Mechanical Behavior of Polymer Gels for RDCs and RCSAs Collection: NMR Imaging Study of Buckling Phenomena

Anisotropic NMR parameters, such as residual dipolar couplings (RDCs), residual chemical shift anisotropies (RCSAs) and residual quadrupolar couplings (RQCs or Δν_Q), appear in solution‐state NMR when the molecules under study are subjected to a degree of order. The tunable alignment by reversible compression/relaxation of gels (PMMA and p‐HEMA) is an easy, user‐friendly, and very affordable method to measure them. When using this method, a fraction of isotropic NMR signals is observed in the NMR spectra, even at a maximum degree of compression. To explain the origin of these isotropic signals we decided to investigate their physical location inside the NMR tube using deuterium 1D imaging and MRI micro‐imaging experiments. It was observed that after a certain degree of compression the gels start to buckle and they generate pockets of isotropic solvent, which are never eliminated. The amount of buckling depends on the amount of cross‐linker and the length of the gel.     

Vehicle emissions,urban air quality and current Italian legislation: the case of Messina. V

In the current program for the preparation of an urban air map, this paper reports data obtained by the five base stations in the period 1997-2000 regarding traditional pollutants and gives the first results obtained in determining continuously benzene, toulene and PM10. Additional measurements have been carried out by a mobile station at the falcate zone, never tested before, which has very low traffic but with the presence of some small metal industries and, under favourable meteorological conditions, the effects of the harbour. A statistical study on the hourly-trend of particulate suspended matter in two zones of the city which have different traffic volume for the period 1995-1997 is also reported. The ozone characteristic peak at 15.00 is fully confirmed in all stations and over all the period contrarily to most Italian cities, which present the peak about three hours earlier. PM10 annual mean value during 1999 was a little higher than the legal one. Base stations "Archimede" and "Minissale" still present some risk of a stop or limitation of traffic even with respect to traditional or "new" pollutants. Statistical analysis of particulate suspended matter confirm the very different characteristics of the base stations under consideration.     

Deuterium NMR spectroscopy is a versatile and economical tool for monitoring reaction kinetics in ionic liquids

Time-resolved 2H NMR spectroscopy is used to monitor the progress of and gain kinetic information for a variety of reactions in different ionic media.     

A highly enantioselective route to either enantiomer of both alpha- and beta-amino acid derivatives

This report describes the unprecedented use of unmodified aldehydes as donors in a catalytic asymmetric Mannich-type reaction. The proline-catalyzed reaction of N-PMP-protected alpha-imino ethyl glyoxylate with unmodified aliphatic aldehydes provided a general and very mild entry to either enantiomer of beta-amino and alpha-amino acids and derivatives in high yield and stereoselectivity. Six of the seven aldehydes studied yielded products with ee values of 99% or greater. The diastereoselectivity of the reaction increased with the bulkiness of the substituents of the aldehyde donor in the order R = Me < Et < i-Pr < n-Pent. In five of the cases studied, excellent syn stereoselectivities were achieved. In addition, the corresponding chiral beta-amino aldehyde adducts can be readily converted to the corresponding amino acid derivatives. Most significantly, this approach provides facile access to substituted beta-lactams.     

Peptide AS-48: prototype of a new class of cyclic bacteriocins

After the discovery of bacteriocin AS-48, a 70-residue cyclic peptide produced by Enterococcus faecalis subsp. liquefaciens, some naturally-occurring cyclic proteins from bacteria have been reported. AS-48 is encoded by the 68-kb pheromone-responsive plasmid pMB2, and the gene cluster involved in production and immunity has been identified and sequenced. This peptide exerts a bactericidal action on sensitive cells (most of the Gram-positive and some Gram-negative bacteria). Its target is the cytoplasmic membrane, in which it opens pores, leading to the dissipation of the proton motive force and cell death, a mechanism similar to that proposed for the action of defensins or, most generally, cationic antibacterial peptides. This fact, together with its remarkable stability and solubility over a wide pH range, suggest that this bacteriocin could be a good candidate as a natural food preservative. The amino acid composition of purified AS-48 shows the absence of modified or dehydrated residues, making it clearly different from lantibiotics. Bacteriocin AS-48 also differs from defensins in that it does not contain cysteines and consequently no disulfide bridges, which makes is high stability even more remarkable. Composition analysis of AS-48 shows a high proportion of basic to acidic amino acids, conferring to this peptide a strong basic character, with an isoelectric point close to 10.5. Determination of the AS-48 structural gene DNA sequence, together with the sequences of AS-48 protease digestion fragments and mass spectrometry determinations, allowed us to determine unambiguously the cyclic structure of the molecule, being the first example of a posttranslational modification in which a cyclic structure arises from a "head-to-tail" linkage. We have solved the three-dimensional structure of AS-48 in solution, and it consists of a globular arrangement of five alpha-helices enclosing a compact hydrophobic core. Interestingly, the head-to-tail peptide link between Trp-70 and Met-1 lies in the middle of alpha-helix 5, which is shown to have a pronounced effect on the stability of the three-dimensional structure. Analysis of structure-function relationship allowed us to propose models to understand the aspects of the molecular function of AS-48. The purpose of this work is to review recent developments in our understanding about the biochemical and biological characteristics and structure of this unusual type of bacteriocin.     

Solid State Reactions of Hemin with Basic Substances: Formation of bis and Mixed Complexes

The solid state reactions of hemin with KCN, Na₂SxH₂O, arginine, imidazole, 1-methylimidazole, 2-methylimidazole, benzimidazole, and mixtures of these basic reagents were monitored using IR, Mössbauer, and XRD techniques. All these basic substances react at the peripheral propionic acid group of hemin-forming salts. Binary mixtures of KCN, arginine, imidazole, 1-methylimidazole, 2-methylimidazole, and benzimidazole were found to form complexes with mixed ligands at the iron site of hemin. According to the structural information obtained for these mixed complexes, mechanisms for their formation are proposed. The solid state synthesis and the properties of the obtained products reveal the specifities of the involved ligands.     

Higher order symmetric spaces and the roots of the identity in a Lie group

Let denote the set of all -roots of the identity in a Lie group . We show that is always an embedded submanifold of , having the conjugacy classes of its elements as open submanifolds. These conjugacy classes are examples of -symmetric spaces and we show, more generally, that every -symmetric space of a Lie group is a covering manifold of an embedded submanifold of . We compute also the Hessian of the inclusions of and into , relative to the natural connection on the domain and to the symmetric connection on .

     

Exo conformers of N‐(pyridin‐2‐yl)‐ and N‐(pyridin‐3‐yl)norbornene‐5,6‐dicarboximide crystals

Two isomeric pyridine‐substituted norbornenedicarboximide derivatives, namely N‐(pyridin‐2‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (I), and N‐(pyridin‐3‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (II), both C₁₄H₁₂N₂O₄, have been crystallized and their structures unequivocally determined by single‐crystal X‐ray diffraction. The molecules consist of norbornene moieties fused to a dicarboximide ring substituted at the N atom by either pyridin‐2‐yl or pyridin‐3‐yl in an anti configuration with respect to the double bond, thus affording exo isomers. In both compounds, the asymmetric unit consists of two independent molecules (Z′ = 2). In compound (I), the pyridine rings of the two independent molecules adopt different conformations, i.e. syn and anti, with respect to the methylene bridge. The intermolecular contacts of (I) are dominated by C—H...O interactions. In contrast, in compound (II), the pyridine rings of both molecules have an anti conformation and the two independent molecules are linked by carbonyl–carbonyl interactions, as well as by C—H...O and C—H...N contacts.     

The first examples of metal-mediated addition of a phosphorus imine to nitriles; the preparation and X-ray crystal structures of [PtCl4{NH=C(Et)N=PPh3}2] and [PtCl2(EtCN){NH=C(Et)N[double bond, length as m-dash]PPh3}

Imino(triphenyl)phosphorane, Ph3P=NH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4{NH=C(R)N=PPh3}2](R=Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN){NH=C(Et)N=PPh3}](3) and [PtCl2{NH=C(Et)N=PPh3}2](4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal nitrogen.