25‐Allyloxy‐5,11,17,23‐tetra‐tert‐butyl‐26,27,28‐trihydroxycalix[4]arene chloroform disolvate

In the title solvated calixarene, C₄₇H₆₀O₄·2CHCl₃, the host chalice displays an almost undistorted cone conformation, stabilized by three strong O—H...O hydrogen bonds at the calixarene's lower rim. One chloroform solvent molecule is fixed in the calixarene cavity by C—H...π interactions, while the second is accommodated in a clathrate‐like mode in elliptical packing voids. These voids are spanned by six host molecules connected via C—H...π contacts and van der Waals interactions. Within the crystal structure, one tert‐butyl group of the calixarene host is disordered over two orientations, with occupancies of 0.884 (4) and 0.116 (4). Furthermore, both solvent molecules show disorder, with occupancies of 0.857 (2) and 0.143 (2) for the cavitate‐type, and 0.9359 (17) and 0.0641 (17) for the clathrate‐type chloroform solvent molecules.     

On-line analysis of volatile fatty acids in anaerobic treatment processes

In this paper, an on-line spectrofluorimetric system is proposed for a simple, rapid and accurate measurement of volatile fatty acids (VFA) in anaerobic treatment processes. The determination method is based on the derivatization of VFA with N-(1-naphthyl)ethylenediamine (EDAN) followed by a spectrofluorimetric detection of the corresponding amide. The analytical procedure is automated with a flow analysis technique, coupling multisyringe (MSFIA) and multi-pumping (MPFS) methods. Operative conditions have been investigated with a special attention paid to the activation and amidation steps and to the liquid-liquid extraction of the derivatized final product. Fluorescence intensities (λ_em = 335 nm, λ_ex = 395 nm) were found to be proportional to the concentration of VFA, expressed as acetic equivalent, in the range 19-1000 mg L⁻¹, with a detection limit (3σ) of 5.1 mg L⁻¹. Our results showed a good selectivity for VFA as compared to other organic and inorganic compounds usually found in sewage sludges. Validation of the on-line system developed has been assessed by application of the procedure to aqueous samples originating from sewage sludge treatment plants. The results were in good agreement with ion chromatography measurements.     

Superamphiphilic Janus fabric

Janus fabrics with superamphiphilicity were fabricated via electrospinning of polyacrylonitrile (PAN). PAN nanofibrous mats were formed on an aluminum foil substrate and then thermally treated to cause hydrolysis. An identical PAN solution was subsequently electrospun onto the hydrolyzed PAN layer, followed by peeling off of the bicomposite film from the collector substrate to produce a free-standing Janus fabric. On one side, the electrospun PAN mat exhibited superhydrophobic properties, with a water contact angle of 151.2°, whereas the initially superhydrophobic PAN sheet on the opposite side of the fabric was converted to a superhydrophilic surface (water contact angle of 0°) through hydrolysis of the surface functional groups induced by the thermal treatment. The resulting Janus fabrics exhibited both superhydrophobicity, repelling water on the one side, and superhydrophilicity, absorbing water on the other side. The organic solvent resistance of the PAN nanofibrous sheets was remarkably improved by incorporation of a tetraethyl orthosilicate. This facile and simple technique introduces a new route for the design and development of functional smart, robust fabrics from an inexpensive, commercially available polymer.     

Sol–gel derived Si/C/O/N‐materials: molecular model compounds,xerogels and porous ceramics

Polymeric Si/C/O/N xerogels, with the idealized polymer network structure comprising [Si O Si(NCN)₃]_n moieties, were prepared by reactions of hexachlorodisiloxane (Cl₃Si O SiCl₃) with bis(trimethylsilyl)carbodiimide (Me₃Si NCN SiMe₃, BTSC). NMR and FTIR spectra indicate the existence of ‐NCN‐ and Si O Si‐ units in the xerogels and also in the ceramic materials obtained upon pyrolysis. The feasibility of this reaction protocol was confirmed on the molecular level by the deliberate synthesis of the macrocyclic compound [SiPh₂ O SiPh₂(NCN)]₂, the crystal structure and spectroscopic data of which are reported. The influence of pyridine as a catalyst for the cross‐linking reaction was studied. The degree of cross‐linking increased within the polymers with the addition of pyridine. It was shown by the reaction of hexachlorodisiloxane with excess pyridine that the latter appears to activate only one out of the two ‐SiCl₃ moieties under formation of hexacoordinated silicon compounds. The crystal structure of Cl₃Si O SiCl₃(pyridine)₂ is presented. Quantum chemical calculations are in support of this adduct being a potential intermediate in the pyridine catalyzed sol–gel process. The ceramic yield after pyrolysis of the Si/C/O/N‐xerogels at 1000 °C, which reaches values up to 50%, was found to depend on the aging protocol (time, temperature), whereas no correlation was found with the amount of pyridine added for xerogel synthesis. The Si/C/N/O‐ceramics obtained after pyrolysis at 1000 °C under NH₃ are completely amorphous. Chemically they have to be considered as hybrids between an ideal [SiOSi(NCN)₃]_n network and glass‐like Si₂N₂O. The products are mesoporous with closed pores and a broad pore size distribution. Copyright © 2011 John Wiley & Sons, Ltd.     

Isolation and Cultivation of a Xylanolytic Bacillus subtilis Extracted from the Gut of the Termite Reticulitermes santonensis

The aim of this work was the isolation of xylanolytic microorganisms from the digestive tract of the termite Reticulitermes santonensis. The reducing sugars released after the hydrolysis of xylans can be further fermented to provide bioethanol. A xylanolytic strain of Bacillus subtilis was isolated from the hindgut of the termite and displayed amylase and xylanase activities. The bacterium was grown on media containing agricultural residues: wheat bran, wheat distiller’s grains, and rapeseed oil cake. Wheat bran led to the highest induction of xylanase activity, although the development of the strain was less fast than in the other media. It was possible to reach maximal xylanase activities of 44.3, 33.5, and 29.1 I.U./ml in the media containing wheat bran, wheat distiller’s grains, and rapeseed oil cake, respectively. Mass spectrometry identified a wide range of xylose oligomers, highlighting an endoxylanase activity. The enzyme was stable up to 45 °C and displayed an optimal pH close to 8.     

Dendrons and Dendritic Terpolymers: Synthesis,Characterization and Self-Assembly Comparison

To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons.     

A novel dual surface modification on titanium in dental use: Characterization and topography

This laboratory study aimed to compare, contrast, and evaluate the effect of a novel dual surface modification method on the adhesion strength of resin composite cement to titanium. C.p.-2 grade titanium samples were silica-coated, etched with HNO₃(69vol %) or a blend of HCl (35vol %) and H₃PO₄ (85vol %), for 1 h at 80°C. Surface roughness was measured by surface roughness profilometry, topographic analysis by scanning electron microscopy (SEM), atomic force microscopy (AFM), and surface analyses by energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS). Silanization of all specimens was carried out after SEM, EDX, and AFM analysis, before enclosed mold microshear bond strength testing (EM-μSBS). Adhesion strengths were measured after artificial ageing: 1 day, 1 week, 4 weeks, and 8 weeks by EM-μSBS testing and failure mode analysis by optical microscopy. Polished titanium was used as a control. The highest surface roughness was observed in titanium samples treated with silica-coating + HCl-H₃PO₄ etching. The elemental composition confirmed the presence of Ti, O, C, with Si and Al in samples treated with silica-coating. A gradual decrease in EM-μSBS values was observed in all titanium samples with adhesive and cohesive failure modes. The novel dual surface modification method applied in this study suggests that silica-coating + HCl-H₃PO₄etching strongly affects titanium surface topography and roughness. The presence of Si on silica-coated surface modified titanium before silanization with an experimental silane has a positive effect on the EM-μSBS of titanium samples treated with silica-coating only or silica-coating + HNO₃ etching.     

Algebraic forms for the leading factor of the two-electron coefficients of fractional parentage for the atomic l shell

The part of a one-electron coefficient of fractional parentage (cfp) depending, for the atomic l shell, on the spin S, seniority υ, and electron number n of the daughter state, is factored into two parts, the first with dependence on n and υ, and the second with dependence on υ and S. Various techniques are used to extend these results to the two-electron cfp. These entail deriving analogues of the 6-j symbols for the symplectic group Sp(4l + 2) and the special orthogonal group SO(2l + 1). Explicit algebraic expressions are provided, and the choice of multiplicity indices and their circumvention are discussed.