Unexpected 5,6,7,8,9,10-hexahydro-6,6-pentamethylenephenanthridines and 2,3,4,5-tetrahydro-4,4-tetramethylene-1H-cyclopenta[c]quinolines from Skraup-Doebner-Von Miller quinoline synthesis and their implications for the mechanism of that reaction

The real mechanism of the Skraup-Doebner-Von Miller quinoline synthesis remains controversial and not well understood despite several mechanistic studies reported on the matter. A series of unexpected and unusual 5,6,7,8,9,10-hexahydro-6,6-pentamethylenephenanthridines and 2,3,4,5-tetrahydro-4,4-tetramethylene-1H-cyclopenta[c]quinolines have been obtained through the Skraup-Doebner-Von Miller quinoline synthesis. On the basis of these unexpected results and in agreement with some of the previously reported quinoline syntheses, an alternative mechanistic pathway is proposed for this variant of the reaction. It involves the formation of a Schiff base through a reaction between the ketone and the aniline derivative in the first step, followed by a cycloalkenylation at the ortho-position to the amine functional group of the aniline derivative, and an annulation in the final step to close the quinoline ring, leading to a dihydroquinoline derivative. To the best of our knowledge, this is the first report of such a mechanistic pathway being proposed for any variant of the Skraup-Doebner-Von Miller quinoline synthesis.     

Catalysis of the arsenic(III)-potassium bromate reaction-I: titrimetric determination of arsenic(III) in the presence of osmium tetroxide

The range of acid concentration available for the titration of arsenic(III) with bromate is considerably extended by the use of osmium tetroxide as catalyst in preference to the use of hydrochloric acid or hydrochloric acid-potassium bromide media. The acid concentration range over which reaction is stoichiometric has been established by potentiometric titration.     

Pasch geometric spaces inducing finite projective planes

Summary A geometric space over a geometric sfield of dimension three induces a protective plane. A relation between the order of the projective plane and that of the geometric sfield is obtained. For a particular order of the sfield, the induced projective plane is shown to be desarguesian.     

PEG-grafted chitosan as an injectable thermoreversible hydrogel

PEG-grafted chitosan was formulated such that its solution undergoes a thermally reversed phase transition from an injectable free-flowing solution at low temperature to a gel at body temperature. Aqueous solutions of PEG-grafted chitosan can be prepared at physiological pH values, thereby allowing safe incorporation of bioactive molecules. This injectable thermoreversible hydrogel is potentially suitable for a wide range of biomedical applications, particularly in sustained in vivo drug release and tissue engineering. An aqueous solution of PEG-grafted chitosan polymer is injectable at low temperatures but forms a gel at body temperature.     

Comparison of energy interaction parameters for the complexation of Pr(III) with glutathione reduced (GSH) in absence and presence of Zn(II) in aqueous and aquated organic solvents using 4f-4f transition spectra as PROBE

The coordination chemistry of glutathione reduced (GSH) is of great importance as it acts as excellent model system for the binding of metal ions. The GSH complexation with metal ions is involved in the toxicology of different metal ions. Its coordination behaviour for soft metal ions and hard metal ions is found different because of the structure of GSH and its different potential binding sites. In our work we have studied two chemically dissimilar metal ions viz. Pr(III), which prefer hard donor site like carboxylic groups and Zn(II) the soft metal ion which prefer peptide-NH and sulphydryl groups. The absorption difference and comparative absorption spectroscopy involving 4f-4f transitions of the heterobimetallic Complexation of GSH with Pr(III) and Zn(II) has been explored in aqueous and aquated organic solvents. The variation in the energy parameters like Slater-Condon (F(K)), Racah (E(K)) and Lande (xi(4f)), Nephelauxetic parameter (beta) and bonding parameter (b(1/2)) are computed to explain the nature of complexation.     

Shape-shifting tetranuclear oxo-bridged manganese cluster: relevance to photosystem II water oxidase active site

The redox properties of the "dimer-of-dimers" complex, [{Mn2(mu-O)2(tphpn)}2]4+ (1) (where Htphpn = N,N,N',N'-tetra(2-methylpyridyl)-2-hydroxypropane-diamine) were investigated. The structure changes dramatically to an adamantane-shaped core upon one-electron oxidation. On the other hand, the one-electron reduced product of 1, [Mn4O4(tphpn)2]3+, exhibits a hyperfine-structured multiline EPR signal very similar to the so-called S0 state of the tetramanganese cluster, which resides at the Photosystem II water oxidase active site.     

Study of EIT resonances in an anti-relaxation coated Rb vapor cell

We study the sign of resonances obtained in electromagnetically induced transparency (EIT). Resonances of both kinds—bright (corresponding to enhanced absorption) and dark (corresponding to reduced absorption)—are obtained when the frequency of a probe beam is scanned. The experimental results, presented earlier, use magnetic sublevels of a hyperfine transition in the D₁ line of ⁸⁷Rb along with a magnetic field of 27 G. The atoms are contained in a vapor cell at room temperature, and with anti-relaxation coating on the walls. A quantitative theoretical model, which reproduces the experimental results quite well, is presented for the first time. The model solves the density matrix of the sublevels involved, and uses two regions—one with both the light and magnetic field, and the second without light and just a magnetic field. This ability to have both bright and dark resonances promises applications in sub- and super-luminal propagation of light.     

Application of wavelet filtering techniques to Lau interferometric fringe analysis for measurement of small tilt angles

This communication presents the results of investigation undertaken towards testing the viability of wavelet filtering techniques in analyzing the Lau interferometric fringes. Towards this, the applicability of Haar, Daubechies and Symlet wavelet based filtering schemes have been tested. Of these schemes, the Symlet based filtering scheme gives the best results in terms of improved signal to noise ratio. This scheme is then used to analyze Lau interferograms recorded in the experimental arrangement for tilt angle measurement. The processed interferograms yield improved accuracy and precision of measurement.