Synthesis and Structures of Two Triorganotin(IV) Polymers R3Sn{O2CC6H4[N=C(H)}{C(CH3)CH(CH3)-3-OH]-p} n (R = Me and Ph) Containing a 4-[(2Z)-(3-Hydroxy-1-methyl-2-butenylidene)amino] benzoic Acid Framework

Two new polymeric triorganotin(IV) complexes R₃Sn{O₂CC₆H₄[N=C(H)}{C(CH₃)CH(CH₃)-3-OH]-p} _n ([Me₃Sn(LH)] _n : 1) and ([Ph₃Sn(LH)] _n : 2) containing a 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)amino]benzoate (LH) framework were prepared. Both compounds have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, IR and ¹¹⁹Sn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of complexes 1 and 2 reveal that they exist as polymeric zig-zag chains in which the LH-bridged Sn-atoms adopt a trans-R₃SnO₂ trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the alcoholic oxygen atom of the next carboxylate ligand in the chain. The carboxylate ligands coordinate in the zwitterionic form with the alcoholic proton moved to the nearby nitrogen atom.     

Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV–vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts.     

Halogen bonding based recognition processes: a world parallel to hydrogen bonding

Halogen bonding is the noncovalent interaction between halogen atoms (Lewis acids) and neutral or anionic Lewis bases. The main features of the interaction are given, and the close similarity with the hydrogen bonding will become apparent. Some heuristic principles are presented to develop a rational crystal engineering based on halogen bonding. The focus is on halogen-bonded supramolecular architectures given by halocarbons. The potential of the interaction is shown by useful applications in the field of synthetic chemistry, material science, and bioorganic chemistry.     

Impact of fluorinated vinylene units on supramolecular organization and optical properties of poly(p-phenylenedifluorovinylene) thin films as a class of blue band gap conjugated polymers

This study is an investigation on the interplay between supramolecular organization and optical properties of thin films of conjugated polymers with fluorinated vinylene units such as poly[2-(2-ethylhexyloxy)-5-methoxy]-1,4-phenylenedifluorovinylene (MEH-PPDFV) and poly(2-methoxy-5-propyloxysulfonatephenylenedifluorovinylene) (MPS-PPDFV), which are both PPV polymers with fluorinated double bonds with alkoxy chains in the 2 and 5 positions. MEH-PPDFV is the fluorinated version of the widely investigated MEH-PPV, and MPS-PPDFV is characterized by the presence of ionic alkoxy side chains. This interplay is elucidated exploiting atomic force microscopy, spectroscopic ellipsometry and photoluminescence to obtain complementary information. It is demonstrated that the presence of F-atoms in the vinylene units of the MEH-PPDFV yields a blue optical band gap with the maximum of the fundamental HOMO-LUMO transition and of the room temperature photoluminescence at 3.74 eV (331 nm) and at 2.71 eV (458 nm), respectively. The blue-absorption and emission in the thin films are ascribed to the fact that fluorine atoms on the vinylene units prevent π-stacking of polymeric chains. Furthermore, the dependence of morphology, anisotropy in optical properties and photoluminescence properties of films on deposition methodology is also discussed. MEH-PPDFV also emits homogeneous blue-greenish electroluminescence at 2.46 eV (504 nm).     

Influence of low‐temperature plasma conditions on wicking properties of PA/PU knitted fabric

Plasma surface treatment has been extensively applied in the textile industry for the modification of polymer materials. In this study low‐temperature plasma (LTP) is used for surface treatment of polyamide/polyurethane (PA/PU) knitted fabric. The envisaged plasma effect is an increase in the surface energy of the treated textile, leading toward improved hydrophilic properties. The knitted fabric was treated by LTP using three non polymerizing gases: oxygen, air, and carbon dioxide. After plasma treatment, wettability of samples was tested through their wicking properties measuring capillary rise after water bath contact. The PA/PU knitted fabric samples treated with different plasma gases exhibited different hydrophilic performances. The influence of plasma variables (discharge power, time, pressure) was investigated. Although the chemical characteristics of elastan (PU) and nylon (PA) threads are different, the study has demonstrated that plasma treatment can in the same time alter the surface‐wetting behavior of both the components of the knitted fabric. It was also shown how these treatments can be regulated to produce the desired level of hydrophilicity dependently on the request application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Highly bright and photostable cyanine dye-doped silica nanoparticles for optical imaging: Photophysical characterization and cell tests

Spherical silica nanoparticles containing fluorescent trimethine indocyanine dyes (λ_abs = 547 nm, λ_em = 570 nm) were prepared using a water-in-oil microemulsion method. The nanoparticles were of 50 nm diameter and were almost monodispersed in aqueous solution at pH 5.5. Entrapment of dye molecules in the silica matrix stabilised photoemission over several hours of continuous irradiation. The photoemission intensity of the indocyanine was increased 13-fold over that recorded in solution. As each nanoparticle contained 110 dye molecules, the photoemission brightness of each particle was enhanced by three orders of magnitude. The fluorescent nanoparticles have been tested as imaging tools in in vitro tests. As an example of non-macrophagic cells, a highly differentiated neuronal cell line (GT1-7) was used and the results showed that the prepared nanoparticles can be incorporated into these cells with no apparent toxicity for up to three days.     

In Situ Measurement of Bridging Stresses in Toughened Silicon Nitride Using Raman Microprobe Spectroscopy

Bridging stresses that result both from elastic tractions and frictional interlocking in the wake of an advancing crack have been evaluated quantitatively via in situ Raman microprobe spectroscopy in a toughened Si₃N₄ polycrystal. Crack opening displacement (COD) profiles of bridged cracks also have been measured quantitatively via scanning electron microscopy to substantiate the piezospectroscopic determination of microscopic stresses via Raman spectroscopy. The highest spatial resolution of the stress measurement in the Raman apparatus was 1 µm, as dictated by the optical lens that was used to focus the laser on the sample. Measurements of the bridging stresses were performed both at fixed sites (as a function of the applied load) and along the profile behind the crack tip (under a constant load). Rather high stress values (i.e., 0.4-1.1 GPa) were measured that corresponded with unbroken ligaments that bridged the crack faces in elastic fashion, whereas frictional sites were typically under a lower tensile stress (0.1-0.5 GPa). Mapping the near-tip COD profile and the bridging stresses at the (normal) critical load for catastrophic fracture enabled us to calculate the crack-tip toughness and to explain the rising R -curve behavior of the material. From a comparison with conventional fracture-mechanics data, a self-consistent view of the mechanics that govern the toughening behavior of the Si₃N₄ polycrystal could be obtained. In particular, crack bridging is proven to be, by far, the most important mechanism that contributes to the toughening of polycrystalline Si₃N₄ materials.     

Effects of Eltrombopag on In Vitro Macrophage Polarization in Pediatric Immune Thrombocytopenia

Immune Thrombocytopenia (ITP) is an autoimmune disease characterized by autoantibodies-mediated platelet destruction, a prevalence of M1 pro-inflammatory macrophage phenotype and an elevated T helper 1 and T helper 2 lymphocytes (Th1/Th2) ratio, resulting in impairment of inflammatory profile and immune response. Macrophages are immune cells, present as pro-inflammatory classically activated macrophages (M1) or as anti-inflammatory alternatively activated macrophages (M2). They have a key role in ITP, acting both as effector cells, phagocytizing platelets, and, as antigen presenting cells, stimulating auto-antibodies against platelets production. Eltrombopag (ELT) is a thrombopoietin receptor agonist licensed for chronic ITP to stimulate platelet production. Moreover, it improves T and B regulatory cells functions, suppresses T-cells activity, and inhibits monocytes activation. We analyzed the effect of ELT on macrophage phenotype polarization, proposing a new possible mechanism of action. We suggest it as a mediator of macrophage phenotype switch from the M1 pro-inflammatory type to the M2 anti-inflammatory one in paediatric patients with ITP, in order to reduce inflammatory state and restore the immune system function. Our results provide new insights into the therapy and the management of ITP, suggesting ELT also as immune-modulating drug.     

The Age-Sensitive Efficacy of Calorie Restriction on Mitochondrial Biogenesis and mtDNA Damage in Rat Liver

Calorie restriction (CR) is the most efficacious treatment to delay the onset of age-related changes such as mitochondrial dysfunction. However, the sensitivity of mitochondrial markers to CR and the age-related boundaries of CR efficacy are not fully elucidated. We used liver samples from ad libitum-fed (AL) rats divided in: 18-month-old (AL-18), 28-month-old (AL-28), and 32-month-old (AL-32) groups, and from CR-treated (CR) 28-month-old (CR-28) and 32-month-old (CR-32) counterparts to assay the effect of CR on several mitochondrial markers. The age-related decreases in citrate synthase activity, in TFAM, MFN2, and DRP1 protein amounts and in the mtDNA content in the AL-28 group were prevented in CR-28 counterparts. Accordingly, CR reduced oxidative mtDNA damage assessed through the incidence of oxidized purines at specific mtDNA regions in CR-28 animals. These findings support the anti-aging effect of CR up to 28 months. Conversely, the protein amounts of LonP1, Cyt c, OGG1, and APE1 and the 4.8 Kb mtDNA deletion content were not affected in CR-28 rats. The absence of significant differences between the AL-32 values and the CR-32 counterparts suggests an age-related boundary of CR efficacy at this age. However, this only partially curtails the CR benefits in counteracting the generalized aging decline and the related mitochondrial involvement.