A schematic overview of the historical evolution of Analytical Chemistry

The historical evolution of Analytical Chemistry is briefly discussed as related to the progress of Chemistry within the 16–19th centuries under the leadership of Paracelsus, Boyle, Lavoisier and Dalton. A clear distinction is made between chemical analysis (up to the end of the 19th c.) and today’s Analytical Chemistry, paying close attention to a number of aspects and consequences related to the chemical revolution which took place at the overlap of the 18–19th c. which resulted in the quantification of Chemistry, causing increasing development and improvement of the chemical metrology which was an essential factor for Chemistry to acquire a scientific dimension and to become more specialised during the 19th century. A panoramic view of the whole development is presented by resorting to the inclusion of a number of synoptical tables outlining the stepwise progress of Chemistry, chemical analysis and Analytical Chemistry within the five last centuries taking into consideration the main protagonists involved as well as the experimental means, techniques and methodologies used and/or developed. Received: 20 February 1996 / Accepted: 21 May 1996     

Strained aromatic oligoamide macrocycles as new molecular clips

Can one join both ends of a helix? A helical aromatic oligoamide was macrocyclized into a saddle-shaped bifunctional clip molecule that self-assembles into discrete circular dodecamers in the solid state and shows great potential for binding aromatic acid guests in solution. The cyclization step requires that the helix is only partly denatured in the reaction medium.     

First-principles calculations of K-edge X-ray absorption near edge spectra of some transition metal dimers

Theoretical X-ray absorption near-edge spectra have been evaluated for different bond lengths of Mn₂, Co₂ and Ni₂ using a modified Xα scattered-wave procedure.     

Mercury removal from aqueous and organo-aqueous solutions by natural Mexican erionite

The sorption of Hg(II) from aqueous and organo aqueous solutions was investigated by Mexican natural erionite. The mercury chemical species (anionic, cationic or neutral) were determined by high voltage electrophoresis, and the mercury chemical species present in the aqueous media were simulated by a program MEDUSA. The mercury sorption process was monitored during 48 hours. The mercury content was determined by neutron activation analysis. Mixtures of benzene/water[Hg(II)], toluene/water[Hg(II)] and ethanol/water[Hg(II)] were chosen as organo-aqueous media. It was found that both the mercury chemical species and the dielectric constant of solvents play an important role in the mercury sorption by erionite.     

Photophysics and redox behavior of chiral transition metal polymers

The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)]](PF(6))(4) and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n) were shifted to lower energies and also exhibited significantly longer luminescence lifetimes when compared to [Ru((-)-ctpy)(2)](PF(6))(2), [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), and ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n). In terms of their electrochemical behavior, all of the complexes studied exhibited one Ru-centered and two ligand-centered redox waves and the [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n), and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n)() complexes were found to electrodeposit upon ligand-based reduction. The difference between the formal potentials of the Ru-centered and the first ligand-centered (least negative) waves corresponded linearly with the changes in the observed emission energies. The shifts in energy are discussed using a particle-in-a-box model, and the luminescence lifetimes are discussed in terms of the structure of the excited-state manifold.     

Synthesis of 5-(4,6-dimethyl-2-pyrimidinyl)-1,3,4-oxadiazole-2-thione and its alkylation,aminomethylation, and acylation

The reaction of the hydrazide of 4,6-dimethyl-2-pyrimidinecarboxylic acid with potassium ethylxnthate gave 5-(4,6-dimethyl-2-pyrimidinyl)-1,3,4-oxadiazole-2-thione. The alkylation of this product in an alkaline medium proceeds at the sulfur atom, while the aminomethylation and acylation proceed at the nitrogen atom. The major criterion for the structure of the S- and N-derivatives is the chemical shift of C₍₂₎ in the 1,3,4-oxadiazole ring in the ¹³C NMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 700–705, May, 1993.     

Allocolchicinoid synthesis via direct arylation

[reaction: see text] A formal enantioselective synthesis of allocolchicine and a synthesis of a C-ring analogue have been achieved by employing an intramolecular direct arylation of an aryl chloride to form the biaryl carbon-carbon bond and the seven-membered ring.     

Dosage de traces de fer total dans les vins

Résumé Le dosage électrophotocolorimétrique des traces de fer total dans les vins au moyen de l'orthophénanthroline a été peu étudié jusqu'à présent. Sous un titre général le mémoire expose les conclusions auxquelles ont abouti diverses recherches consacrées à l'étude du dosage en question. L'application raisonnée de la méthode deBencze a permis d'établir une technique d'évaluation photocolorimétrique du fer dans les vins et les jus de fruits. Intéressante par sa simplicité et sa rapidité d'exécution, la technique en question indique le moyen de doser cet élément directement dans les liquides obtenus à partir des vins, suivant le procédé du traitement oxydatif au perhydrol. Ce traitement a permis de revaloriser le dosage du fer au point de vue de la rapidité par rapport à la minéralisation sèche, sans apporter en même temps des complications dans les manipulations analytiques et sans affecter la sensibilité et la précision de la réaction colorimétrique.

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Summary There has been little study of the electrophotocolorometric determination of the total iron content of wines by means of orthophenanthroline. Under a general title, the paper gives the general conclusions reached as a result of various studies of this determination. An intelligent application of theBencze method has resulted in a photocolorimetric evaluation of iron in wines and fruit juices. Characterized by simplicity and rapidity, this technique provides a means of determining this element directly in the liquids obtained from wines after oxidative treatment with perhydrol. This procedure compares, favorably with respect to speed with mineralization by the dry method, but is free from the complications in the analytical manipulations and there is no adverse effect on the sensitivity and the precision of the colorimetric reaction.

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Zusammenfassung Die elektrokolorimetrische Bestimmung der geringen Gesamtmengen an Eisen in Wein mit Hilfe von o-Phenanthrolin wurde bisher nur wenig untersucht. Die beim Studium dieses Verfahrens gesammelten Erfahrungen werden in Form eines allgemeinen Überblicks mitgeteilt. Die Anwendung der Methode vonBencze führte zur Ausarbeitung einer Arbeitsvorschrift zur kolorimetrischen Bestimmung des Eisens in Wein und Fruchtsäften. Diese ist wegen der Einfachheit und Geschwindigkeit ihrer Durchführung von praktischem Interesse. In der durch Oxydation des Weines mit Wasserstoffperoxyd erhaltenen Lösung kann das Eisen unmittelbar bestimmt werden. Diese Art des Aufschlusses ist besser geeignet als die trockene Veraschung, ohne die Empfindlichkeit oder die Genauigkeit der Farbreaktion zu beeinträchtigen.

     

Mass spectra of the coordination compounds of nickel with the tetradentate Schiff bases of S-substituted thiosemicarbazides with 2,4-pentanedione and 3-oxo-2,4-pentanedione

The mass spectra of the coordination compounds of nickel(II) with the bis-S-substituted thiosemicarbazones of 2,4-pentanedione (R₂H₂L) with the general formula [NiR₂HL]X and of 3-oxo-2,4-pentanedione (H₂R₂LO) with the general formula NiR₂LO were studied. A distinguishing feature of the mass spectra of [NiR₂HL]X is the absence of molecular ion peaks. The initial point of fragmentation is the [M - HX] ions. The strongest lines in spectra of NiR₂LO are those due to the elimination of R and R-H. At the first stage the fragmentation of all the investigated compounds takes place mainly through only one of the thiosemicarbazide residues. At the second stage the 2,4-pentanedione (3-oxo-2,4-pentanedione) residue is eliminated, after which the remaining thiosemicarbazide part dissociates. A significant part of the fragmentation paths was confirmed by the peaks of the metastable ions and also by the mass spectra of the deuterated analogs.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 2, 205–211, March–April, 1991. Original article submitted August 19, 1986.