Ring-closing metathesis towards functionalised pentacyclic steroids

A new synthetic pathway towards pentacyclic steroids was described via a ring-closing metathesis reaction as the key step.     

Naphthalene‐1,5‐diammonium bis[trifluoridostannate(II)]

The structure of the title compound, (C₁₀H₁₂N₂)[SnF₃]₂, is made up of alternating layers of cations and anions, where the anion layers form extended polymeric sheets through a series of secondary Sn...F bonds. Strong N—H...F hydrogen bonds crosslink adjacent cation and anion layers, thereby building a three‐dimensional network.     

A new isoflavone glycoside from the aerial parts of <Emphasis Type="Italic">Retama sphaerocarpa</Emphasis>

A new isoflavone glycoside, genistein 7-O-xylosyl 8-C-glucoside (1), was isolated from the leaves of Retama sphaerocarpa. Its structure was elucidated by spectroscopic methods.     

Left and right generalized Drazin invertible operators

In this paper, we define and study the left and the right generalized Drazin inverse of bounded operators in a Banach space. We show that the left (resp. the right) generalized Drazin inverse is a sum of a left invertible (resp. a right invertible) operator and a quasi-nilpotent one. In particular, we define the left and the right generalized Drazin spectra of a bounded operator and also show that these sets are compact in the complex plane and invariant under additive commuting quasi-nilpotent perturbations. Furthermore, we prove that a bounded operator is left generalized Drazin invertible if and only if its adjoint is right generalized Drazin invertible. An equivalent definition of the pseudo-Fredholm operators in terms of the left generalized Drazin invertible operators is also given. Our obtained results are used to investigate some relationships between the left and right generalized Drazin spectra and other spectra founded in Fredholm theory.     

Characterization of the coincidence set for mixed signorini problems

For a mixed Signorini problem, reduction to a boundary variational inequality is derived. It is shown that its solution is a function constituted, on one portion of the boundary, of the upper-skirting function of solutions family of some associated linear mixed boundary value problems and, on the other portion, of the lower-skirting function of the same family. Qualitative behavior of the solution on different portions when perturbing the unknown boundary is analyzed. This shows in particular the usefulness of reduction to the boundary in some linear and nonlinear elliptic problems, even when usual variational methods cannot be applied for such purpose.     

Structural and antitumor properties of the YSNSG cyclopeptide derived from tumstatin

We previously demonstrated that the NC1[alpha3(IV)185-191] CNYYSNS peptide inhibited in vivo tumor progression. The YSNS motif formed a beta turn crucial for biological activity. The aim of the present study was to design a YSNSG cyclopeptide with a constrained beta turn on the YSNS residues more stable than CNYYSNS. By nuclear magnetic resonance and molecular modeling, we demonstrated that the YSNSG cyclopeptide actually adopted the expected beta-turn conformation. It promoted melanoma cell adhesion and prevented their adhesion to the native peptide. It inhibited in vitro cell proliferation and migration through Matrigel by downregulating proteolytic cascades. Moreover, intraperitoneal administration of the YSNSG cyclopeptide inhibited melanoma progression far more efficiently than the native peptide. The increased solubility and stability at low pH of the YSNSG cyclopeptide suggest this peptide as a potent antitumor therapeutic agent.     

A laboratory investigation of noise reduction by riblike structures on the ground

This paper investigates the use of periodically spaced edges or wells for the control of road traffic noise. The wells have uniform height and width and are placed on the ground. Physical scale modeling is used to assess the acoustic performance of these structures under laboratory conditions. It is shown that, in certain situations where the use of conventional barriers would not be appropriate, strategically designed riblike structures can provide insertion losses of typically 10-15 dB. The findings are explained in terms of acoustic scattering with the approaches used in the study of resonators and diffraction/interference gratings.     

Hydrogen bonding and structure of Ba2Ru2Cl10O·10H2O

Dibarium μ‐oxido‐bis[pentachloridoruthenate(IV)] decahydrate, Ba₂Ru₂Cl₁₀O·10H₂O, has been prepared from ruthenium(III) chloride and barium chloride in hydrochloric acid. It crystallizes in the monoclinic system (space group C2/c). The structure consists of alternating layers of [Ru₂Cl₁₀O]⁴⁻ and [Ba(H₂O)₇]²⁺ complex ions along the a direction. The O atom bonded to ruthenium occupies the 4e site, with symmetry, while the other atoms occupy general 8f sites. The overall structure is held together by O—H...O hydrogen bonds and O—H...Cl dipole–dipole interactions.     

Crystal structure and Mössbauer spectroscopic study of FeSnF6·6H2O

Large single crystals of FeSnF₆·6H₂O were grown when aqueous hydrofluoric solutions of SnF₂ and FeF₂ were allowed to evaporate in air. Tin-119 Mössbauer spectroscopy at ambient temperature shows a single line at slightly negative isomer shift relative to CaSnO₃ at room temperature (=–0.380(6) mm/s, =0). This is characteristic of tetravalent tin octahedrally coordinated by fluorine. The X-ray crystal structure shows that tin(IV) is coordinated by 6 fluorine atoms, and Fe(II) by 6 water molecules. Both sites show a slight distortion from octahedral symmetry: the six distances are equal (Sn-Fe=1.941(3) Å and Fe-O=2.112(3) Å), whereas there are two values of angles (Fe-Sn-F=90.4(1)° and 89.6(1)°; O-Fe-O=91.1(1)° and 88.9(1)°). The material is an ionic compound [SnF₆]^2–[Fe(H₂O)₆]²⁺.     

The first barium tin(II) bromide fluoride

In an effort to prepare barium tin(II) bromide fluorides for the first time, possibly similar to the chloride fluorides obtained earlier in our laboratory, precipitation reactions were carried out by mixing aqueous solutions of SnF₂ and of BaBr₂.2H₂O. In contrast with the chloride fluoride system, a single powdered phase was obtained throughout the SnF₂ – BaBr₂ system, with the yield being maximum at X ≈ 0.25, where X is the molar fraction of barium bromide in the reaction mixture. Phase identification with the JCPDS database failed to produce a match, confirming that a new phase had been produced. The exact chemical composition of the new compound has not been obtained yet. Based on the X value for the maximum yield, the Sn/Ba ratio is likely to be 3/1 or 2/1. The Mössbauer spectrum at ambient conditions shows that bonding to tin(II) is covalent, therefore with the tin lone pair being stereoactive. The Mössbauer parameters (δ = 3.68 mm/s, Δ = 0.99 mm/s) are similar to those of SnBrF and of Sn₂BrF₅, thereby showing that tin is bonded to both fluorine and bromine. The larger isomer shift and lower quadrupole splitting than in tin(II) fluorides show that the stereoactivity of the tin lone pair is lower than in the fluorides. The Mössbauer parameters fit well the linear correlation of the quadrupole splitting versus the isomer shift” that has been shown to be present in other series of tin(II) compounds. The linear decrease on this correlation shows that the contribution of non-spherical orbitals (p and d) to the lone pair is a much larger contributor to the quadrupole splitting than lattice distortions. The structure is likely made of Ba²⁺ cations and tin(II) fluoride bromide polyatomic anions, with covalent bonding withinthe anions.