Intertwined Detection and Recognition Roles of Tetrazine in Synergistic Anion-π and H-bond Based Anion Receptor

The intrinsic properties of tetrazine as a π-anion receptor and as an on/off recognition probe merged with H-bond ability of an urea motif into a single architecture constitutes a new generation of well-defined anion receptors. Complexation properties directly benefit from the dual and synergistic contribution of tetrazine and urea. In this study, we report on the synthesis and assessment of binding properties to anions of diverse geometries. Association constants have been predicted by theoretical calculations and evaluated by multiple and complementary experimental techniques including electrospray-mass tandem spectroscopy, NMR, UV-visible, steady state fluorescence spectroscopies and time resolved fluorescence. These results provide the basis for a better understanding of both the complexation and the anion-dependent quenching mechanism.     

Independent components analysis coupled with 3D-front-face fluorescence spectroscopy to study the interaction between plastic food packaging and olive oil

Olive oil is one of the most valued sources of fats in the Mediterranean diet. Its storage was generally done using glass or metallic packaging materials. Nowadays, plastic packaging has gained worldwide spread for the storage of olive oil. However, plastics are not inert and interaction phenomena may occur between packaging materials and olive oil. In this study, extra virgin olive oil samples were submitted to accelerated interaction conditions, in contact with polypropylene (PP) and polylactide (PLA) plastic packaging materials. 3D-front-face fluorescence spectroscopy, being a simple, fast and non destructive analytical technique, was used to study this interaction. Independent components analysis (ICA) was used to analyze raw 3D-front-face fluorescence spectra of olive oil. ICA was able to highlight a probable effect of a migration of substances with antioxidant activity. The signals extracted by ICA corresponded to natural olive oil fluorophores (tocopherols and polyphenols) as well as newly formed ones which were tentatively identified as fluorescent oxidation products. Based on the extracted fluorescent signals, olive oil in contact with plastics had slower aging rates in comparison with reference oils. Peroxide and free acidity values validated the results obtained by ICA, related to olive oil oxidation rates. Sorbed olive oil in plastic was also quantified given that this sorption could induce a swelling of the polymer thus promoting migration.     

Gas‐phase interactions of organotin compounds with glycine

Gas‐phase interactions of organotins with glycine have been studied by combining mass spectrometry experiments and quantum calculations. Positive‐ion electrospray spectra show that the interaction of di‐ and tri‐organotins with glycine results in the formation of [(R)₂Sn(Gly)‐H]⁺and [(R)₃Sn(Gly)]⁺ ions, respectively. Di‐organotin complexes appear much more reactive than those involving tri‐organotins. (MS/MS) spectra of the [(R)₃Sn(Gly)]⁺ ions are indeed simple and only show elimination of intact glycine, generating the [(R)₃Sn]⁺ carbocation. On the other hand, MS/MS spectra of [(R)₂Sn(Gly)‐H]⁺complexes are characterized by numerous fragmentation processes. Six of them, associated with elimination of H₂O, CO, H₂O + CO and formation of [(R)₂SnOH]⁺ (?57 u),[(R)₂SnNH₂]⁺( ?58 u) and [(R)₂SnH]⁺ (?73 u), are systematically observed. Use of labeled glycines notably concludes that the hydrogen atoms eliminated in water and H₂O + CO are labile hydrogens. A similar conclusion can be made for hydrogens of [(R₂)SnOH]⁺and [(R₂)SnNH₂]⁺ions. Interestingly, formation [(R)₂SnH]⁺ ions is characterized by a migration of one the α hydrogen of glycine onto the metallic center. Finally, several dissociation routes are observed and are characteristic of a given organic substituent. Calculations indicated that the interaction between organotins and glycine is mostly electrostatic. For [(R)₂Sn(Gly)‐H]⁺complexes, a preferable bidentate interaction of the type η²‐O,NH2 is observed, similar to that encountered for other metal ions. [(R)₃Sn]⁺ ions strongly stabilize the zwitterionic form of glycine, which is practically degenerate with respect to neutral glycine. In addition, the interconversion between both forms is almost barrierless. Suitable mechanisms are proposed in order to account for the most relevant fragmentation processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Structures of [M(Ura‐H)(H2O)n]+ (M = Mg,Ca, Sr,Ba; n = 1–3) complexes in the gas phase by IRMPD spectroscopy and theoretical studies

The structures of singly and doubly (and for Mg, triply) hydrated group 2 metal dications bound to deprotonated uracil were explored in the gas phase using infrared multiple photon dissociation spectroscopy in the mid‐infrared region (1000–1900 cm^?1) and the O–H/N–H stretching region (2700–3800 cm^?1) in a Fourier transform ion cyclotron resonance mass spectrometer. The infrared multiple photon dissociation spectra were then compared with the computed IR spectra for various isomers. Calculations were performed using B3LYP with the 6‐31 + G(d,p) basis set for all atoms except Ba²⁺ and Sr²⁺, for which the LANL2DZ or the def2‐TZVPP basis sets with relativistic core potentials were used. Atoms‐in‐molecules analysis was conducted for all lowest energy structures. The lowest energy isomers in all cases are those in which the one uracil is deprotonated at the N3 position, and the metal is coordinated to the N3 and O4 of uracil. Regardless of the degree of solvation, all water molecules are bound to the metal ion and participate in a hydrogen bond with a carbonyl of the uracil moiety. Copyright © 2016 John Wiley & Sons, Ltd.     

Conductance and transport numbers of acidified sodium aluminate solutions and the zero point of charge of aluminium hydroxide

Summary Conductance measurements of acidified sodium aluminate solutions showed a gradual drop as the alumina content of the solution increases. This behaviour was explained by adsorption of H⁺ ions, as visualised from linear plots of ( ₀–) per mole of alumina against (where ₀ is the specific conductance of the corresponding (NaOH + HCl), is the specific conductance of (sodium aluminate + HCl) and is the amount of H⁺ ions adsorbed per mole of alumina). Transport number experiments showed that alumina behaves as a non-electrolyte and that the transport number of the Cl– ion increases with increase in alumina content. This behaviour was explained on the basis of aggregation of water molecules around alumina.The zero point of charge of colloidally dispersed aluminium hydroxide was determined from potentiometric and conductance measurements.

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Zusammenfassung Leitfähigkeitsmessung von angesäuerten Natrium-Aluminat-Lösungen zeigen einen Abfall, wenn der Aluminat-Gehalt der Lösungen wächst. Dieses Verhalten wird durch Adsorption von Wasserstoff-Ionen erklärt, erkennbar aus der linearen Auftragung von ( ₀–) pro Mol/Aluminat gegen Dabei ist ₀ die spezifische Leitfähigkeit der entsprechenden (NaOH + HCl)-Lösung, die spezifische Leitfähigkeit vom Gemisch Natriumaluminat + HCl und der Betrag an Wasserstoffionen, adsorbiert pro Mol/Aluminat. überführungszahl-Experimente zeigen, daß Alumina sich nicht als Elektrolyt verhält und daß die überführungszahl für Cl^–-Ionen mit dem Alumina-Anteil wächst. Dieses Verhalten wird erklärt auf Grund einer Aggregation von Wassermolekülen um das Alumina.Der Neutralpunkt für Ladung von kolloidal dispergiertem Alumiumhydroxid wurde aus potentiometrischen und Leitfähigkeitsmessungen bestimmt.

     

Ni(+) reactions with aminoacetonitrile, a potential prebiological precursor of glycine

The gas-phase reactions between Ni(+) ((2)D(5/2)) and aminoacetonitrile, a molecule of prebiological interest as possible precursor of glycine, have been investigated by means of mass spectrometry techniques. The mass-analyzed ion kinetic energy (MIKE) spectrum reveals that the adduct ions [NC--CH(2)--NH(2), Ni(+)] spontaneously decompose by loosing HCN, H(2), and H(2)CNH, the loss of hydrogen cyanide being clearly dominant. The structures and bonding characteristics of the aminoacetonitrile-Ni(+) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by density functional theory (DFT) calculations carried out at B3LYP/6-311G(d,p) level. A cyclic intermediate, in which Ni(+) is bisligated to the cyano and the amino group, plays an important role in the unimolecular reactivity of these ions, because it is the precursor for the observed losses of HCN and H(2)CNH. In all mechanisms associated with the loss of H(2), the metal acts as hydrogen carrier favoring the formation of the H(2) molecule. The estimated bond dissociation energy of aminoacetonitrile-Ni(+) complexes (291 kJ mol(-1)) is larger than those measured for other nitrogen bases such as pyridine or pyrimidine and only slightly smaller than that of adenine.     

Impact of crystallinity of poly(lactide) on helium and oxygen barrier properties

The helium and oxygen gas barrier properties of poly(lactide) were investigated as a function of stereochemistry and crystallinity degree. Poly(l-lactide) and poly(d,l-lactide) films were obtained by extrusion and thermally cold crystallized in either α′- or α-crystalline form with increasing crystallinity degree. Annealing of the films at low temperatures yielded to α′-crystals as well as the creation of a rigid amorphous fraction in the amorphous phase. Unexpectedly, the quantity of the rigid amorphous fraction was highest in poly(l-lactide) crystallized under α′-form. Unexpectedly, the gas permeability increased with increasing quantity of α′-crystals in poly(l-lactide) and remained constant with increasing quantity of α′-crystals in poly(d,l-lactide). A gain in gas barrier properties was obtained upon crystallization at higher temperatures yielding α-crystals. The analysis of the oxygen transport parameters, in particular the diffusion and the solubility coefficient showed that the diffusion was accelerated upon crystallization, while the solubility coefficient decreased in an expected manner which led to conclude that it remained constant in the amorphous phase. The acceleration of the diffusion seems to be correlated to the occurrence of the rigid amorphous fraction, which holds larger free volume. To conclude, for optimization of poly(lactide) gas barrier properties by focussing on the decrease of the diffusion coefficient it can be suggested to work with poly(d,l-lactide) and to aim a crystallization in α-form avoiding the formation of a rigid amorphous fraction.     

LOW TEMPERATURE POLARIZED ABSORPTION MICROSPECTROSCOPY OF SINGLE CRYSTALS OF THE REACTION CENTER FROM Rhodobacter sphaeroides WILD TYPE STRAIN 2.4.1

The absorbance and polarized absorbance spectra of single crystals of the reaction center complex isolated from Rhodobacter sphaeroides wild type strain 2.4.1 have been measured at 85 K. The crystals of the complex were obtained by the vapor diffusion technique. The spectroscopic experiments on the crystals were performed using an optical microspectrometer featuring a custom-built, liquid N2-flowing cold stage, the details of which are presented herein. These data demonstrate the feasibility of conducting optical spectroscopic experiments at cryogenic temperatures on single crystals of photosynthetic pigment-protein complexes.     

Structure-based design and solid-phase parallel synthesis of phosphorylated nonpeptides to explore hydrophobic binding at the Src SH2 domain

Using a novel, solid-phase parallel synthetic route and a computational docking program, a series of phosphorylated nonpeptides were generated to determine their structure-activity relationships (SAR) for binding at the SH2 domain of pp60src (Src). A functionalized benzoic acid intermediate was attached to solid support via Rink amide linkage, which upon acid cleavage generated the desired benzamide template-based nonpeptides in a facile manner. Compounds were synthesized using a combination of solid- and solution-phase techniques. Purification using reversed-phase, semipreparative HPLC allowed for quantitative SAR studies. Specifically, this work focused on functional group modifications, in a parallel fashion, designed to explore hydrophobic binding at the pY+3 pocket of the Src SH2 domain.