A structural study of new tetrakis(1H-pyrazol-1-yl)methanes

Tetrakis(1H-pyrazol-1-yl)methanes are very rare compounds of which only two are known: the unsubstituted 1 obtained classically by Hückel in 1937 from carbon tetrachloride and prepared again several times and the 3,5-dimethyl substituted 2 obtained serendipitously by Pombeiro in 2009. We have now extended this group to include four new derivatives 8, 9, 11 and 12 bearing methyl groups. The X-ray crystal structure of the four compounds has been determined. They have been studied by NMR both in solution (¹H, ¹³C, ¹⁵N) and in the solid state (¹³C and ¹⁵N). DFT calculations of the six compounds (geometries, energies and absolute shieldings) have been used to discuss the experimental observations.     

Determination of the substituent effect on the O-H bond dissociation enthalpies of phenolic antioxidants by the EPR radical equilibration technique

The bond dissociation enthalpies (BDE) of several phenols containing electron-withdrawing substituents in the para position have been determined by means of the EPR radical equilibration technique. It has been found that CN, NO(2), CHO, COOR, and COOH induce an increase of the BDE value of the O-H bond, thus producing a worsening of the antioxidant activity of phenols, while Cl, Ph, and CH[double bond]CHPh show an opposite effect. The contributions of these substituents for the calculation of the BDE values in polysubstituted phenols by using the group additivity rule have also been derived. It is shown that this rule provides quite reliable predictions of bond strengths, so that the method can be conveniently used to estimate new data on substituted phenols.     

Rose Bengal‐Sensitized Photooxidation of the Dipeptides l‐Tryptophyl‐l‐Phenylalanine,l‐Tryptophyl‐l‐Tyrosine and l‐Tryptophyl‐l‐Tryptophan: Kinetics,Mechanism and Photoproducts¶

The Rose Bengal‐sensitized photooxidations of the dipeptides l ‐tryptophyl‐l ‐phenylalanine (Trp‐Phe), l ‐tryptophyl‐l ‐tyrosine (Trp‐Tyr) and l ‐tryptophyl‐l ‐tryptophan (Trp‐Trp) have been studied in pH 7 water solution using static photolysis and time‐resolved methods. Kinetic results indicate that the tryptophan (Trp) moiety interacts with singlet molecular oxygen (O₂(¹Δ_g)) both through chemical reaction and through physical quenching, and that the photooxidations can be compared with those of equimolecular mixtures of the corresponding free amino acids, with minimum, if any, influence of the peptide bond on the chemical reaction. This is not a common behavior in other di‐ and polypeptides of photooxidizable amino acids. The ratio between chemical (k_r) and overall (k_t) rate constants for the interaction O₂(¹Δ_g)‐dipeptide indicates that Trp‐Phe and Trp‐Trp are good candidates to suffer photodynamic action, with k_rlk_t values of 0.72 and 0.60, respectively (0.65 for free Trp). In the case of Trp‐Tyr, a lower k_rlk_t value (0.18) has been found, likely as a result of the high component of physical deactivation of O₂(¹Δ_g) by the tyrosine moiety. The analysis of the photooxidation products shows that the main target for O₂(¹Δ_g) attack is the Trp group and suggests a much lower accumulation of kynurenine‐type products, as compared with free Trp. This is possibly because of the occurrence of another accepted alternative pathway of oxidation that gives rise to 3a‐oxidized hydrogenated pyrrolo[2,3‐b]indoles.     

Quantum trajectories in atom-surface scattering with single adsorbates: the role of quantum vortices

In this work, a full quantum study of the scattering of He atoms off single CO molecules, adsorbed onto the Pt(111) surface, is presented within the formalism of quantum trajectories provided by Bohmian mechanics. By means of this theory, it is shown that the underlying dynamics is strongly dominated by the existence of a transient vortitial trapping with measurable effects on the whole diffraction pattern. This kind of trapping emphasizes the key role played by quantum vortices in this scattering. Moreover, an analysis of the surface rainbow effect caused by the local corrugation that the CO molecule induces on the surface, and its manifestation in the corresponding intensity pattern, is also presented and discussed.     

Different rotamer states of cytosine nucleobases in heteronuclear PtPd-, PtPd2, and Pt2Pd2Ag complexes derived from [Pt(2,2'-bpy)(1-MeC-N3)2]2+ (1-MeC = 1-methylcytosine): first examples of species with head-head oriented 1-MeC(-) ligands

[Pt(2,2'-bpy)(1-MeC-N3)(2)](NO(3))(2) (1) (2,2'-bpy = 2,2'-bipyridine; 1-MeC = 1-methylcytosine) exists in water in an equilibrium of head-tail and head-head rotamers, with the former exceeding the latter by a factor of ca. 20 at room temperature. Nevertheless, 1 reacts with (en)Pd(II) (en = ethylenediamine) to give preferentially the dinuclear complex [Pt(2,2'-bpy)(1-MeC(-)-N3,N4)(2)Pd(en)](NO(3))(2)·5H(2)O (2) with head-head arranged 1-methylctosinato (1-MeC(-)) ligands and Pd being coordinated to two exocyclic N4H(-) positions. Addition of AgNO(3) to a solution of 2 leads to formation of a pentanuclear chain compound [{Pt(2,2'-bpy)(1-MeC(-))(2)Pd(en)}(2)Ag](NO(3))(5)·14H(2)O (5) in which Ag(+) cross-links two cations of 2 via the four available O2 sites of the 1-MeC(-) ligands. 2 and 5 appear to be the first X-ray structurally characterized examples of di- and multinuclear complexes derived from a Pt(II) species with two cis-positioned cytosinato ligands adopting a head-head arrangement. (tmeda)Pd(II) (tmeda = N,N,N',N'-tetramethylethylenediamine) and (2,2'-bpy)Pd(II) behave differently toward 1 in that in their derivatives the head-tail orientation of the 1-MeC(-) nucleobases is retained. In [Pt(2,2'-bpy)(1-MeC(-))(2){Pd(2,2'-bpy)}(2)](NO(3))(4)·10H(2)O (4), both (2,2'-bpy)Pd(II) entities are pairwise bonded to N4H(-) and O2 sites of the two 1-MeC(-) rings, whereas in [Pt(2,2'-bpy)(1-MeC(-))(2){Pd(tmeda)}(2)(NO(3))](NO(3))(3)·5H(2)O (3) only one of the two (tmeda)Pd(II) units is chelated to N4H(-) and O2. The second (tmeda)Pd(II) is monofunctionally attached to a single N4H(-) site. On the basis of these established binding patterns, ways to the formation of mixed Pt/Pd complexes and possible intermediates are proposed. The methylene protons of the en ligand in 2 are special in that they display two multiplets separated by 0.64 ppm in the (1)H NMR spectrum.     

Preferred conformers of proteinogenic glutamic acid

The molecular shape of proteinogenic glutamic acid has been determined for the first time. Vaporization of the solid amino acid by laser ablation in combination with Fourier transform microwave spectroscopy made possible the detection of five different structures in a supersonic jet. These structures have been identified through their rotational and (14)N quadrupole coupling constants. All conformers show hydrogen bonds linking the amino and alpha carboxylic group through N-H···O═C (type I) or N···H-O (type II) interactions. In three of them there are additional hydrogen bonds established between the amino group and the carboxylic group in the gamma position. Entropic effects related to the side chain have been found to be significant in determining the most populated conformations.     

Electrochemical and structural coupling of the naphthoquinone amino acid

As a prelude to engineering artificial energy conversion proteins emulating biology, we examine the inclusion of a synthetic naphthoquinone amino acid in a characterized host-guest protein and determine the effects of its quinone and hydroquinone forms on the helix-coil distribution.     

AFM-based force-clamp monitors lipid bilayer failure kinetics

The lipid bilayer rupture phenomenon is here explored by means of atomic force microscopy (AFM)-based force clamp, for the first time to our knowledge, to evaluate how lipid membranes respond when compressed under an external constant force, in the range of nanonewtons. Using this method, we were able to directly quantify the kinetics of the membrane rupture event and the associated energy barriers, for both single supported bilayers and multibilayers, in contradistinction to the classic studies performed at constant velocity. Moreover, the affected area of the membrane during the rupture process was calculated using an elastic deformation model. The elucidated information not only contributes to a better understanding of such relevant process, but also proves the suitability of AFM-based force clamp to study model structures as lipid bilayers. These findings on the kinetics of lipid bilayers rupture could be extended and applied to the study of other molecular thin films. Furthermore, systems of higher complexity such as models mimicking cell membranes could be studied by means of AFM-based force-clamp technique.     

Mycotoxin profile of Fusarium langsethiae isolated from wheat in Italy: production of type‐A trichothecenes and relevant glucosyl derivatives

Fusarium langsethiae, formally described as a new species over a decade ago, has been identified as the main producer of HT‐2 (HT2) and T‐2 (T2) toxins in Europe in small cereal grains. Mycotoxin contamination caused by this Fusarium species can represent a food safety hazard that deserves further attention. In the present work, the mycotoxin profile in wheat cultures of F. langsethiae is presented with particular reference to the production of major type‐A trichothecenes and their glucosyl derivatives. F. langsethiae isolates, representative of the major Italian wheat cultivation areas, were tested for the production of T2, HT2, diacetoxyscirpenol (DAS) and neosolaniol (NEO), and relevant glucosyl derivatives. Liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) was used for the identification and chemical characterization of these metabolites. F. langsethiae isolates under investigation resulted to be potent producers of T2, HT2 and NEO. Furthermore, a well‐defined set of isolates, all originating from Central Italy, produced also DAS. All isolates were found to be able to produce HT2 glucosyl derivatives, whereas only traces of T2 glucoside were detected in one sample. Furthermore, two mono‐glucosyl derivatives of NEO and one mono‐glucoside derivative of DAS were identified and characterized. The screening for the presence/absence of glucosylated trichothecenes in analyzed fungal extracts revealed a general co‐occurrence of these derivatives with the parent toxin at levels that could be roughly estimated to account up to 37% of the relevant unconjugated toxin. This is the first report of the production of glucosylated trichothecenes by F. langsethiae cultured on small grains. Copyright © 2013 John Wiley & Sons, Ltd.