Continuous quantum phase transitions in the one-dimensional spin-1/2 axial next-nearest-neighbour Ising model in two orthogonal magnetic fields

We have investigated the one-dimensional spin-1/2 axial next-nearest-neighbour Ising (ANNNI) model in two orthogonal magnetic fields at zero temperature. There are four different possible ground state configurations for the ANNNI model in a longitudinal field, in the thermodynamic limit. The inclusion of a transverse field introduces quantum fluctuations which destroy the existing spin order along certain critical lines. The effects of the fluctuations in three of the four ordered regions were investigated using the finite-size scaling technique. The phase boundaries of the ANNNI model in two orthogonal magnetic fields were thus determined numerically. For certain limits of the Hamiltonian we compared the obtained results with the existing literature and our results were in good agreement with the results in the existing literature.     

Polycyclic nitrogen compounds. Part iii. Synthesis of 3,3a-dihydrothiazolo[3,4-α]quinoxalin-4-ones

New tricyclic quinoxalinone skeletons with bridge-head nitrogen atoms and containing sulphur in a fully-reduced five-membered ring C were obtained. 3,3a-Dihydrothiazolo[3,4-α]quinoxalin-4-ones I-III were prepared by metal-acid reductive cyclisation of N-(nitrophenyl)- and N-(dinitrophenyl)thiazolidine-4-carboxylic acids IVa,b,c. Attempts to obtain the skeleton by selective hydrogen transfer reductive cyclisation of the corresponding esters Va,b,c were unsuccessful.     

Trace elements in Nigerian oil sands and extracted bitumens

The Nigerian oil sands are very extensive with an estimated in place reserves of bitumen/heavy oil of over 30 billion barrels. Instrumental Neutron Activation Analysis (INAA) has been used to determine the trace and minor elements in the raw oil sands and bitumens. About 43 trace elements in the raw oil sands and 30 in bitumen extracts were determined. The results are compared with values of Canadian bitumens and some Nigerian conventional light crude oils. In general, the Nigerian bitumens has higher hydrocarbon concentration than the Athabasca bitumen but slightly lower than in the Nigerian crude oils. The sulphur, vanadium and nickel contents of the Nigerian bitumens and crude oils are appreciably lower than those of Athabasca bitumen, thus indicating that the extraction and refining of Nigerian tar sand oil would pose less technological and environmental problems than the Athabasca syncrude.     

Outer-Sphere electron-transfer and the effect of linkage isomerism in the titanium(III) reduction of nitro-pentacyanocobaltate(III) and nitro-, and nitrito-pentaamminecobalt(III) complexes in aqueous acidic media

The reductions of [Co(CN)₅NO₂]³⁻, [Co(NH₃)₅NO₂]²⁺ and [Co(NH₃)₅ONO]²⁺, by Ti^III in aqueous acidic solution have been studied spectrophotometrically. Kinetic studies were carried out using conventional techniques at an ionic strength of 1.0 mol dm⁻³ (LiCl/HCl) at 25.0 ± 0.1 °C and acid concentrations between 0.015 and 0.100 mol dm⁻³. The second-order rate constant is inverse—acid dependent and is described by the limiting rate law:- k₂ ≈ k₀ + k[H⁺]⁻¹,where k=k′K_a and K_a is the hydrolytic equilibrium constant for [Ti(H₂O)₆]³⁺. Values of k₀ obtained for [Co(CN)₅NO₂]³⁻, [Co(NH₃)₅NO₂]²⁺ and [Co(NH₃)₅ONO]²⁺ are (1.31 ± 0.05) × 10⁻² dm³ mol⁻¹ s⁻¹, (4.53 ± 0.08) × 10⁻² dm³ mol⁻¹ s⁻¹ and (1.7 ± 0.08) × 10⁻² dm³ mol⁻¹ s⁻¹ respectively, while the corresponding k′ values from reductions by TiOH²⁺ are 10.27 ± 0.45 dm³ mol⁻¹ s⁻¹, 14.99 ± 0.70 dm³ mol⁻¹ s⁻¹ and 17.93 ± 0.78 dm³ mol⁻¹ s⁻¹ respectively. Values of K _a obtained for the three complexes lie in the range (1–2) × 10⁻³ mol dm⁻³ which suggest an outer-sphere mechanism.     

Tabernaesine J,a Novel Vincamine-Type Indole Alkaloid with 6/5/6/6/6/5/5 Heptacyclic-Ring System Scaffold from Tabernaemontana pachysiphon

Tabernaesine J(1),an unprecedented vincamine-type indole alkaloid with 6/5/6/6/6/5/5 heptacyclic-ring system,as well as one new biogenetically related vincamine...     

Determination of swertianolin in rat plasma by LC‐MS/MS and its application to a pharmacokinetic study

A sensitive and rapid LC‐MS/MS method has been developed and validated for quantifying swertianolin in rat plasma using rutin as an internal standard (IS). Following liquid–liquid extraction with ethyl acetate, chromatographic separation for swertianolin was achieved on a C₁₈ column with a gradient elution using 0.1% formic acid as mobile phase A and acetonitrile as mobile phase B at a flow rate of 0.3 mL/min. The detection was performed on a tandem mass spectrometer using multiple reaction monitoring via an electrospray ionization source and operating in the negative ionization mode. The optimized mass transition ion pairs (m/z) for quantitation were 435.1/272.0 for swertianolin and 609.2/300.1 for IS. The lower limit of quantitation was 0.5 ng/mL within a linear range of 0.5–500 ng/mL. Intra‐day and inter‐day precision was less than 6.8%. The accuracy was in the range of ?13.9 to 12.0%. The mean recovery of swertianolin was >66.7%. The proposed method was successfully applied in evaluating the pharmacokinetics of swertianolin after an oral dose of 50 mg/kg Swertia mussotii extract in rats. Copyright © 2014 John Wiley & Sons, Ltd.     

Orientation effects in the nitration of the dithieno[b,d]pyridine N-oxides. Its dependence on acidity of the reaction medium

The nitration of three dithienopyridine-N-oxides was investigated. The regiochemistry of the reaction was dependent on the reaction conditions used. Under strongly acidic conditions the positional preference is similar for the N-oxides and free bases. However, under mildly acidic or neutral conditions a completely different substitution pattern was obtained. In the latter case those ring positions were substituted which are expected to be unfavored or forbidden in electrophilic substitution of the free bases. The structures of the nitro derivatives were proven by extensive use of ¹H and ¹³C nmr spectroscopy.     

Spectrophotometric determination of metronidazole and tinidazole via charge transfer complexation using chloranilic acid

A new spectrophotometric method was developed for the determination of two important nitroimidazoles; metronidazole (MZ) and tinidazole (TZ). The method was based on the charge-transfer (CT) complexation reaction of reduced forms of metronidazole and tinidazole as n-electron donors and chloranilic acid (CAA) as π-electron acceptor to form a purple-colored complex with a new absorption band at 520 nm which was adopted as the analytical wavelength. Molar absorptivities of 2.741 × 10² L M^?1 cm^-1 and 2.681 × 10² L M^?1 cm^?1 were obtained for MZ and TZ, respectively. Optimization of reducing agent and time of reduction revealed the superiority of metal hydrides over reducing metals. Reduction of MZ and TZ was completed at 30 °C within 10 min. Optimizations of temperature and time for the complexation reaction revealed that the reaction was completed at 30 °C within 5 min. A 60:40 mixture of 1,4-dioxane:acetonitrile was found to be the best diluting solvent for optimal detector response. The complexes were stable at room temperatures for weeks. Beer’s law was observed in the concentration of 5–40 ?g ml (MZ) and 4.8–79.2 ?g ml^?1 (TZ) with low limits of detection of 1.88 and 0.74 ?g ml^?1, respectively. Overall recoveries of MZ and TZ from quality control samples were 103.19 ± 2.05 (%RSD = 1.99, n = 12) and 101.63 ± 1.41 (%RSD = 1.39) over three days. There was no interference from commonly utilized tablet excipients. No significant difference existed between the results of the new method and the BP titrimetric procedures (p > 0.05). The new CT procedure described in this paper is simple, fast, convenient, accurate and precise and has the novelty of carrying out the reactions at room temperature compared to previously described procedures. The new method could be adopted as an alternative procedure for the quality assessment of MZ and TZ in bulk and dosage forms.     

Unsymmetrically Substituted Nickel Triazatetra-Benzcorrole and Phthalocynanine Complexes: Conjugation to Quantum Dots and Applications as Fluorescent “Turn ON” Sensors

We report on the design and application of fluorescent nanoprobes based on the covalent linking of _L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg²⁺ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg²⁺ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg²⁺ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs.     

A new spectrophotometric method for the determination of nadolol

A new spectrophotometric method has been developed for the assay of nadolol in pure form and in tablets. The assay procedure is based on a derivatization methodology employing 4-carboxyl-2,6-dinitrobenzene diazonium ion (CDNBD) as a diazo coupling reagent. The azo dye formed between nadolol and CDNBD absorbed visible light at the wavelength maximum of 416 nm (λ_max) demonstrating a bathochromic shift from the absorption maximum of nadolol. Optimization studies established an optimal reaction time of 10 min at 60 °C. The assays were linear over 1.25–10 μg ml^?1 of nadolol, and the reaction occurred by a 3:1 reagent/drug stoichiometric ratio. The method is found to be selective and has a lower detection limit of 0.29 μg ml^?1. Recovery studies over three days gave mean recovery of 101.4% (RSD 3.0%). This new method has been successfully applied in the determination of nadolol and nadolol/bendroflumethiazide tablets with accuracy and precision similar to the official (USP) HPLC procedure (p > 0.05). The new procedure has the advantages of high sensitivity, lower limit of detection and could find application as an in-process quality control method for nadolol.