Understanding the Effects of Binders in Gas Sorption and Acidity of Aluminium Fumarate Extrudates

Understanding the impact of shaping processes on solid adsorbents is critical for the implementation of MOFs in industrial separation processes or as catalytic materials. Production of MOF-containing shaped particles is typically associated with loss of porosity and modification of acid sites, two phenomena that affect their performance. Herein, we report a detailed study on how extrusion affects the crystallinity, porosity, and acidity of the aluminium fumarate MOF with clays or SiO₂ gel binders. Thorough characterization showed that the clay binders confer the extrudates a good mechanical robustness at the expense of porosity, while silica gel shows an opposite trend. The CO₂ selectivity towards CH₄, of interest for natural gas separation processes, is maintained upon the extrusion process. Moreover, probe FTIR spectroscopy revealed no major changes in the types of acid sites. This study highlights that these abundant and inexpensive clay materials may be used for scaling MOFs as active adsorbents.     

SBA‐15 pore‐width decrease via a one‐ or a two‐step covalent bonding of a Fischer tungsten carbene as measured by N2 sorption

The chemical attachment of Fischer tungsten carbene molecules around the cylindrical walls of SBA‐15 causes a pore‐width diminution with respect to the diameters of the voids existing in the pristine substrate. The attachment is made via a bridging unit of aminopropyltriethoxysilane (APTES) that, at its ethoxysilane end, anchors on the SBA‐15 surface while, at its amino end, reacts with the tungsten carbene. The attachment can either be made in a single stage by adding the whole molecule, i.e. bridging + carbene units, or stepwise, i.e. the bridging unit is firstly attached to the silica surface and afterward the carbene group is linked to the amine end of the previous species. A remarkable result is that a uniform pore‐width decrease of 0.30 nm is achieved when the ethoxysilane bridging units are anchored on the SiO₂ surface; this decrease being independent of the pore size. An additional decrease of 0.37 nm is observed when the tungsten carbene is fixed to the amine end of the bridging molecule; the total pore‐width decrease is thus 0.67 nm. In turn, the one‐stage insertion of the whole carbene molecules causes a uniform pore‐width decrease of 0.78 nm. The central cores of the functionalized pore entities remain free for the molecular transport of species that are taking place in catalytic, separation, and controlled release processes. The chemical anchoring of molecules on the surface of SBA‐15 pores can be tailor sized and occlude the existing micropores, thus representing important and fundamental industrial applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of Conformationally Restricted Carbocyclic Nucleosides: The Role of the O(4′)-Atom in the Key Hydration Step of Adenosine Deaminase

Conformationally restricted carbocyclic nucleosides with either a northern(N)-type conformation, i.e., N-type 2′-deoxy-methanocarba-adenosine 8 ((N)MCdAdo), or a southern(S)-type conformation, i.e. S-type 2′-deoxy-methanocarba-adenosine 9 , ((S)MCdAdo), were used as substrates for adenosine deaminase (ADA) to assess the enzyme's preference for a fixed conformation relative to the flexible conformation represented by the carbocyclic nucleoside aristeromycin ( 10 ). Further comparison between the rates of deamination of these compounds with those of the two natural substrates adenosine (Ado; 1 ) and 2′-deoxyadenosine (dAdo; 2 ), as well as with that of the conformationally locked nucleoside LNA-Ado ( 11 ), which, like the natural substrates, has a furanose O(4′) atom, helped differentiate between the roles of the O(4′) anomeric effect and sugar conformation in controlling the rates of deamination by ADA. Differences in rates of deamination as large as 10000 can be attributed to the combined effect of the O(4′) atom and the enzyme's preference for an N-type conformation. The hypothesis proposed is that ADA's preference for N-type substrates is not arbitrary; it is rather the direct consequence of the conformationally dependent O(4′) anomeric effect, which is more efficient in N-type conformers in promoting the formation of a covalent hydrate at the active site of the enzyme. The formation of a covalent hydrate at the active site of ADA precedes deamination. A new and efficient synthesis of the important carbobicyclic template 14a , a useful intermediate for the synthesis of (N)MCdAdo ( 8 ) and other conformationally restricted nucleosides, is also reported.     

Application of solid-state nuclear track detectors for studies of fast ion beams within PF-1000 and other plasma-focus facilities

The paper presents results of studies of the fast ion emission from two plasma facilities: PF-1000 and PF-II. The measurements were carried out mainly with solid-state nuclear track detectors (SSNTDs). To register ion mass- and energy-spectra, obtained when primary ion beams are deflected by magnetic and electric fields of a Thomson-type spectrometer, the SSNTDs plates were installed inside the analyzer. To measure ion angular distributions the SSNTDs were located within the main discharge chamber, at different angles to the electrode axis. The SSNTDs were also applied to register ion beam images formed within an ion pinhole camera, and to determine a spatial location of the fast ion sources.     

Self-condensation of β-(isoxazol-5-yl) enamines under treatment with acetyl chloride and acids. Synthesis of novel 1,3-diisoxazolyl-1,3-dieneamines and 1,3,5-triisoxazolyl benzenes

Two directions for self-condensation of β-(isoxazol-5-yl) enamines under treatment with either acetyl chloride or acids were found leading to new 1,3-diisoxazolyl-1,3-dieneamines and 1,3,5-triisoxazolyl benzenes. The effect of solvent, acid, temperature and the reaction time on the ratio of reaction products were investigated. Trans-E-cis configuration of prepared 1,3-diisoxazolyl-1,3-dieneamines was unambiguously confirmed by 2D NMR spectra and X-ray analysis. A new mechanism of 1,3-diisoxazolyl-1,3-dieneamines formation was proposed.     

Self-assembly and lipid interactions of diacylglycerol lactone derivatives studied at the air/water interface

Synthetic diacylglycerol lactones (DAG-lactones) have been shown to be effective modulators of critical cellular signaling pathways. The biological activity of these amphiphilic molecules depends in part upon their lipid interactions within the cellular plasma membrane. This study explores the thermodynamic and structural features of DAG-lactone derivatives and their lipid interactions at the air/water interface. Surface-pressure/area isotherms and Brewster angle microscopy revealed the significance of specific side-groups attached to the terminus of a very rigid 4-(2-phenylethynyl)benzoyl chain of the DAG-lactones, which affected both the self-assembly of the molecules and their interactions with phospholipids. The experimental data highlight the formation of different phases within mixed DAG-lactone/phospholipid monolayers and underscore the relationship between the two components in binary mixtures of different mole ratios. Importantly, the results suggest that DAG-lactones are predominantly incorporated within fluid phospholipid phases rather than in the condensed phases that form, for example, by cholesterol. Moreover, the size and charge of the phospholipid headgroups do not seem to affect DAG-lactone interactions with lipids.     

Factors affecting the synthesis of polymeric nanostructures from template assisted admicellar polymerization

Template assisted admicellar polymerization (TAAP) utilizes a surfactant layer adsorbed on a surface to localize a monomer to the surface prior to polymerization of the monomer. Nanostructures are formed by restricting adsorption to the uncovered sites of an already-templated surface, in this case, to the interstitial sites between adsorbed latex spheres. This work studies the factors affecting the synthesis of polymeric nanostructures from TAAP for three different monomers, aniline, pyrrole, and methyl methacrylate, and three different surfaces, highly ordered pyrolytic graphite (HOPG), gold, and SiO2. Among the parameters discussed are the effects of monomer and surfactant concentration, surfactant chain length, polymerization time and temperature, and solution ionic strength. Control of the aforementioned parameters allows some control over the nanostructure morphology. Polymer nanopillars, nanorings, honeycombs, and "honeytubes" have been synthesized. Important conclusions regarding the conditions favoring admicellar polymerization relative to polymerization in solution are drawn from the experimental results as well. Sample characterization includes scanning electron microscopy (SEM), Raman spectroscopy, and alternating current (ac) impedance measurements.