Use of novel cardanol-porphyrin hybrids and their TiO₂-based composites for the photodegradation of 4-nitrophenol in water

Cardanol, a well known hazardous byproduct of the cashew industry, has been used as starting material for the synthesis of useful differently substituted "cardanol-based" porphyrins and their zinc(II), copper(II), cobalt(II) and Fe(III) complexes. Novel composites prepared by impregnation of polycrystalline TiO? powder with an opportune amount of "cardanol-based" porphyrins, which act as sensitizers for the improvement of the photo-catalytic activity of the bare TiO?, have been used in the photodegradation in water of 4-nitrophenol (4-NP), which is a toxic and bio-refractory pollutant, dangerous for ecosystems and human health.     

Flow‐Injection Amperometric Method for Indirect Determination of Dopamine in the Presence of a Large Excess of Ascorbic Acid

A simple flow injection amperometric system for fast and indirect quantification of dopamine (DA) in the presence of a large excess of ascorbic acid (AA) is reported. The method consists of the application of three sequential potential pulses to an unmodified glassy carbon‐working electrode positioned in a wall‐jet cell. DA is indirectly detected at +0.35 V through the reduction of the oxidation product (o‐dopaminoquinone) electrochemically generated at +0.80 V. The third potential pulse (0.00 V) is applied for the regeneration (cleaning) of the unmodified working electrode. The limits of detection (LOD) and quantification (LOQ) were calculated as 50 and 170 nmol L^?1, respectively. Considering the LOQ value, the present methodology allows DA quantification in the presence up to 5000‐fold more of AA (1.0 mmol L^?1).     

Improve-and-Branch Algorithm for the Global Optimization of Nonconvex NLP Problems

A new algorithm to solve nonconvex NLP problems is presented. It is based on the solution of two problems. The reformulated problem RP is a suitable reformulation of the original problem and involves convex terms and concave univariate terms. The main problem MP is a nonconvex NLP that outer-approximates the feasible region and underestimate the objective function. MP involves convex terms and terms which are the products of concave univariate functions and new variables. Fixing the variables in the concave terms, a convex NLP that overestimates the feasible region and underestimates the objective function is obtained from the MP. Like most of the deterministic global optimization algorithms, bounds on all the variables in the nonconvex terms must be provided. MP forces the objective value to improve and minimizes the difference of upper and lower bound of all the variables either to zero or to a positive value. In the first case, a feasible solution of the original problem is reached and the objective function is improved. In general terms, the second case corresponds to an infeasible solution of the original problem due to the existence of gaps in some variables. A branching procedure is performed in order to either prove that there is no better solution or reduce the domain, eliminating the local solution of MP that was found. The MP solution indicates a key point to do the branching. A bound reduction technique is implemented to accelerate the convergence speed. Computational results demonstrate that the algorithm compares very favorably to other approaches when applied to test problems and process design problems. It is typically faster and it produces very accurate results.     

Precision of Flash Pyrolysis-GC-MS Analysis: Experimental Evaluation of the Sources of Variability

The present study was carried out to evaluate the precision and to identify significant sources of variability in flash pyrolysis-GC-MS experiments. The analysis of variance has been applied to the example of polyethylene pyrolysis to estimate the impact of several controlled factors: sample handling, flash pyrolysis filament ageing and calibration. It was demonstrated that to get the best precision in experimental results, it is recommended to set the operator to reduce the impact of sample handling procedure and the filament to avoid variability due to changes in filament characteristics. In comparison, filament ageing and filament calibration are shown to influence in a limited extent the experimental results.     

Discovery by serendipity: a new context for an old riddle

In the last years there has been a great improvement in the development of computational methods for combinatorial chemistry applied to drug discovery. This approach to drug discovery is sometimes called a “rational way” to manage a well known phenomenon in chemistry: serendipity discoveries. Traditionally, serendipity discoveries are understood as accidental findings made when the discoverer is in quest for something else. This ‘traditional’ pattern of serendipity appears to be a good characterization of discoveries where “luck” plays a key role. In this sense, some initial failures in combinatorial chemistry are frequently attributed to a naïf appropriation of a “serendipity model” for discovery (a “serendipity mistake”). In this paper we try to evaluate this statement by criticizing its foundations. It will be suggested that the notion of serendipity has different aspects and that the criticism to the first attempts could be understood as a “serendipity mistake.” We will suggest that “serendipity” strategies, a kind of blind search, can be seen sometimes as a “genuine part” of scientific practice. A discussion will ensue about how this characterization can give us a better understanding of some aspects of serendipity discoveries.     

Interaction of human gingival fibroblasts with PVA/gelatine sponges

Tissue engineering scaffolds should be able to reproduce optimal microenvironments in order to support cell attachment, three-dimensional growth, migration and, regarding fibroblasts, must also promote extracellular matrix production. Various bioactive molecules are employed in the preparation of spongy scaffolds to obtain biomimetic matrices by either surface-coating or introducing them into the bulk composition of the biomaterial. The biomimetic properties of a spongy matrix composed of PVA combined with the natural component gelatine were evaluated by culturing human gingival fibroblasts on the scaffold. Cell adhesion, morphology and distribution within the scaffold were assessed by histology and electron microscopy; viability and metabolic activity as well as extracellular matrix production were analyzed by MTT assay, cytochemistry and immunocytochemistry. Fibroblasts interacted positively with PVA/gelatine. They adhered to the PVA/gelatine matrix in which they had good spreading activity and active metabolism; fibroblasts were also able to produce extracellular matrix molecules (type I collagen, fibronectin and laminin) compared to bi-dimensionally grown cells. The in situ creation of a biological matrix by human fibroblasts together with the ability to produce growth factor TGF-beta1 and the intracellular signal transduction molecule RhoA, suggests that this kind of PVA/gelatine sponge may represent a suitable support for in vitro extracellular matrix production and connective tissue regeneration.     

Structures of poly(p-hydroxybenzoic acid) (PHBA) at ambient temperature

The molecular structure of poly (p-hydroxybenzoic acid) (C₆H₄COO)_x at ambient temperature was determined by x-ray powder diffraction analysis. The diffraction pattern is explained as a mixture of two orthorhombic phases having the same space group Pbc2₁ with four C₆H₄COO chemical repeats in the unit cell and the following cell parameters: a = 7.42 Å, b = 5.70 Å, and c = 12.45 Å for phase I (ρ_calc = 1.51 g cm^?3); and a = 3.83 Å, b = 11.16 Å, and c = 12.56 Å for phase II (ρ_calc = 1.48 g cm^?3). The chain conformation is the same in both phases, involving two benzoyl rings staggered by ca. 120° along the chain. Disorder has been considered in the packing of phase I by giving equal occupancy to the two molecules oriented up or down along the c chain axis. ©1995 John Wiley & Sons, Inc.     

Giant first-forbidden resonances

Recent experimental data on first-forbidden charge-exchange resonances are discussed in the framework of a schematic model. We also evaluate the screening of the weak coupling constants induced by both the giant resonances and the Δ-isobar. It is shown that the last effect does not depend on the multipolarity of the one-particle moment. Due to the same reason, the fraction of the reaction strength pushed up into the Δ-resonance region is always the same regardless of the quantum numbers carried by the excitation. Simple expressions are derived for the dependence of the excitation energies of the first-forbidden giant resonances on the mass number and isospin of the target. The model reproduces consistently both the Gamow-Teller and the first-forbidden resonances.