Synthesis and antitumor activity of new thiosemicarbazones of 2‐acetylimidazo[4,5‐b]pyridine

A number of thiosemicarbazones of 2‐acetyl‐imidazo[4,5‐b]pyridine were prepared in order to investigate their in vitro antineoplastic activities. Three compounds: (i) 2‐acetylimidazo[4,5‐b]pyridin‐4‐ sec ‐butyl‐3‐thiosemicarbazone [(A₇), NSC674098], (ii) 2‐acetylimidazo[4,5‐b]pyridin‐4‐tert‐butyl‐3‐thiosemi‐carbazone [(A₉), NSC674099], (iii) 2‐acetylimidazo[4,5‐b]pyridin‐4‐cyclohexyl‐3‐thiosemicarbozone [(A₁₁), NSC674101] showed remarkable activity against some of the cell lines tested. The Biological Evaluation Committee of N.C.I. determined that further secondary testing should be carried out (these compounds were tested against prostate cancer).     

A multi-parametric programming approach for multilevel hierarchical and decentralised optimisation problems

In this paper, we outline the foundations of a general global optimisation strategy for the solution of multilevel hierarchical and general decentralised multilevel problems, based on our recent developments on multi-parametric programming and control theory. The core idea is to recast each optimisation subproblem, present in the hierarchy, as a multi-parametric programming problem, with parameters being the optimisation variables belonging to the remaining subproblems. This then transforms the multilevel problem into single-level linear/convex optimisation problems. For decentralised systems, where more than one optimisation problem is present at each level of the hierarchy, Nash equilibrium is considered. A three person dynamic optimisation problem is presented to illustrate the mathematical developments.     

Development and validation of a rapid HPLC method for the determination of five banned fat-soluble colorants in spices using a narrow-bore monolithic column

This work reports a fast and simple liquid chromatographic method for the simultaneous determination of five banned fat-soluble synthetic colorants, namely Sudan I-IV and Para-Red, in spice samples. The analytes were successfully separated isocratically in less than 5 min on the new narrow bore monolithic column, FastGradient^® Chromolith (50 mm × 2.0 mm i.d.) using a mobile phase of 0.1% (v/v) HCOOH/acetonitrile (35/65%, v/v) at a flow rate of 1.5 mL min⁻¹. All colorants were detected at 506 nm. The main parameters (mobile phase composition, flow rate, injection volume) affecting the separation were studied. The proposed method was thoroughly validated in terms of linearity, LODs, precision and accuracy. The method was applied to the determination of the studied azo-dyes in various spices (paprika, chilli and mixed spice powders) after ultrasound-assisted extraction. Satisfactory recoveries, ranging from 92% to 109% were obtained.     

Interpolymer association between hydrophobically modified poly(sodium acrylate) and poly(N-isopropylacrylamide) in water: The role of hydrophobic interactions and polymer structure

The association between hydrophobically modified poly(sodium acrylate) (HMPA) and poly(N-isopropylacrylamide) (PNIPAM) in aqueous solution was studied using turbidimetry, viscometry and fluorescence measurements. Both the polymeric and the amphiphilic nature of the HMPA influence the association process. The tendency for association, as reflected by the increase in the cloud point and the reduced viscosity of PNIPAM, increases with the length of the alkyl group and the degree of substitution of HMPA. The fluorescence study, using pyrene as a probe, ascertains that the association is of hydrophobic nature and the association process is gradual and less cooperative than the association of PNIPAM with ionic surfactants. When high molar mass HMPA is used, the hydrophobic association between HMPA and PNIPAM leads to the formation of a reversible network with significantly enhanced thickening properties as compared to the thickening ability of the corresponding pure HMPA in aqueous solution.     

Twisting stresses in tape

An analysis is presented of the stresses induced in a thin tape by bending over pulleys, by axial tension and by twisting of the tape when running between two out-of-plane pulleys. Analytical results are compared with some photoelastic tests on tape models made of epoxy resin. The weak retardation produced by the thin tape is multiplied by repeated light passage through the tape and is measured by a bent-beam compensator. The tests are of especial interest because the rate of rotation of the principal stresses is higher than had been encountered before. Surprisingly, the experimental results uncorrected for rotation are in good agreement with the calculated stresses.     

Bonding and ion-ion interactions of Mn ions in fluoride-phosphate and boro-silicate glasses probed by EPR and fluorescence spectroscopy

Electron paramagnetic resonance (EPR) and fluorescence spectroscopy are sensitive and selective methods for probing coordination and bonding of Mn²⁺ ions in glasses. Both methods provide additional information on Mn-Mn ion interactions and cluster formation. Mn²⁺ was found to be tetrahedrally coordinated in boro-silicate glasses of high optical basicity, and octahedrally coordinated in low alkaline boro-silicate glasses (duran-type) as in fluoride-phosphate glasses. Broad emission bands and multicomponent fluorescence decay curves in duran glasses indicate very strong Mn-Mn ion interactions and the presence of multiple Mn²⁺ sites. Site distribution is more homogenous in metaphosphate glasses, though concentration quenching is apparent at high Mn-levels. As the Mn-content increases the EPR spectra show exchange narrowing due to a decrease in the Mn-Mn distances in the duran series, but show extreme linewidth broadening due to increased cluster sizes at constant Mn-Mn distances for metaphosphate glasses. For the fluoride-phosphate and boro-silicate systems investigated, fluorescence lifetimes are found to decrease as the wavelength of the emission maximum increases and with increasing g-values of the sextet at g = 2. For octahedral coordination of Mn²⁺ ions the EPR hyperfine splitting constant decreases linearly with increasing optical basicity, as a result of an increasing covalent character of the Mn²⁺-ligand bond.     

A “Discretization” Technique for the Solution of ODEs II

A functional analytic technique was recently presented for finding discrete equivalent counterparts of initial value problems of ODEs and obtaining their real analytic solutions. In the current paper, this technique is extended to boundary value problems of ODEs and to the complex solutions of ODEs. In order to demonstrate this technique, it is applied to the classic Blasius problem of fluid mechanics. Apart from its real solution, its complex solution is also studied. The obtained results indicate that the complex Blasius function exhibits an oscillatory behavior and strengthen a conjecture regarding its singularities in the complex plane.     

Adjustable robust optimization through multi-parametric programming

Adjustable robust optimization (ARO) involves recourse decisions (i.e. reactive actions after the realization of the uncertainty, ‘wait-and-see’     

A “discretization” technique for the solution of ODEs

A functional-analytic technique was developed in the past for the establishment of unique solutions of ODEs in H₂(D) and H₁(D) and of difference equations in ?₂ and ?₁. This technique is based on two isomorphisms between the involved spaces. In this paper, the two isomorphisms are combined in order to find discrete equivalent counterparts of ODEs, so as to obtain eventually the solution of the ODEs under consideration. As an application, the Duffing equation and the Lorenz system are studied. The results are compared with numerical ones obtained using the 4th order Runge-Kutta method. The advantages of the present method are that, it is accurate, the only errors involved are the round-off errors, it does not depend on the grid used and the obtained solution is proved to be unique.     

Synthesis and characterization of novel 99gTc(V) and Re(V) complexes with water-soluble tetraaza diamido dipyridino ligands: single-crystal X-ray structural investigations of mono- and dinuclear complexes

Rhenium and technetium are known for their useful applications in nuclear medicine with similar properties. In this study, new diamido dipyridino (N(4)) water-soluble ligands (2-C(5)H(4)NCH(2)NHCO)(2)CH(2), 1 (L(1)H2), (2-C(5)H(4)NNHNHCO)(2)CH(2), 2, and [2-C(5)H(4)N(+)(O)(-)CH(2)NHCO](2)CH(2), 3, were synthesized. Reaction of L(1)H2 with ReOCl(3)(PPh(3))(2) resulted in the novel six-coordinated rhenium(V) complex, trans-ReO(L(1))(OEt), 4. The complex was characterized by spectroscopic methods, and its X-ray crystallographic analysis revealed that rhenium is coordinated to four nitrogen atoms of the ligand and to two oxygen atoms from the deprotonated ethanol and the oxo group respectively in a distorted octahedral geometry. In solution, complex 4 was transformed to a new complex 5, which was proved to be the dinuclear complex mu-oxo [ReO(L(1))](2)O. Reaction of 1 with [n-Bu(4)N][ReOCl(4)] resulted in the neutral complex 6, trans-[ReO(L(1))]Cl. Similarly, when ligand 1 was reacted with [n-Bu(4)N][(99g)TcOCl(4)], the neutral trans-[(99)TcO(L(1))]Cl complex 7 was formed, which upon dissolution transformed into a cationic complex 8, trans-[(99)TcO(L(1))(OH(2))](+)Cl(-). The single-crystal X-ray structure of 8 reveals that the coordination sphere about technetium is a distorted octahedron with four nitrogen atoms in the equitorial plane, while doubly bonded oxygen and coordinated water occupy the apical positions. Further dissolution of 8 resulted in the formation of dinuclear mu-oxo [TcO(L(1))](2)O, 9. This study shows that Tc and Re have similar metal core structures in solution for diamido dipyridino systems, besides similarity in geometrical structure, proved by the X-ray structures on the same ligands.