Electrical properties of monoazacrown ether-substituted phthalocyanines

D.c. conductivities of polycrystalline monoazacrown ether-substituted phthalocyanines (M=2H, Ni, Zn, Pb, Cu) and diphthalocyanine (M=Lu) are measured as Au-MPc-Au sandwiches to be of the order 10^–10–10^–12 S m^–1. Chemical doping with oxidants (e.g. NOBF₄) and enhancing the stacking of planar phthalocyanine moieties through the formation of alkali metal adducts with sodium and potassium ions leads to increase in conductivity of the order 10¹–10². The low conductivity and the diamagneticity of the bis(phthalocyaninato)-lutetium can be ascribed to the lack of radical nature in LuH(Pc)₂. For the a.c. conductivities, lead and lutetium complexes form a group with higher conductivities and the rest show lower conductivity. The conduction activation energies calculated from Arrhenius plots exhibit the lowest value (0.40 eV) for the lutetium compound.Part of this work was presented at NATO-ASI on Semiconductor Materials and Processing Technologies, Erice, Sicily, 1–13 July 1991.     

Qualitative and Quantitative Comparison of Plasma Exosomes from Neonates and Adults

Exosomes are extracellular vesicles that contain nucleic acids, lipids and metabolites, and play a critical role in health and disease as mediators of intercellular communication. The majority of extracellular vesicles in the blood are platelet-derived. Compared to adults, neonatal platelets are hyporeactive and show impaired granule release, associated with defects in Soluble N-ethylmaleimide-sensitive fusion Attachment protein REceptor (SNARE) proteins. Since these proteins participate in biogenesis of exosomes, we investigated the potential differences between newborn and adult plasma-derived exosomes. Plasma-derived exosomes were isolated by ultracentrifugation of umbilical cord blood from full-term neonates or peripheral blood from adults. Exosome characterization included size determination by transmission electron microscopy and quantitative proteomic analysis. Plasma-derived exosomes from neonates were significantly smaller and contained 65% less protein than those from adults. Remarkably, 131 proteins were found to be differentially expressed, 83 overexpressed and 48 underexpressed in neonatal (vs. adult) exosomes. Whereas the upregulated proteins in plasma exosomes from neonates are associated with platelet activation, coagulation and granule secretion, most of the underexpressed proteins are immunoglobulins. This is the first study showing that exosome size and content change with age. Our findings may contribute to elucidating the potential “developmental hemostatic mismatch risk” associated with transfusions containing plasma exosomes from adults.     

Pharmacological Evidence on Augmented Antiallodynia Following Systemic Co-Treatment with GlyT-1 and GlyT-2 Inhibitors in Rat Neuropathic Pain Model

The limited effect of current medications on neuropathic pain (NP) has initiated large efforts to develop effective treatments. Animal studies showed that glycine transporter (GlyT) inhibitors are promising analgesics in NP, though concerns regarding adverse effects were raised. We aimed to study NFPS and Org-25543, GlyT-1 and GlyT-2 inhibitors, respectively and their combination in rat mononeuropathic pain evoked by partial sciatic nerve ligation. Cerebrospinal fluid (CSF) glycine content was also determined by capillary electrophoresis. Subcutaneous (s.c.) 4 mg/kg NFPS or Org-25543 showed analgesia following acute administration (30–60 min). Small doses of each compound failed to produce antiallodynia up to 180 min after the acute administration. However, NFPS (1 mg/kg) produced antiallodynia after four days of treatment. Co-treatment with subanalgesic doses of NFPS (1 mg/kg) and Org-25543 (2 mg/kg) produced analgesia at 60 min and thereafter meanwhile increased significantly the CSF glycine content. This combination alleviated NP without affecting motor function. Test compounds failed to activate G-proteins in spinal cord. To the best of our knowledge for the first time we demonstrated augmented analgesia by combining GlyT-1 and 2 inhibitors. Increased CSF glycine content supports involvement of glycinergic system. Combining selective GlyT inhibitors or developing non-selective GlyT inhibitors might have therapeutic value in NP.     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

SUL-151 Decreases Airway Neutrophilia as a Prophylactic and Therapeutic Treatment in Mice after Cigarette Smoke Exposure

Chronic obstructive pulmonary disease (COPD) caused by cigarette smoke (CS) is featured by oxidative stress and chronic inflammation. Due to the poor efficacy of standard glucocorticoid therapy, new treatments are required. Here, we investigated whether the novel compound SUL-151 with mitoprotective properties can be used as a prophylactic and therapeutic treatment in a murine CS-induced inflammation model. SUL-151 (4 mg/kg), budesonide (500 μg/kg), or vehicle were administered via oropharyngeal instillation in this prophylactic and therapeutic treatment setting. The number of immune cells was determined in the bronchoalveolar lavage fluid (BALF). Oxidative stress response, mitochondrial adenosine triphosphate (ATP) production, and mitophagy-related proteins were measured in lung homogenates. SUL-151 significantly decreased more than 70% and 50% of CS-induced neutrophils in BALF after prophylactic and therapeutic administration, while budesonide showed no significant reduction in neutrophils. Moreover, SUL-151 prevented the CS-induced decrease in ATP and mitochondrial mtDNA and an increase in putative protein kinase 1 expression in the lung homogenates. The concentration of SUL-151 was significantly correlated with malondialdehyde level and radical scavenging activity in the lungs. SUL-151 inhibited the increased pulmonary inflammation and mitochondrial dysfunction in this CS-induced inflammation model, which implied that SUL-151 might be a promising candidate for COPD treatment.     

Polylactide films formed by immersion precipitation: Effects of additives,nonsolvent, and temperature

The influence of nonsolvent, crystallinity of the polymer film, and addition of dodecane (a poor solvent for the polymer and for the nonsolvent) on the morphology of polylactides films has been investigated and was related to phase separation behavior. Both amorphous poly‐DL ‐lactide (PDLLA) and crystalline poly‐L ‐lactide (PLLA) were dissolved in dichloromethane, and subsequently films were made by immersion in nonsolvent baths. PDLLA gave dense films without any internal structure, since the structure was not solidified by crystallization or glassification. PLLA films show varying structure depending on the nonsolvent. With methanol, asymmetric morphologies were observed as a result from combined liquid‐liquid demixing and crystallization, while with water symmetric spherulitic structures were formed. As a next step, dodecane was added, which is not miscible with the nonsolvent, and we found it to have a strong influence on the morphology of the films. The PDLLA films with dodecane did not collapse: a closed cell structure was obtained. In PLLA films, dodecane speeds up phase separation and induces faster crystallization in the films, and the porosity, size of the pores, and interconnectivity increased. When the PLLA solutions were subjected to a heat pretreatment, crystallization could be postponed, which yielded a cellular structure around dodecane, which did not contain spherulites anymore. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 959–971, 2007     

SOLUBILITY AND DIFFUSIVITY OF GASES IN AN ORGANIC SOLUTION OF AMINE

Solubilities and diffusivities of carbon dioxide and nitrous oxide in a mixture of toluene and isopropanol organic solution of cyclohexylamine were measured at 20°C in the range of pressures of solute from 1 to 3 bars. This was performed with an original chromatographic technique taking into account the presence of the product of the reaction.     

Crystallinity in PPS–carbon composites: A study using diffuse reflection FT-IR spectroscopy and differential scanning calorimetry

A method based on diffuse reflection Fourier transform infrared (FT-IR) spectroscopy has been developed for determining the state of crystallinity in composite materials made from poly(phenylene sulfide) (PPS) reinforced with carbon fibers. Using this technique, good-quality spectra can be obtained directly from the surface of prepreg or molded composite; thus the method is rapid and nondestructive. Several peaks in the spectrum are sensitive to the crystallinity and can be used for quantitative characterization purposes. The recommended indicator is the ratio of the heights of the peaks at 1075 and 1093 cm^?1. Using a range of samples of varying crystallinity prepared by annealing amorphous prepreg, it has been shown that there is a very good correlation between this ratio and the enthalpy of crystallization as determined by differential scanning calorimetry. The effects of such annealing, as well as heating in air at high temperatures, have been investigated.     

Lead recovery from aqueous environment by using porous carbon of citrus fruits waste: equilibrium,kinetics and thermodynamic studies

ABSTRACT

The mixture of citrus fruits (orange, grapefruit, mandarin, and lemon) wastes was utilized to obtain high surface area activated carbon (AC) by H₃PO₄ activation. The production conditions were optimized and the optimum conditions were determined. The optimal-activated carbon (CFWAC) was characterized by various physicochemical techniques. CFWAC was also used as a sorbent for Pb (II) ions from water. Batch experiments were performed to explore the adsorption capacity and mechanism. The Langmuir isotherm and pseudo-second-order kinetic model showed good fitness to the experimental data. The maximum Pb (II) adsorption capacity of CFWAC was found to be 163.93 mg/g.     

Effect of Adding Transition Metals to Copper on the Dehydrogenation Reaction of Ethanol

The present work aims to investigate the effect adding Ag, Co, Ni, Cd and Pt to copper on ethanol dehydrogenation. The catalysts synthesized by deposition–precipitation method were characterized using various physicochemical methods such as N₂ adsorption–desorption, TPR, SEM–EDX, XRD, XPS and TGA–DSC-MS. Catalytic evaluation results revealed that the predominant product of the reaction was acetaldehyde. Monometallic copper or mixed with Cd, Ag or Co show good catalytic performances. Adding nickel to copper improves the process conversion but reduces acetaldehyde selectivity, giving rise to methane in produced hydrogen. Pt-Cu/SiO₂ catalyst guides the reaction towards diethyl ether. Time on stream tests performed during 12 h at 260 °C, showed that adding Cd to Cu enhances its stability by over 30% of conversion, this is explained by the reduction of copper crystallites sintering, which makes Cd-Cu/SiO₂ a promising catalyst for the production of acetaldehyde by ethanol dehydrogenation.

Graphic Abstract