First palladium(II) and platinum(II) complexes from employment of 2,6-diacetylpyridine dioxime: synthesis, structural and spectroscopic characterization, and biological evaluation

Employment of the monoanion of 2,6-diacetylpyridine dioxime (dapdoH(2)) as a tridentate chelate in palladium(II) and platinum(II) chemistry is reported. The syntheses, crystal structures, spectroscopic and physicochemical characterization, and biological evaluation are described of [PdCl(dapdoH)] (1) and [PtCl(dapdoH)] (2). Reaction of PdCl(2) with 2 equivs of dapdoH(2) in MeOH under reflux gave 1, whereas the same reaction with PtCl(2) in place of PdCl(2) gave 2 in comparable yields (70-80%). The divalent metal center in both compounds is coordinated by a terminal chloro group and a N,N',N"-tridentate chelating (η(3)) dapdoH(-) ligand. Thus, each metal ion is four coordinate with a distorted square planar geometry. Characterization of both complexes with (1)H and (13)C NMR and UV-vis and electrospray ionization mass spectroscopies confirmed their integrity in DMSO solutions. Interaction of the complexes with human and bovine serum albumin has been studied with fluorescence spectroscopy, revealing their affinity for these proteins with relatively high values of binding constants. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they can bind to CT DNA, and the corresponding DNA binding constants have been evaluated. Cyclic voltammograms of the complexes in the presence of CT DNA solution have shown that the interaction of the complexes with CT DNA is mainly through intercalation, which has been also shown by DNA solution viscosity measurements. Competitive studies with ethidium bromide (EB) have revealed the ability of the complexes to displace the DNA-bound EB, suggesting competition with EB. The combined work demonstrates the ability of pyridyl-dioxime chelates not only to lead to polynuclear 3d-metal complexes with impressive structural motifs and interesting magnetic properties but also to yield new, mononuclear 4d- and 5d-metal complexes with biological implications.     

Warfarin Sodium Stability in Oral Formulations

Warfarin sodium is a low-dose pharmaceutical blood thinner that exists in two forms: the clathrate form and the amorphous form. In commercially available warfarin sodium oral suspension, the active pharmaceutical ingredient (API) is added in the amorphous state. This study investigates the apparent instability of the commercially available warfarin liquid oral formulation using Raman and IR spectroscopy, X-ray diffraction, differential scanning calorimetry, UV spectroscopy, and optical microscopy. Warfarin, not its sodium salt, was identified as the undissolved solid existing in the suspension. This was found to be due to the dissociation of sodium salt and the protonation of the warfarin ion in the liquid phase, which triggered the crystallization of the sparingly soluble unsalted form. The coexistence of protonated and unprotonated warfarin ions in the supernatant, as detected by Raman and UV spectroscopy, confirmed this assumption. Study of the dissolution of warfarin sodium amorphous salt and crystalline sodium clathrate in the placebo and pure water verified the results. The effect of pH and temperature on warfarin precipitation was also explored.     

A multicriteria accreditation system for information technology skills and qualifications

Employees must acquire new competences and qualifications throughout their lives, in order to be able to deal with the multiple changes in the labour market. The specific knowledge and competences, acquired either formally or non-formally, must be recognized so that they can be transferred and utilized. The existing titles of studies and accreditation mechanisms do not generally cover this need. This paper aims to propose an integrated approach for the evaluation of information technology knowledge and skills, regardless of where and how they have been acquired, so as to apply a continuous education and training policy. The proposed multicriteria methodology for the evaluation of qualifications and skills concerns candidates wishing to be accredited in an information technology specialization or profession. The methodology refers to the evaluation of the professional experience, studies and vocational training of the candidates for accreditation. It contains the analysis and modelling of the qualitative criteria as well as the implementation of multicriteria aggregation–disaggregation techniques attributing value to each criterion. Then, the candidates are classified in categories of professionals using the Electre Tri method, accepting as input data the multicriteria assessments on each criterion. The proposed evaluation approach has been adapted to the Greek educational system and is applied to a specific example of candidate.     

Performance of octene in fluorous biphasic hydroformylation: octene distribution and reversible transfer between perfluoromethylcyclohexane and nonanal

During fluorous biphasic hydroformylation 1-octene is transferred from the fluorous into the organic product phase and then from the product layer back to the fluorous layer again, due to the immiscibility of nonanal with PFMCH. The effect of the temperature and the total amount of octene on the above behaviour were also studied.     

Synthesis,Kinetic and Conformational Studies of 2-Substituted-5-(β-d-glucopyranosyl)-pyrimidin-4-ones as Potential Inhibitors of Glycogen Phosphorylase

Dysregulation of glycogen phosphorylase, an enzyme involved in glucose homeostasis, may lead to a number of pathological states such as type 2 diabetes and cancer, making it an important molecular target for the development of new forms of pharmaceutical intervention. Based on our previous work on the design and synthesis of 4-arylamino-1-(β-d-glucopyranosyl)pyrimidin-2-ones, which inhibit the activity of glycogen phosphorylase by binding at its catalytic site, we report herein a general synthesis of 2-substituted-5-(β-d-glucopyranosyl)pyrimidin-4-ones, a related class of metabolically stable, C-glucosyl-based, analogues. The synthetic development consists of a metallated heterocycle, produced from 5-bromo-2-methylthiouracil, in addition to protected d-gluconolactone, followed by organosilane reduction. The methylthio handle allowed derivatization through hydrolysis, ammonolysis and arylamine substitution, and the new compounds were found to be potent (μM) inhibitors of rabbit muscle glycogen phosphorylase. The results were interpreted with the help of density functional theory calculations and conformational analysis and were compared with previous findings.     

Synthesis of novel pyridocoumarins and benzo-fused 6-azacoumarins

Benzo[7,8]-fused 6-azacoumarins are prepared from 4-quinolinol by treatment with PPh₃ and DMAD, or from 3-formyl-4-quinolinol by Wittig reaction with carbalkoxyalkylidene(triphenyl)phosphoranes. Angular pyridocoumarins are prepared from 8- or 6-quinolinols with PPh₃ and DMAD, or from the reactions of 5,6- or 7,8-quinolinediones with carbalkoxymethylene(triphenyl)phosphoranes.     

Pyrolytic degradation of common polymers present in packaging materials

Journal of Thermal Analysis and Calorimetry - Pyrolysis of polymers with widespread use, such as PET, HDPE, PVC, LDPE, PP and PS, been utilized extensively as plastic packaging materials, is the...     

Reactions of 2,3-bishydroxyimino-1,2,3,4-tetrahydro-quinoxalines and 2,3-bishydroxyimino-2,3-dihydro-4H-1,4-benzoxazines with ethyl chloroformate

Bishydroxyiminoquinoxalines 3a-b react with ethyl chloroformate 4 to afford the furazano[3,4-b]quinoxalines 5a-b . Bishydroxyiminobenzoxazines 6a-c on treatment with 4 are converted into the fused oxadiazolones 7a-c and 8a-c along with the bisethoxycarbonyloxyimino-derivatives 9a-c . From the reactions of 4 with the oxanilide dioximes 12a-c compounds 13a-c and 14a-b are obtained.