Multi-analyte HPLC–DAD Method for Concurrent Analysis of Six Antimicrobials and Three Proton Pump Inhibitors Frequently used in Management of Helicobacter pylori Infection: Application to Simulated Intestinal Fluid Samples

Chromatographia - The present work deals with the optimization, validation and application of a versatile HPLC–DAD method for concurrent estimation of nine antimicrobials and proton pump...     

A second-order accurate numerical method for a fractional wave equation

We study a generalized Crank–Nicolson scheme for the time discretization of a fractional wave equation, in combination with a space discretization by linear finite elements. The scheme uses a non-uniform grid in time to compensate for the singular behaviour of the exact solution at t = 0. With appropriate assumptions on the data and assuming that the spatial domain is convex or smooth, we show that the error is of order k ² + h ², where k and h are the parameters for the time and space meshes, respectively.     

Site-to-site peptide transport on a molecular platform using a small-molecule robotic arm

Peptides attached to a cysteine hydrazide ‘transporter module’ are transported selectively in either direction between two chemically similar sites on a molecular platform, enabled by the discovery of new operating methods for a molecular transporter that functions through ratcheting. Substrate repositioning is achieved using a small-molecule robotic arm controlled by a protonation-mediated rotary switch and attachment/release dynamic covalent chemistry. A polar solvent mixtures were found to favour Z to E isomerization of the doubly-protonated switch, transporting cargo in one direction (arbitrarily defined as ‘forward’) in up to 85% yield, while polar solvent mixtures were unexpectedly found to favour E to Z isomerization enabling transport in the reverse (‘backward’) direction in >98% yield. Transport of the substrates proceeded in a matter of hours (compared to 6 days even for simple cargoes with the original system) without the peptides at any time dissociating from the machine nor exchanging with others in the bulk. Under the new operating conditions, key intermediates of the switch are sufficiently stabilized within the macrocycle formed between switch, arm, substrate and platform that they can be identified and structurally characterized by ¹H NMR. The size of the peptide cargo has no significant effect on the rate or efficiency of transport in either direction. The new operating conditions allow detailed physical organic chemistry of the ratcheted transport mechanism to be uncovered, improve efficiency, and enable the transport of more complex cargoes than was previously possible.

Peptides are transported in either direction between chemically similar sites on a molecular platform, substrate repositioning is achieved using a cysteine hydrazide transporter module and a small-molecule robotic arm controlled by a rotary switch.     

Thermodynamic studies on the ferroelectric phase transition in neutron irradiated (LixK1−x)2SO4 crystals at high temperature

Thermodynamic studies of (Li_xK_1?x)₂SO₄, LKS, mixed crystals have been made in the concentration range (x=0.1, 0.2, ...,x=0.5). The thermal behaviour has been investigated by differential thermal analysis, DTA, and differential scanning calorimeter, DSC, in the vicinity of high temperature phases. Also, the effect of the thermal neutron irradiations on the thermal properties of mixed crystals was studied. The results showed a change in the transition temperatureT _c, as well as the value of specific heatC _p at transition temperature, due to the change of stoichiometric ratio and radiation doses. The change of enthalpy and entropy of mixed crystals have been estimated numerically.     

Highly selective asymmetric acetate aldol reactions of an N-acetyl thiazolidinethione reagent

[reaction: see text] A highly diastereoselective acetate aldol reaction that uses a tert-leucine-derived thiazolidinethione auxiliary and dichlorophenylborane has been developed. The reaction proceeds in excellent yields and with high diastereoselectivities (drs range from 9.5:1 to >100:1).     

Shift to Pseudomonic acid B production in P. fluorescens NCIMB10586 by mutation of mupirocin tailoring genes mupO, mupU, mupV, and macpE

Mupirocin, a polyketide-derived antibiotic from Pseudomonas fluorescens NCIMB10586, is a mixture of pseudomonic acids (PA) that target isoleucyl-tRNA synthase. The mup gene cluster encodes both type I polyketide synthases and monofunctional enzymes that should play a role during the conversion of the product of the polyketide synthase into the active antibiotic (tailoring). By in-frame deletion analysis of selected tailoring open-reading frames we show that mupQ, mupS, mupT, and mupW are essential for mupirocin production, whereas mupO, mupU, mupV, and macpE are essential for production of PA-A but not PA-B. Therefore, PA-B is not simply produced by hydroxylation of PA-A but is either a precursor of PA-A or a shunt product. In the mupW mutant, a new metabolite lacking the tetrahydropyran ring is produced, implicating mupW in oxidation of the 16-methyl group.     

Synthesis and Properties of Mononuclear and Homobinuclear Chelates of Mn(II), Co(II), Ni(II), and Cu(II) with Phthalein Purple

Mono- and homobinuclear complexes of Mn(II), Co(II), Ni(II), and Cu(II) with phthalein purple are prepared and characterized by elemental analysis, thermal studies (TGA and DTA), spectral methods (IR, UV/Vis, and ESR), magnetic moment determination, and electrochemical reduction (DC polarography at DME and CV at HMDE). Thermal degradation of the complexes was studied by TGA and DTA where some thermodynamic parameters were determined. The mode of bonding and geometry of the complexes were determined from the spectral studies. Magnetic moment values showed some antiferromagnetism in the homobinuclear complexes. The reduction of the metal ions proceeds to the metallic state along an irreversible process.     

Effect of an admixture on the electrical and thermal properties of triglycine sulphate crystals

The influence of chloroacetic acid amide (AC) on the temperature-dependence of the electrical conductivity (), thermal expansion (_ij) and specific heat ((C _p) of triglycine sulphate crystals was studied in the phase transition range (T _c=49°). The addition of isostructural AC increased the electrical conductivity, decreased the thermal expansion and changed theC _p peak. The mechanism is discussed on a thermodynamic basis.

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Zusammenfassung Der Einfluß der Zumischung von Chloressigsäureamid (AC) auf die Temperaturabhängigkeit der elektrischen Leitfähigkeit, der Wärmeausdehnung _ij und der spezifischen WärmeC _p von Triglycinsulfat-Kristallen wurde im Phasenübergangsgebiet (T _c=49 °C) untersucht. Die Beimischung von isostrukturellem AC erhöht die elektrische Leitfähigkeit und vermindert die Wärmeleitfähigkeit, während derC _p-Peak verändert wird. Der Mechanismus kann thermodynamisch diskutiert werden.

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(), () _ij) () , T _c=49°. , , , , C _p. .

     

UV-vis, IR and 1H NMR spectroscopic studies of some mono- and bis-azo-compounds based on 2,7-dihydroxynaphthalene and aniline derivatives

The absorption spectra of mono- and bis-azo-derivatives obtained by coupling the diazonium salts of aromatic amines and 2,7-dihydroxynaphthalene have been studied in six organic solvents. The different absorption bands have been assigned and the effect of solvents on the charge transfer band is also discussed. The diagnostic IR spectral bands and 1H NMR signals are assigned and discussed in relation to molecular structure. Also, semi-empirical molecular orbital calculations using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory have been performed to investigate the molecular and electronic structures of these compounds. According to these calculations, an intramolecular hydrogen bonding is essential for stabilization of such molecules.