A mesh microcontactor for 2-phase reactions

The design, fabrication and use of mesh microcontactor structures is described. These allow contact between immiscible fluid phases (liquid/liquid or gas/liquid) enabling mass transfer and reaction between and within the phases. The phases are not mixed and are removed separately for subsequent use or analysis. The structures were designed for kinetic studies on biphasic reactions with the ability to handle sequential samples without excessive sample dispersion. Mass transport conditions are defined by fluid layer depths of 100 microm and the volume for each phase contacting in the reaction region was selected at 100 microl as sufficient for a range of analytical techniques. Micromeshes with pore diameter, depth, and spacing each of approximately 5 microm were formed by electrodeposition of nickel onto substrates with defined photoresist layers, and released by etching a copper sub-layer. Reactor enclosures defining chambers on each side of the mesh were formed from milled glass and metal components. The assembled structures have been used in flow-through and static fluid modes. System function has been demonstrated for both liquid/liquid and gas/liquid reactions. Test chemistries selected for ease of optical monitoring were hydrolysis of colourless fluorescein diacetate in toluene with transfer as fluorescein anion to aqueous alkali, and oxygen absorption into aqueous alkaline pyrogallol solution generating a coloured product, purpurogallin.     

Three novel tetracyclic triterpenoids of biogenetic interest from the leaves of Azadirachta indica

From the methanolic extract of Azadirachta indica leaves, we have isolated three new tetracyclic triterpenoids of biogenetic interest, namely, melianol 1, desfurano-desacetylnimbin-17-one 2 and meliatetraone 3. The structure elucidation is based on extensive spectral studies including ¹H–¹H-COSY, NOESY, HMQC, and HMBC experiments.     

Preparation, structure and spasmolytic activities of some derivatives of harmine series of alkaloids

Keeping in view the interesting chemistry and pharmacological importance of harmine series of bases -- the beta-carboline alkaloids, a number of new derivatives of tetrahydroharmine and harmalol have been prepared and characterized through spectral studies. Some of these derivatives showed spasmolytic activity. It was observed that all the N-acyl tetrahydroharmine derivatives are stable, not labile and no ring opening occurs in these compounds, as reported recently.     

Solvable dynamics of N driven two-level atoms coupled to a dissipative cavity mode

We solve exactly the dynamics of N strongly driven two-level atoms equally coupled on resonance to a dissipative cavity mode. Analytical results are derived on decoherence, entanglement, purity, atomic correlations and cavity field mean photon number. Decoherence-free subspaces are predicted for the whole system and the N-qubit subsystem. Multi-partite entangled states and cavity cat-like states can be conditionally generated. The decay of quantum coherence and purity can be monitored by joint measurements on atomic populations. Atoms prepared in states invariant under permutation of any two components evolve within the subspace spanned by the completely symmetric Dicke states. Applications to N = 3, 4 are discussed.     

Group actions on graphs related to Krishnan-Sunder subfactors

We describe the principal graphs of the subfactors studied by Krishnan and Sunder in terms of group actions on Cayley-type graphs. This leads to the construction of a tower of tree algebras, for every positive integer , which are symmetries of the Krishnan-Sunder subfactors of index . Using our theory, we prove that the principal graph of the irreducible infinite depth subfactor of index 9 constructed by Krishnan and Sunder is not a tree, contrary to their expectations. We also show that the principal graphs of the Krishnan-Sunder subfactors of index 4 are the affine A and D Coxeter graphs.

     

Substrate-binding in quinoprotein ethanol dehydrogenase from pseudomonas aeruginosa studied by electron paramagnetic resonance at 94 GHz

Pyrroloquinoline quinone (2,7,9-tricarboxypyrroloquinoline quinone, PQQ) is one of several quinone cofactors that is utilized in a class of dehydrogenases known as quinoproteins. In this contribution, we have used continuous-wave high-field/high-frequency electron paramagnetic resonance (EPR) at 94 GHz (W-band) to study substrate binding in ethanol dehydrogenase (QEDH) from Pseudomonas aeruginosa, taking advantage of the fact that the enzyme is isolated with a substantial proportion of the PQQ cofactor in the paramagnetic semiquinone form. In the substrate-free enzyme, the principal values of the g-tensor, obtained by spectral simulation are: gx = 2.00585(2), gy = 2.00518(2), and gz = 2.00212(2), giving giso = 2.00438(2). All three principal values of the g-tensor decrease when ethanol is bound to the protein: gx = 2.00574(2), gy = 2.00511(2), and gz = 2.00207(2), giving giso = 2.00431(2). The results represent the first direct evidence for the tight binding of an alcohol to a PQQ-dependent alcohol dehydrogenase and show that ethanol also binds to the enzyme even when the PQQ cofactor is in the semiquinone form. The decrease in g is consistent with an increase in polarity in the immediate vicinity of the PQQ cofactor and probably reflects a changed geometry of the PQQ-Ca2+ complex when ethanol binds.     

The chemistry of THPC–urea polymers and relationship to flame retardance on wool and wool-polyester blends. I. Chemistry of THPC–urea polymers

Polymer formation from THPOH-urea, THPOH-dichloropropanol-urea, and THPC-urea was studied. Order and rate of urea addition were shown to influence insoluble polymer yields as well as polymer structure. The polymers were characterized by elemental analyses and infrared spectroscopy, and predominant structures proposed. The structures were correlated with thermogravimetric and differential scanning calorimetry data and probable thermal decomposition paths.     

A simple, rapid and mild one pot synthesis of benzene ring acylated and demethylated analogues of harmine under solvent-free conditions

A simple, rapid, solvent-free, room temperature one pot synthesis of benzene ring acylated and demethylated analogues of harmine using acyl halides/acid anhydrides and AlCl(3) has been developed. Eight different acyl halides/acid anhydrides were used in the synthesis. The resulting mixture of products was separated by column chromatography to afford 10- and 12-monoacyl analogues, along with 10,12-diacyl-11-hydroxy products. In five cases the corresponding 10-acyl-11-hydroxy analogues were also obtained. Yields from the eight syntheses (29 products in total) were in the 6-34% range and all compounds were fully characterized.     

Isolation and structure determination of two new constituents from the fruits of Morinda citrifolia Linn

Studies on the chemical constituents of the fruits of Morinda citrifolia Linn. have led to the isolation of two new compounds, morinaphthalene (=1,3,6,7-tetrahydroxy-2-hydroxymethyl-1,2,3,4-tetrahydronaphthalene, (1); and morindafurone (=5-hydroxy-1,10b-dihydro-6H-anthra [1,9-bc] furan-6-one, (2); as well as two known constituents, 1,8-dihydroxy-6-methoxy-3-methyl-9-anthrone (3) and 2,4-dimethoxy-9-anthrone (4). Their structures were elucidated by spectral analysis including 2D NMR techniques.