Synthesis of α-amino γ-butyrolactone derivatives by aziridination of α-ylidene γ-butyrolactones

The reactions of exocyclic α,β-unsaturated γ-lactones with NsONHCO₂Et and CaO produce N-(ethoxycarbonyl) spiroaziridino γ-lactones. By reaction with acetic acid these products give ring opening reaction and acetylated N-protected α-amino γ-butyrolactones are obtained. The ring opening reaction is quantitative and highly regioselective.     

Addition reactions of ethoxycarbonylnitrene and ethoxycarbonylnitrenium ion to allylic ethers

Ethoxycarbonylnitrene (EtOCON) generated by α-elimination adds cleanly to allylic ethers giving substituted aziridines. Similar addition via nitrenium ion (EtOCONH⁺) gives derivatives of β-amino alcohols.     

Synthesis of β,β-branched β-amino ester derivatives through spiroaziridination of (α-trimethylsilanylmethyl)cyclohexylidene esters

The reaction of (α-trimethylsilanylmethyl)cyclohexylidene esters with NsONHCO₂Et and CaO produces the N-(ethoxycarbonyl)spiroaziridines which, after ring-opening, gives the corresponding β,β-disubstituted β-amino ester derivatives. The stereochemical outcome of the reaction is influenced by substituents on the cyclohexyl group.     

Metal complexes of phytohormones. Part II. Copper(II) complexes of 6-benzylaminopurine

Summary Copper(II) complexes with 6-benzylaminopurine (BAPH) of the types Cu(BAPH)₂(ClO₄)₂·2H₂O (1) Cu(BAP)₂·4H₂O (2), and Cu(BAPH₂)Cl₃·MeOH (3), have been synthesized and characterized by conductivity, magnetic measurements, i.r., electronic and e.s.r. spectroscopy.     

Metal-cinnamic acids interactions. Part III. Synthesis and study of copper(II) complexes of 3, 4- and 3, 5-dimenthoxycinnamic acid

Summary Copper(II) complexes derived from substituted cinnamic acids 3, 4-dimethoxycinnamic acid (3, 4-DMCH) and 3, 5-dimethoxycinnamic acid (3, 5-DMCH), of the formula [Cu(3, 4-DMC)₂]·H₂O (1), [Cu(3, 5-DMC)₂]·H₂O (2) were prepared. The magnetic properties of the complexes suggest dimeric structures typical of copper(II) acetate monohydrate-like complexes. X-band e.s.r. spectra of polycrystalline samples at low temperature are typical of triplet state systems S=1. Their ability to catalyze the aerial oxidation of 3, 5-di-t-butylcatechol was measured spectrophotometrically at 30°C. The complexes are models for oxidases.     

X-ray spectroscopic characterization of Cu2+-phenanthroline complexes intercalated in α-zirconium phosphate

X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)₂]²⁺(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO₃-OH groups of the host. XPS also provides evidence for coordination of the Cu²⁺ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu²⁺ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed.     

Synthesis,binding and fluorescence studies of a new neutral H-bonding receptor for anions based on 3,5-bis(trifluoromethyl)phenylurea

The synthesis and anion binding studies of the new neutral receptor 1,1′-(2,2′-(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(2-oxoethane-2,1-diyl))bis(3-(3,5-bis(trifluoromethyl)phenyl)urea) (L1) are reported. L1 is a macrocyclic ligand containing the 3,5-trifluoromethylphenylureido-binding fragment attached as a side arm on the tetraazacyclododecane. L1 is soluble in numerous organic solvents; the binding properties of L1 towards several simple anions (G) were investigated by NMR, UV–vis and fluorescence techniques in DMSO and CH₃CN solutions. L1 is able to bind F^? , Cl^?  and AcO^?  in both solvents; in addition, it binds Br^?  in CH₃CN. Fluoride shows the highest constant values in the halide series (F^?  > Cl^?  > Br^? ) and AcO^?  is the most strongly bound among all the anions investigated. L1 is able to signal the presence of the anions in solution by fluorescence change; in the case of acetate, this occurs in the visible range.     

Scrambling of autoinducing precursor peptides investigated by infrared multiphoton dissociation with electrospray ionization and Fourier transform ion cyclotron resonance mass spectrometry

Two synthetic precursor peptides, H₂N-CVGIW and H₂N-LVMCCVGIW, involved in the quorum sensing of Lactobacillus plantarum WCFS1, were characterized by mass spectrometry (MS) with electrospray ionization and 7-T Fourier transform ion cyclotron resonance (ESI-FTICR) instrument. Cell-free bacterial supernatant solutions were analyzed by reversed-phase liquid chromatography with ESI-FTICR MS to verify the occurrence of both pentapeptide and nonapeptide in the bacterial broth. The structural characterization of both protonated peptides was performed by infrared multiphoton dissociation using a continuous CO₂ laser source at a wavelength of 10.6 μm. As their fragmentation behavior cannot be directly derived from the primary peptide structure, all anomalous fragments were interpreted as neutral loss of amino acids from the interior of both peptides, i.e., loss of V, G, VG and M, MC, V, CC, from H₂N-CVGIW and H₂N-LVMCCVGIW, respectively. Mechanisms of this scrambling are proposed. FTICR MS provides accurate masses of all fragment ions with very low absolute mass errors (<1.6 ppm), which facilitated the reliable assignment of their elemental compositions. The resolving power was more than sufficient to resolve closely isobaric product ions with routine subparts per million mass accuracies. Only the occurrence of pentapeptide was found in the cell-free culture of L. plantarum, grown in Waymouth’s medium broth, with a low content of 5.2?±?2.6 μM by external calibration. Most of it was present as oxidized H₂N-CVGIW, that is, the soluble disulfide pentapeptide with a level tenfold higher (i.e., 50?±?4 μM, n?=?3).

Trace elements in sediments and bioaccumulation in European silver eels (Anguilla anguilla L.) from a Mediterranean lagoon (SE Italy)

Samples of surface sediments and tissues (liver and muscle) of commercially available European silver eels (Anguilla anguilla L.) collected from Varano lagoon (Italy) were analysed to determine trace element contents. Univariate and multivariate analyses were performed to highlight both the differences between sampling sites and the influence of channel discharges. Atomic ratios indices for sediment data and biological enrichment factors (BEF) for eel tissues were calculated in order to evaluate the enrichment factor due to human activities. The highest levels of As (11.9?µg?g^?1) and Zn (14.1?µg?g^?1) were observed in the south-eastern zone of the lagoon, which is influenced by urban and agricultural discharges. The low levels of Hg observed in this study (0.04?µg?g^?1) led us to exclude both natural and human local sources of this element. Trace element concentrations of all elements were lower in muscle than in liver tissue. Significant enrichment of Cu and Zn was found in livers.     

Valorization of Apple Peels through the Study of the Effects on the Amyloid Aggregation Process of κ-Casein

Waste valorization represents one of the main social challenges when promoting a circular economy and environmental sustainability. Here, we evaluated the effect of the polyphenols extracted from apple peels, normally disposed of as waste, on the amyloid aggregation process of κ-casein from bovine milk, a well-used amyloidogenic model system. The effect of the apple peel extract on protein aggregation was examined using a thioflavin T fluorescence assay, Congo red binding assay, circular dichroism, light scattering, and atomic force microscopy. We found that the phenolic extract from the peel of apples of the cultivar “Fuji”, cultivated in Sicily (Caltavuturo, Italy), inhibited κ-casein fibril formation in a dose-dependent way. In particular, we found that the extract significantly reduced the protein aggregation rate and inhibited the secondary structure reorganization that accompanies κ-casein amyloid formation. Protein-aggregated species resulting from the incubation of κ-casein in the presence of polyphenols under amyloid aggregation conditions were reduced in number and different in morphology.