Unexpected and expeditious entry into trifluoromethyl aziridines from substituted beta-dicarbonyl compounds

[Reaction: see text]. One-pot aziridinations were obtained starting from substituted 2,2,2-trifluoroethyl beta-dicarbonyl compounds with nosyloxycarbamates in the presence of an excess of CaO as base. The unexpected ring closure reaction takes place at room temperature, leading to the N-protected alpha-trifluoromethyl aziridines with good yields. The reaction pathway seems to be influenced by the choice of the base.     

Copper(II) complexes of N-terminal protected tri- and tetra-peptides containing histidine residues

Copper(II) complexes of peptides containing two or three histidyl residues (Ac-HisGlyHis-OH, Ac-HisGlyHis-NHMe, Ac-HisHisGlyHis-OH and Ac-HisHisGlyHis-NHMe) have been studied by potentiometric, UV-Vis, EPR and CD spectroscopic measurements. The imidazole nitrogen atoms are described as the primary metal binding sites of all ligands resulting in the formation of various macrochelates in the pH range 4 to 7. The (Nim, N-, Nim)-co-ordinated [CuH-1L]0+ complexes were mainly detected in samples containing free carboxylates at the C-termini, whilst the [CuH-2L]-(0) complexes were the predominant species in slightly alkaline solution and their binding modes were described via 4N-co-ordination (Nim, N-, N-, Nim) in (7,5,6)-membered fused chelate rings. Deprotonation and co-ordination of the third amide nitrogens were detected above pH approximately 9 in all cases.     

Site-specific ligation of anthracene-1,8-dicarboxylates to an Mn12 core: a route to the controlled functionalisation of single-molecule magnets

A novel single-molecule magnet of the Mn12 family, [Mn12O12(O2CC6H5)8(L)4(H2O)4].8CH2Cl2, has been synthesised by site-specific ligand exchange using a tailor-made dicarboxylate (L2-), which leads to selective occupation of axial binding sites.     

On the reaction of Ph2PNHPPh2 with RNCS (R=Et, Ph, p-NO2C6H4): preparation of the zwitterionic ligand EtNHC(S)Ph2P==NPPh2C(S)NEt (HSNS) and the zwitterionic metalate [(SNS)Rh(CO)

The reaction of Ph(2)PNHPPh(2) (PNP) with RNCS (Et, Ph, p-NO(2)(C(6)H(4))) gives addition products resulting from the attack of the P atoms of PNP on the electrophilic carbon atom of the isothiocyanate. When PNP is reacted with EtNCS in a 1:2 molar ratio, the zwitterionic molecule EtNHC(S)PPh(2)==NP(+)Ph(2)C(S)N(-)Et (HSNS) is obtained in high yield. HSNS can be protonated (H(2)SNS(+)) or deprotonated (SNS(-)), behaving in the latter form as an S,N,S-donor pincer ligand. The reaction of HSNS with [(acac)Rh(CO)(2)] (acac=acetylacetonate) affords the zwitterionic metalate [(SNS)Rh(CO)]. Other products can be obtained depending on the R group, the PNP/RNCS ratio (1:1 or 1:2), and the reaction temperature. The proposed product of the primary attack of PNP on RNCS, Ph(2)PN==PPh(2)C(S)NHR (A), cannot be isolated. Reaction of A with another RNCS molecule leads to 1:2 addition compounds of the general formula RNHC(S)PPh(2)==NP(+)Ph(2)C(S)N(-)R (1), which can rearrange into the non-zwitterionic product RNHC(S)PPh(2)==NP(S)Ph(2) (2) by eliminating a molecule of RNC. Two molecules of A can react together, yielding 1:1 PNP/RNCS zwitterionic products of the formula RNHCH[PPh(2)==NP(S)Ph(2)]PPh(2)==NP(+)Ph(2)C(S)N(-)R (3). Compound 3 can then rearrange into RNHCH[PPh(2)==NP(S)Ph(2)](2) (4) by losing a RNC molecule. When R=Et (a), compounds 1 a, 2 a (HSNS), and 4 a have been isolated and characterized. When R=Ph (b), compounds 2 b and 4 b can be prepared in high yield. When R=p-NO(2)C(6)H(4) (c), only compound 3 c is observed and isolated in high yield. The crystal structures of HSNS, [(SNS)Rh(CO)], and of the most representative products have been determined by X-ray diffraction methods.     

A new procedure for bovine milk digestion in a focused microwave oven: gradual sample addition to pre-heated acid

Milk samples can be efficiently digested using a focused microwave oven, however the conventional procedure of addition of concentrated acids to the liquid sample leads to digestates with elevated acidity and residual carbon concentrations. In this work a focused microwave oven was applied for acid digestion of bovine milk samples using a conventional and an alternative procedure based on gradual sample addition to hot and concentrated acids. A two-level 2³ full factorial design experiment with eight runs was carried out to evaluate the optimum experimental conditions for reducing both the residual carbon and the final acidity of digestates. The three studied parameters were: temperature of the digestion medium for sample addition, addition of sulfuric acid before the sample or during the first step, and number of aliquots of the sample gradually added. The best conditions were attained by adding small aliquots of milk (ten-fold a volume of 0.5 ml added during 5.0 min) to a digestion mixture containing 3.0 ml nitric acid plus 1.0 ml sulfuric acid heated at 105 °C. It was demonstrated that the digestion efficiency of the alternative procedure was better than the conventional procedure, i.e. 98 and 80%, respectively. The alternative procedure was applied for determination of Ba, Ca, Cu, K, Mg, Na, P, and Zn in whole and non-fat bovine milk. The accuracy was proved using two certified reference materials (whole and non-fat milk powder).     

Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Simultaneous determination of β2‐agonists in human urine by fast‐gas chromatography/mass spectrometry: method validation and clinical application

A fast screening protocol was developed and validated for the simultaneous determination of 15 β₂‐agonists in human urine (bambuterol, cimbuterol, clenbuterol, fenoterol, formoterol, isoproterenol, mapenterol, metaproterenol, procaterol, ractopamine, ritodrine, salbutamol, salmeterol, terbutaline, tulobuterol). The overall sample processing includes deconjugation with enzyme hydrolysis, liquid–liquid extraction, followed by derivatization of the extract and detection of β₂‐agonists trimethylsilyl‐derivatives by fast‐gas chromatography/electron impact–mass spectrometry (fast‐GC/EI‐MS). Sample extraction and derivatization were optimized with the purpose of improving recoveries and reaction yields for a variety of analytes with different structures simultaneously, while keeping the procedure simple and reliable. Validation parameters were determined for each analyte under investigation, including selectivity, linearity, intra‐ and inter‐assay precision, extraction recoveries and signal to noise ratio (S/N) at the lowest calibration level. Fast‐GC/MS sequences, based on the use of short columns, high carrier‐gas velocity and fast temperature ramping, allow considerable reduction of the analysis time (7 min), while maintaining adequate chromatographic resolution. The overall GC cycle time was less than 9 min, allowing a processing rate of 6 samples/h. High MS‐sampling rate, using a benchtop quadrupole mass analyzer, resulted in accurate peak shape definition under both scan and selected ion monitoring modes, and high sensitivity in the latter mode. The method was successfully tested on real samples arising from clinical treatments. Copyright © 2009 John Wiley & Sons, Ltd.     

Biradicaloid Character of Thiophene‐Based Heterophenoquinones: The Role of Electron–Phonon Coupling

The quinoidal versus biradicaloid character of the ground state of a series of thiophene‐based heterophenoquinones is investigated with quantum‐chemical calculations. The role of the ground‐state electronic character on molecular structure and vibrational properties is emphasized. The vibrational activities are experimentally determined and their analysis is performed by taking advantage of the definition of a collective vibrational coordinate (the

     

Elucidating the higher‐order structure of biopolymers by structural probing and mass spectrometry: MS3D

Chemical probing represents a very versatile alternative for studying the structure and dynamics of substrates that are intractable by established high‐resolution techniques. The implementation of MS‐based strategies for the characterization of probing products has not only extended the range of applicability to virtually all types of biopolymers but has also paved the way for the introduction of new reagents that would not have been viable with traditional analytical platforms. As the availability of probing data is steadily increasing on the wings of the development of dedicated interpretation aids, powerful computational approaches have been explored to enable the effective utilization of such information to generate valid molecular models. This combination of factors has contributed to making the possibility of obtaining actual 3D structures by MS‐based technologies (MS3D) a reality. Although approaches for achieving structure determination of unknown targets or assessing the dynamics of known structures may share similar reagents and development trajectories, they clearly involve distinctive experimental strategies, analytical concerns and interpretation paradigms. This Perspective offers a commentary on methods aimed at obtaining distance constraints for the modeling of full‐fledged structures while highlighting common elements, salient distinctions and complementary capabilities exhibited by methods used in dynamics studies. We discuss critical factors to be addressed for completing effective structural determinations and expose possible pitfalls of chemical methods. We survey programs developed for facilitating the interpretation of experimental data and discuss possible computational strategies for translating sparse spatial constraints into all‐atom models. Examples are provided to illustrate how the concerted application of very diverse probing techniques can lead to the solution of actual biological systems. Copyright © 2010 John Wiley & Sons, Ltd.