Synthesis and characterization of chitosan-graft-polycaprolactone copolymers

The graft copolymers of chitosan with polycaprolactone (PCL) were prepared through a protection-graft-deprotection route using phthaloylchitosan as intermediate. PCL macromonomers terminated with isocyanate groups reacted with hydroxyl groups of phthaloyl-protected chitosan regioselectively, and then phthaloyl groups were deprotected to give the free amino groups. The graft reaction was carried out in homogeneous system and yielded copolymers with high grafting content due to solubilization. FTIR, NMR and XRD were detected to characterize the resultant chitosan-graft-PCL copolymers.     

Electrophilic isomerization of fluoroaliphatic oxygen-containing compounds

An unusual electrophilic cyclization of fluorine-containing carbonyl compounds and -oxides was discovered. Upon the action of SbF₅, perfluorinated ketones, diketones, and -oxides isomerize to oxolanes. This reaction proceeds with the obligatory participation of the terminal CF₃ group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2611–2618, November, 1991.     

Ion Association in Lanthanide Chloride Solutions

A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of Ln^III association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl₃(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd³⁺, Gd³⁺ and Er³⁺ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of Ln^III–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water.     

Diastereoselective protonation of lactam enolates derived from (R)-phenylglycinol. A novel asymmetric route to 4-phenyl-1,2,3, 4-tetrahydroisoquinolines

Highly diastereoselective protonation of chiral lactam enolates of 4-substituted-1,4-dihydroisoquinolin-3-ones is reported. Protonation and alkylation processes of these lactam enolates derived from phenylglycinol occur with opposite diastereofacial selectivity. This diastereoselective protonation has been applied to the asymmetric synthesis of (4S)-N-methyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline 9 obtained in up to 97% ee.     

Etude sur l'interaction de certains complexes de l'Iode au moyen de Diantipyrilméthane (DAM). II

Résumé Le présent travail constitue une application analytique de nos recherches sur l'interaction des complexes interhalogénés de l'iode au moyen de diantipyrilméthane (DAM). On à étudié les conditions d'échange des ligands chlore et iode dans le complexe extrasphérique DAMH₃ [ICl₂]₃. Sur la base de cet échange on a élaboré une méthode photométrique de détermination de microquantités d'ions iodures, soit 1 à 10g d'ions iodures par ml. Les ions Br^–, Cl^–, NO₃ ^–, SO₄ ², C₂O₄ ^2– ne gênent pas la détermination.

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Investigation of the interaction of certain iodine complexes by means of diantipyrilmethane (DAM). II

Summary The present paper constitutes an analytical application of our studies on the interaction of interhalogen complexes of iodine by means of diantipyrilmethane (DAM). The exchange conditions of the chlorine and iodine ligands in the extraspheric complex DAMH₃ (ICl₂)₃ have been examined. On the basis of this exchange a photometric method of determining microquantities of iodide ions (1 to 10g iodide ions per ml) has been developed. The ions Br^–, Cl^–, SO₄ ^2–, C₂O₄ ^2– do not interfere with the determination.

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Zusammenfassung Die Ergebnisse unserer Untersuchungen über die Reaktion von Interhalogenkomplexen des Jods mit Diantipyrilmethan (DAM) wurden für analytische Zwecke verwendet. Die Bedingungen für den Austausch der Liganden Chlor und Jod im außersphärischen Komplex (DAM)H₃ · [JCl₂]₃ wurden untersucht. Auf der Grundlage dieses Austausches wurde eine photometrische Methode zur Bestimmung von Mikromengen, d. h. 1–10g Jodid/ml ausgearbeitet. Br^–, Cl^–, NO₃ ^–, SO₄ ^2–, C₂O₄ ^2– stören die Bestimmung nicht.

     

Trace crossings in cyclic voltammetry and electrochemic electrochemical inducement of chemical reactions: Aromatic nucleophilic substitution

Crossing of anodic and cathodic traces is frequently observed on cyclic voltammograms featuring the electrochemical induction of a chemical reaction in the case where the product standard potential is positive to the reactant reduction potential. The theory of this phenomenon has been established in the contaxt of aromatic nucleophilic substitution. The reaction of potassium diethyl phosphite on 4-chlorobenzonitrile in liquid ammonia was investigated as an example illustrating this type of phenomenon and its interpretation. The simulation of the experimental voltammograms demonstrates the proposed mechanistic and kinetic model and allows the rate constants of the various steps to be determined. Much higher rate constants can thus been attained than by the standard application of electrochemical techniques (the gain may reach five or six orders of magnitude). A procedure is derived from these observations and then a rationalization for inducing chemical reactions with a very low electricity consumption as opposed to that which occurs when the electrode potential is settled at the level of the reactant wave.     

Fitting the boron peak and resolving interferences in the 450–490 keV region of PGAA spectra

Prompt gamma activation analysis (PGAA) is one of the most powerful analytical methods for the determination of boron because of its very large neutron capture cross section. The peak of boron in the PGAA spectra is highly broadened due to the Doppler-effect. An improved method is presented to fit the boron peak, and to resolve interference with the gamma-rays of sodium and other matrix components. The method has been checked on test samples and on geological samples as well.     

Liquid chromatographic/electrospray ionization tandem mass spectrometric study of the phenolic composition of cocoa (Theobroma cacao)

Liquid chromatography coupled with ionspray mass spectrometry in the tandem mode (LC/MS/MS) with negative ion detection was used for the identification of a variety of phenolic compounds in a cocoa sample. Gradient elution with water and acetonitrile, both containing 0.1% HCOOH, was used. Standard solutions of 31 phenolic compounds, including benzoic and cinnamic acids and flavonoid compounds, were studied in the negative ion mode using MS/MS product ion scans. At low collisional activation, the deprotonated molecule [M - H](-) was observed for all the compounds studied. For cinnamic and benzoic acids, losses of CO(2) or formation of [M - CH(3)](-*) in the case of methoxylated compounds were observed. However, for flavonol and flavone glycosides, the spectra present both the deprotonated molecule [M - H](-) of the glycoside and the ion corresponding to the deprotonated aglycone [A - H](-). The latter ion is formed by loss of the rhamnose, glucose, galactose or arabinose residue from the glycosides. Different fragmentation patterns were observed in MS/MS experiments for flavone-C-glycosides which showed fragmentation in the sugar part. Fragmentation of aglycones provided characteristic ions for each family of flavonoids. The optimum LC/MS/MS conditions were applied to the characterization of a cocoa sample that had been subjected to an extraction/clean-up procedure which involved chromatography on Sephadex LH20 and thin-layer chromatographic monitoring. In addition to compounds described in the literature, such as epicatechin and catechin, quercetin, isoquercitrin (quercetin-3-O-glucoside) and quercetin-3-O-arabinose, other compounds were identified for the first time in cocoa samples, such as hyperoside (quercetin-3-O-galactoside), naringenin, luteolin, apigenin and some O-glucosides and C-glucosides of these compounds.