obtained with diphenylphosphoryl azide, supported the mechanism of energy transfer from the singlet excited phenyl ring to the azide moiety, followed by nitrogen extrusion to form the singlet phosphorylnitrene. Ultrafast time-resolved studies performed on diphenylphosphoryl azide with the singlet nitrene quencher, tris(trimethylsilyl)silane, confirmed the spectroscopic assignment of singlet diphenylphosphorylnitrene to the 525 nm absorption band.     

Visualization of water and surfactant floods in oil-saturated porous media

The flow of water and 1% surfactant solution displacing oil through homogeneous and non-homogeneous porous media have been studied experimentally. The results are shown by taking the photographs of unstable interface at regular interval of time. These photographs suggest that the spreading of the moving interface in lateral direction is more for 1% surfactant solution displacing oil than for water displacing oil and also the interface is more stable for surfactant flooding in the bed. The wavelengths of viscous fingers measured from the experiments are found to be in good agreement with the theoretical predictions for homogeneous bed. The percentage oil recovery at breakthrough is improved considerably with the use of surfactant solution. Effect of flow rate on recovery and breakthrough time has also been studied. Finally, the effect of non-homogeneous packing on the growth of fingers has been studied by creating non-homogeneous medium in an otherwise homogeneous porous medium.     

An Adaptive Non Reference Anchor Array Framework for Audio Retrieval in Teleconferencing Environment

In this paper, an adaptive framework for audio retrieval in live teleconferencing environments with multiple participants is proposed. The framework uses a non reference anchor array (NRA) to capture the interfering speech sources, in addition to the primary array that captures the speech source of interest (SOI). A linearly constrained-minimum variance (LC-MV) beamformer is used herein such that the signal coming from the look direction is preserved while interferences coming from the non look direction are nulled. Additionally, the reverberant component of the speech acquired by this framework is removed by a novel method that uses the linear prediction (LP) residual cepstrum. This method does not require the computation of the acoustic impulse response (AIR) of the teleconferencing room and hence is computationally efficient. The NRA framework is therefore able to remove correlated noise coming from the direction of the SOI and also dereverberating the noise free signal. The performance of the proposed framework is evaluated by conducting experiments on clean speech acquisition from distant microphone arrays. Experiments on distant speech recognition are also conducted using the TIMIT and MONC databases. Experimental results obtained from the proposed framework indicate a reasonable improvement over correlation, subspace and standard minimum variance beamforming methods. The application of the framework in audio retrieval in a live teleconferencing environment with multiple participants is also discussed.     

Ligand-free nickel catalyzed perfluoroalkylation of arenes and heteroarenes

We describe a “ligand-free” Ni-catalyzed perfluoroalkylation of heteroarenes to produce a diverse array of trfiluoromethyl, pentafluoroethyl and heptafluoropropyl adducts. Catalysis proceeds at room temperature via a radical pathway. The catalytic protocol is distinguished by its simplicity, and its wide scope demonstrates the potential in the late-stage functionalization of drug analogues and peptides.

A ligand-free, room temperature, Ni-catalyzed perfluoroalkylation of heteroarenes produced a diverse array of polyfluorinated adducts; potential in the late-stage functionalization of drugs and peptides is also demonstrated.     

Ab initio quantum chemical investigation of intramolecular magnetic interaction in some diradical derivatives of imino nitroxide and nitronyl nitroxide

The magnetic properties of the monoradicals 2-(4-phenyl acetylene)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidozolyl-oxyl (1) and 2-(4-phenyl acetylene)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl-3-oxide (2) and the diradicals 2,2'-(1,2-ethynediyldi-4,1-phenylene)bis[4,4,5,5-tetramethyl-4,5-dihydro-1H-imidozolyl-oxyl] (3), 2,2'-(1,2-ethynediyldi-4,1 3,1-phenylene)bis[4,4,5,5-tetramethyl-4,5-dihydro-1H-imidozolyl-oxyl] (4), and 2,2'-(1,2-ethynediyldi-4,1 3,1-phenylene)bis[4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl-3-oxide] (5) are investigated by ab initio quantum chemical methods. The rule of spin alternation in the unrestricted Hartree-Fock (UHF) method clearly shows that the radical sites are antiferromagnetically coupled in 3 and ferromagnetically coupled in 4 and 5, which is consistent with a previous experiment. The molecular geometries are optimized at Hartree-Fock levels. This is followed by single-point calculations using the density functional (UB3LYP) treatment and the multiconfigurational complete active space self-consistent field (CASSCF) methodology. Magnetic exchange coupling constants are determined from the broken-symmetry approach. The calculated J values, -3.60 cm(-1) for 3, 0.16 cm(-1) for 4, and 0.67 cm(-1) for 5, are in excellent agreement with the observed values. Because of the very large size of the diradicals 3-5, the CASSCF (10,10) calculations cannot yield realistic J values. Nevertheless, the CASSCF calculations support the antiferromagnetic nature of the magnetic coupling in 3 and the ferromagnetic nature of the coupling in 4 and 5. The existence of an intramolecular magnetic coupling in 3-5 is also confirmed through computations of the isotropic hyperfine coupling constants for monoradicals 1 and 2 as well as diradicals 3-5.