Enhancement of Fatty Acid‐based Polyurethanes Cytocompatibility by Non‐covalent Anchoring of Chondroitin Sulfate

For tissue engineering purpose biopolymer chondroitin sulfate (CS), one of the major components of cartilage and bone extracellular matrix, was immobilized onto the surface of amino‐functionalized polyurethane (PU) films derived from naturally occurring oleic and 10‐undecenoic acids. The amino‐functionalized PUs were prepared by aminolysis with 1,6‐hexamethylenediamine of synthesized PUs containing methyl ester groups. FTIR‐ATR, XPS, SEM, and water contact angle measurements were used to confirm the surface changes at each step of treatment, both in morphologies and chemical composition. Cytotoxicity and cell morphology analysis using osteoblast cell line MG63 showed that PU‐CS films are suitable materials for cell growth, spreading, and differentiation.

     

Iridium(III) molecular catalysts for water oxidation: the simpler the faster

We report on three Ir(iii) molecular catalysts for water oxidation: 1, [Cp*Ir(ppy)Cl]; 2, [Cp*Ir(bzpy)NO(3)]; 3, [Cp*Ir(H(2)O)(3)](NO(3))(2). 2 and 3 are water-soluble and show a long-term activity ca. 2 and 3 times higher than 1. It is remarkable that 3, having the simplest structure, is the catalyst with the highest activity.     

Comparison of noncontact and fiber-based fluorescence-mediated tomography

We present a comparative experimental phantom study of fiber-based and noncontact fluorescence tomography with respect to quantitation and localization of reconstructed fluorescent inclusions in turbid media such as tissue. Noncontact acquisition is usually considered potentially superior to fiber-based techniques because of the availability of a large number of detector readouts through a CCD. Our results indicate, however, that noncontact acquisition itself might improve the quality of reconstructions significantly, even without increasing the number of detectors and thus keeping the inverse problem moderately complex.     

Dominulin A and B: Two new antibacterial peptides identified on the cuticle and in the venom of the social paper wasp Polistes dominulus using MALDI-TOF, MALDI-TOF/TOF, and ESI-ion trap

Two new antibacterial peptides, denominated as Dominulin A and B, have been found on the cuticle and in the venom of females of the social paper wasp Polistes dominulus. The amino acidic sequence of the two peptides, determined by mass spectrometry, is INWKKIAE VGGKIL SSL for Dominulin A (MW = 1854 Da) and INWKKIAEIGKQVL SAL (MW = 1909 Da) for Dominulin B. Their presence on the cuticle was confirmed using MALDI-TOF by means of micro-extractions and direct analyses on body parts. The presence in the venom and the primary structure of the dominulins suggest their classification in the mastoparans, a class of peptides found in the venom of other Aculeate hymenoptera. Their antimicrobial action against Gram+ and Gram- bacteria fits in the range of the best natural antimicrobial peptides. Dominulins can represent an important defense of the colony of Polistes dominulus against microbial pathogens.     

Powerful approach to heterocyclic skeletal diversity by sequential three-component reaction of amines, isothiocyanates, and 1,2-diaza-1,3-dienes

By highly efficient, one-pot, three-component reactions, combining one set of 1,2-diaza-1,3-dienes (DDs), primary amines, and isothiocyanates in a different sequential order of addition, heterocyclic skeletal diversity can be achieved. The key feature discriminating the different heterocyclic core formation is the availability of the N or S heteronucleophile to give the first Michael addition step affording regioselective substituted 2-thiohydantoins or 2-iminothiazolidinones. The hydrazone or enehydrazino side chain at the 5-position of both heterocycles represents a valuable functionality to reach novel 5-hydroxyethylidene derivatives difficult to obtain by other methods.     

Gas-phase doubly charged complexes of cyclic peptides with copper in +1, +2 and +3 formal oxidation states: formation, structures and electron capture dissociation

Copper complexes with a cyclic D-His-β-Ala-L-His-L-Lys and all-L-His-β-Ala-His-Lys peptides were generated by electrospray which were doubly charged ions that had different formal oxidation states of Cu(I), Cu(II) and Cu(III) and different protonation states of the peptide ligands. Electron capture dissociation showed no substantial differences between the D-His and L-His complexes. All complexes underwent peptide cross-ring cleavages upon electron capture. The modes of ring cleavage depended on the formal oxidation state of the Cu ion and peptide protonation. Density functional theory (DFT) calculations, using the B3LYP with an effective core potential at Cu and M06-2X functionals, identified several precursor ion structures in which the Cu ion was threecoordinated to pentacoordinated by the His and Lys side-chain groups and the peptide amide or enolimine groups. The electronic structure of the formally Cu(III) complexes pointed to an effective Cu(I) oxidation state with the other charge residing in the peptide ligand. The relative energies of isomeric complexes of the [Cu(c-HAHK + H)](2+) and [Cu(c-HAHK - H)](2+) type with closed electronic shells followed similar orders when treated by the B3LYP and M06-2X functionals. Large differences between relative energies calculated by these methods were obtained for open-shell complexes of the [Cu(c-HAHK)](2+) type. Charge reduction resulted in lowering the coordination numbers for some Cu complexes that depended on the singlet or triplet spin state being formed. For [Cu(c-HAHK - H)](2+) complexes, solution H/D exchange involved only the N-H protons, resulting in the exchange of up to seven protons, as established by ultra-high mass resolution measurements. Contrasting the experiments, DFT calculations found the lowest energy structures for the gas-phase ions that were deprotonated at the peptide C(α) positions.     

Identification and structural characterization by LC-ESI-IONTRAP and LC-ESI-TOF of some metabolic conjugation products of homovanillic acid in urine of neuroblastoma patients

The levels of urinary catecholamine metabolites, such as homovanillic acid (HVA) and vanillylmandelic acid, are routinely used as a clinical tool in the diagnosis and follow-up of neuroblastoma (NB) patients. Recently, in the Clinical Pathology Laboratory Unit of G. Gaslini Children Hospital, a commercial method that employs liquid chromatography coupled to electrochemical detection (LC-EC) has been introduced for the measurement of these metabolites in the routine laboratory practice. Using this LC-EC method, an unknown peak could be observed only in samples derived from NB patients. To investigate the nature of this peak, we used a combination of liquid chromatography-time-of-flight mass spectrometry (LC-TOF-MS) and liquid chromatography-ion trap tandem mass spectrometry (LC-IT-MS). The first approach was used to obtain the elemental composition of the ions present in this new signal. To get additional structural information useful for the elucidation of unknown compounds, the ion trap analyzer was exploited. We were able to identify not just one, but three unknown signals in urine samples from NB patients which corresponded to three conjugated products of HVA: HVA sulfate and two glucuronoconjugate isomers. The enzymatic hydrolysis with β-glucuronidase confirmed the proposed structures, while the selective alkaline hydrolysis allowed us to distinguish the difference between phenol- and acyl-glucuronide of HVA. The latter was the unknown peak observed in LC-EC separations of urine samples from NB patients.     

Subvarieties of general type on a general projective hypersurface

We study subvarieties of a general projective degree hypersurface . Our main theorem, which improves previous results of L. Ein and C. Voisin, implies in particular the following sharp corollary: any subvariety of a general hypersurface , for and , is of general type.

     

Fourier treatment of near-field synchrotron radiation theory

In this paper, we couple synchrotron radiation (SR) theory with a branch of physical optics, namely laser beam optics. We show that the theory of laser beams is successful in characterizing radiation fields associated with any SR source. Both radiation beam generated by an ultra-relativistic electron in a magnetic device and laser beam are solutions of the wave equation based on paraxial approximation. It follows that they are similar in all aspects. In the space-frequency domain SR beams appear as laser beams whose transverse extents are large compared with the wavelength. In practical situations (e.g. undulator, bending magnet sources), radiation beams exhibit a virtual “waist” where the wavefront is often plane. Remarkably, the field distribution of a SR beam across the waist turns out to be strictly related with the inverse Fourier transform of the far-field angle distribution. Then, we take advantage of standard Fourier Optics techniques and apply the Fresnel propagation formula to characterize the SR beam. Altogether, we show that it is possible to reconstruct the near-field distribution of the SR beam outside the magnetic setup from the knowledge of the far-field pattern. The general theory of SR in the near-zone developed in this paper is illustrated for the special cases of undulator radiation. Using known analytical formulas for the far-field pattern and its inverse Fourier transform we find analytical expressions for near-field distributions in terms of far-field distributions.     

Central potentials with closed cruise orbits

A particle will be said to be in cruise motion if it is nonholonomically constrained to have constant speed. When the particle is placed in a central force field, the resulting mechanical system is known to be integrable. Cruise orbits in a central force field may be closed (periodic in time) or not, depending on the potential and on the speed. Here we give a constructive characterization of all central potentials for which all cruise motions of a given speed are closed. As a consequence, we also give a new proof of the fact that for any such potential the set of speeds for which all cruise motions are closed has always empty interior.