Synthesis monitoring of SBA-15 nanostructured materials

The SBA-15 materials were synthesized by the hydrothermal method using tetraethyl orthosilicate as silica source and P123 as template agent. The synthesis process was accomplished varying the time during the hydrothermal processing. For the synthesis monitoring, a small amount of sample was removed at different times, and analyzed by thermal analysis in order to determine the temperature ranges related to water desorption, template decomposition and silanol condensation for the SBA-15 nanostructured materials, as well as to estimate their quality. The samples were characterized by X-ray diffraction, infrared absorption spectroscopy, scanning electron microscopy, BET surface area and pore size distribution. The activation energy relative to decomposition of P123 template was determined from TG curves, using multiple heating rates and applying the model free kinetics. From the obtained data, it is possible to monitor the hydrothermal synthesis of SBA-15 in order to control the properties and conditions to prepare ordered materials.     

Faraday’s Form and Maxwell’s Equations in the Heisenberg Group

In this note we present a geometric formulation of Maxwell’s equations in Carnot groups (connected simply connected nilpotent Lie groups with stratified Lie algebra) in the setting of the intrinsic complex of differential forms defined by M. Rumin. Restricting ourselves to the first Heisenberg group \mathbbH¹{\mathbb{H}^{1}}, we show that these equations are invariant under the action of suitably defined Lorentz transformations, and we prove the equivalence of these equations with differential equations “in coordinates”. Moreover, we analyze the notion of “vector potential”, and we show that it satisfies a new class of 4th order evolution differential equations.     

D'Alembert formula on finite one-dimensional networks

We find a d'Alembert type formula for the solution of the Cauchy problem for the wave equation on finite weighted networks. We also discuss the periodicity in time of the solution in terms of the spectrum of the discrete graph associated with the network and finally we present two significant examples to illustrate and clarify the general analysis.     

On Blaschke's extension of Bonnesen's inequality

W. Blaschke established a Bonnesen-style inequality for the relative inradius and circumradius of a planar convex bodyK with respect to another. We sharpen this inequality by considering the radii of the minimal convex annulus ofK.     

Electrochemically Aided Control of Solid Phase Micro-Extraction (EASPME) Using Conducting Polymer-Coated Solid Substrates Applicable to Neutral Analytes

A method for the extraction and selective determination of the neutral species arsenobetaine (AsB) is proposed using electro-synthesized organic conducting polymer (OCP) films. The polymer films are used as solid phase micro-extraction (SPME) elements for the direct and specific extraction of trace levels of AsB. The separation and detection of the arsenic (As) species is attained using an HPLC-ICP-MS interfaced system. The selectivity of the method towards neutral AsB in the presence of other anionic As-species is explained in terms of the change in the hydrophobic nature of the film during the doping/undoping processes. The type of OCP, the thickness of the film, the applied potential during uptake and release of AsB are among the factors studied for the method. The uptake and release time/potential profiles are given, and a thermodynamic model is proposed. The performance of poly(3-octylthiophene), poly(3-dodecylthiophene), and poly(3-hexadecylthiophene) films were compared, with the best results obtained using poly(3-octylthiophene). The detection limit and linear dynamic range using this method are 14ngmL^–1 and 70–1200ngmL^–1, respectively. The method was validated using a standard reference material and tested for the determination of AsB in artificial environmental soil samples.     

The signature molecular descriptor. 2. Enumerating molecules from their extended valence sequences

We present a new algorithm that enumerates molecular structures matching a predefined extended valence sequence or signature. The algorithm can construct molecular structures composed of about 50 non-hydrogen atoms in CPU seconds time scale. The algorithm is run to produce all molecular structures matching the binding affinities (IC(50)) of some HIV-1 protease inhibitors. The algorithm is also used to compute the degeneracy, or the number of molecular structures, corresponding to a given signature. Signature degeneracy is systematically studied for varying signature heights on four molecular series, alkanes, alcohols, fullerene-type structures, and peptides. Signature degeneracy is compared with similar results obtained with popular topological indices (TIs). As a general rule, we find that signature degeneracy decreases as the signature height increases. We also find that alkanes, alcohols, and fullerene-type structures comprising n non-hydrogen atoms are uniquely characterized by signatures of height n/4, while peptides up to 4000 amino acids can be singled out with signatures of heights as small as 2 and 3.     

Ion pairing in fast-exchange host-guest systems: concentration dependence of apparent association constants for complexes of neutral hosts and divalent guest salts with monovalent counterions

An equilibrium treatment of complexation of neutral hosts with dicationic guests having univalent counterions includes two possible modes: (1) dissociation of the ion pair prior to interaction of the free dication with the host to produce a complex that is not ion paired and (2) direct complexation of the ion pair to produce an ion paired complex. This treatment is easily modified for complexation of neutral guests by dianionic hosts, or divalent hosts by neutral guests. The treatment was tested by a study of fast-exchange host-guest systems based on paraquats or viologens (G(2+)2X(-)) and crown ethers (H). The bis(hexafluorophosphate) salts of viologens are predominantly ion paired in acetone; the value of the dissociation constant of paraquat bis(hexafluorophosphate) was determined to be 4.64 (+/- 1.86) x 10(-4) M(2). The complex based on dibenzo-24-crown-8 and paraquat bis(hexafluorophosphate) is not ion paired in solution, resulting in concentration dependence of the apparent association constant K(a,exp), (= [complex]/[H][G(2+)2X(-)]) which is well fit by the treatment, according to mode (1), yielding K(ap) = 106 (+/-42) M(-1). However, the four complexes of two different bis(m-phenylene)-32-crown-10 derivatives and bis(p-phenylene)-34-crown-10 with paraquat derivatives are all ion paired in solution and therefore K(a,exp) is not concentration dependent for these systems, mode (2). X-ray crystal structures support these solution-based assessments in that there is clearly ion pairing of the cationic guest with its PF(6)(-) counterions in the solid states of the latter four examples in which access of the counterions to the guests is granted by the relatively large cavities of the hosts and dispositions of the guest species within them.     

Chromatographic evaluation of self-immobilized stationary phases for reversed-phase liquid chromatography

The preparation of stationary phases for HPLC using polymers deposited on silica usually includes an immobilization step involving cross-linking by free radicals induced by ionizing radiation or by other radical initiators. The present paper reports changes which occur at ambient temperature in the character of poly(methyloctylsiloxane) deposited on porous silica particles as a function of the time interval between particle loading and column packing. Column performance and retention factors increase with time and these changes are attributed to rearrangement (self-assembly) which result in "self-immobilization" of the polymer molecules on the silica surface.     

New method for separation and determination of denatured caseins by hydrophobic interaction chromatography

A new method for the separation of denatured alpha-, beta- and kappa- caseins by hydrophobic interaction chromatography (HIC) is proposed. The method is based on an easy solubilization of commercial and real samples by 4.0 M guanidine thiocyanate (GdmSCN) and elution on a TSK-Gel(R) Phenyl-5PW column (TosoHaas) in the presence of 8.0 M urea in the mobile phase. The procedure, applied to commercial caseins and to real, raw samples (whole milk powder and fat-free yoghurt) is not expensive, it requires common high performance liquid chromatography (HPLC) instrumentation and allows the separation of caseins also in the presence of whey proteins. Quantitative results on the analysis of alpha-, beta- and kappa-caseins in real samples are also reported.