Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells

In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast ¹⁵N‐edited NMR spectroscopic experiments. To this aim, ¹⁵N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including ¹⁵N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.     

Fracture behavior and mechanical,thermal, and rheological properties of biodegradable films extruded by flat die and calender

The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.     

Inhomogeneous Gevrey classes and ultradistributions

The inhomogeneous Gevrey classes, defined in terms of Fourier transform, are a natural extension of the standard Gevrey classes. We find equivalent characterizations and discuss algebraic and topological properties. We therefore introduce the dual spaces, the inhomogeneous ultradistributions, giving some equivalent definitions and corresponding algebraic and topological properties; in particular, a version of the Paley-Wiener-Schwartz theorem is proved in our framework. Finally, as an important example, the multianisotropic Gevrey classes and ultradistributions are considered.     

Characterization of Ultrathin Films of Cellulose Esters

The adsorption of cellulose acetate (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from solutions prepared in acetone onto silicon wafers led to ultrathin films, which were characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The polysaccharides films were characterized in the air just after their formation and after annealing at temperatures higher than their glass transition temperature or melt temperature. The films thickness close to 2 nm and surface roughness did not vary significantly upon annealing. AFM images revealed the presence of small clumps dispersed on a homogeneous layer, which covered completely the Si wafers. Such topographic details were also observed after annealing. However, upon annealing the films surfaces changed from hydrophilic to hydrophobic, evidencing molecular re-orientation at the solid–air interface. The adhesion of bovine serum albumin (BSA) and lipase onto the cellulose esters films was quantified in order to evaluate the possibility of applying such films as selective support for biomolecules.     

Triorganotin 4-isopropylbenzoates as model transesterification catalysts for triorganotin carboxylates grafted to cross-linked polystyrene

Starting from 4-isopropylbenzoic acid, three new triorganotin carboxylates bearing methyl, butyl and phenyl substituents at tin, respectively, were prepared and fully characterized by spectroscopic and thermal techniques, with particular regard to the coordination number of tin atom, in solution as well as in the solid state. The triorganotin compounds, tested as transesterification catalysts in the reaction between ethyl acetate and primary, secondary or tertiary alcohol, respectively, displayed, as expected, a strong decrease of activity on passing from the primary to the tertiary alcohol reactant. Different activities by the tin carboxylates were also observed in the reaction between primary alcohol and ethyl acetate. The reaction mechanism, as elucidated by Sn NMR, involves coordination of both ester substrate and alcohol reactant to the triorganotin compound, the reaction conversion appearing related not only to the Lewis acidity of the tin atom, but also to the nature of the reactants. Preliminary catalytic tests were also carried out in the reaction between glyceryl tridodecanoate (as a model of natural triglyceride) and ethanol, mimicking the preparation of biodiesel fuel. Although in this case lower conversions were obtained with respect to the reactions on ethyl acetate, the catalytic activity of organotin derivatives appears considerable.     

Sugli insiemi di permutazioni strettamente k-transitivi (k ≥ 3)

Summary Let G be a sharply 3-transitive permutation set on a finite set E of even cardinality and let 1 be in G. The following theorems are proved. G is one of the known examples if and only if there exists a non-identity normal subgroup N of G and an element of E such that NG G.G is a group if and only if G for every G and for every G and for every G .By using the classification of finite single groups a result concerning sharply k-transitive permutation sets k>3 is also proved.

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Dedicato a Guido Zappa in occasione del suo 70° compleanno

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Lavoro eseguito nell'ambito dei progetti finanziati dal Ministero della Pubblica Istruzione.     

Nickel-Ruthenium Mixed-Metal Carbonyl Clusters Syntheses and Solid State Structures of the Two Tetrahedral Clusters [PPh4][NiRu3(μ3 H)(CO)9(μ-CO)3] and [NEt4]2[NiRu3(CO)8(μ-CO)4]

Redox condensation of [Ru₃H(CO)₁₁]- with Ni(CO)₄, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRu_H(CO)₁₁)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh₄][NiRu₃H(CO)₁₂] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu₃, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu₂ basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C _b = 2.084 Å, Ni-C _b = 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O _b = 1.159 Å, M-C-O, = 176.3°,M-C--O _b = 139.3°;other distances are: Ni-C₁ = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt₄]₂[NiRu₃(CO)₁₂] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu₃ core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C _t = 1.878 Å, Ru-C _b 2.045 Å, Ni-C _b = 2.055 Å, C-O _t = 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O _b = 138.6°; other distance is: Ni-C _t = 1.754(10) Å,t = terminal,b = bridging.     

Amphiphilic cyclodextrin carriers embedding porphyrins: charge and size modulation of colloidal stability in heterotopic aggregates

The interaction between the anionic 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphyrin (TPPS) and cationic vesicles formed by heptakis(2-omega-amino-O-oligo(ethylene oxide)-6-hexylthio)-beta-cyclodextrin (SC6CDNH2) has been investigated in detail through a combination of elastic light scattering (ELS), quasi-elastic light scattering (QELS), zeta potential measurements, and time-resolved fluorescence anisotropy. ELS experiments provided the first structural characterization of these cationic vesicles both in the absence and in the presence of TPPS porphyrin, modeling the system as a spherical particle described by a single thin shell form factor. The structure of mixed hetero-aggregates is modulated by charge and size of the two components as function of different porphyrin/cyclodextrin (CD) molar ratios. At the limiting molar ratio studied, the absolute value of zeta potential (/zeta/ = 12.5 mV) seems to be a reference value for the formation of stable colloidal CD vesicular aggregates at thermodynamic equilibrium. New insights on the structure of these heterotopic colloids have been obtained by analysis of rotational correlation times at different molar ratios exploiting time-resolved fluorescence anisotropy experiments. At high porphyrin loads, the anisotropy decays behave as monoexponentials and the rotational correlation times (1-2 ns) together with the r(0) values close to zero suggest the presence of small amounts of TPPS embedded in a hydrophobic environment either in monomeric or in aggregated form. At the lower porphyrin/CD molar ratios, the anisotropy decays exhibit a double-exponential behavior showing a predominant component with a slow rotational correlation time (20-25 ns) and limiting anisotropy values of approximately 0.15. This component has been assigned to molecules that are more stabilized onto the CD vesicles, that is, porphyrins embedded into the oligo-ethylene "wall" of the CD vesicles. Scanning near-field optical microscopy of the samples evaporated on glass surfaces gave further insights on the morphology and optical properties of these systems, confirming the embedding of TPPS on the vesicles and evidencing the role of the solvent.