Solvent effects in the reaction of 2-thiophenesulfonyl chloride with aniline

The second order rate constants k₂ and the activation parameters for the reaction of 2-thiophenesulfonyl chloride with aniline together with solution enthalpies of the reactants have been measured in methanol, ethanol, 2-propanol, acetonitrile and acetone. The reaction rates are slower in dipolar aprotic solvents than in protic ones due to a remarkable activation negative entropy. The rate constants k₂ are correlated with empirical solvent polarity parameters. The data seem in accord with a S_AN reaction mechanism.     

Inner solvers for interior point methods for large scale nonlinear programming

This paper deals with the solution of nonlinear programming problems arising from elliptic control problems by an interior point scheme. At each step of the scheme, we have to solve a large scale symmetric and indefinite system; inner iterative solvers, with an adaptive stopping rule, can be used in order to avoid unnecessary inner iterations, especially when the current outer iterate is far from the solution. In this work, we analyse the method of multipliers and the preconditioned conjugate gradient method as inner solvers for interior point schemes. We discuss the convergence of the whole approach, the implementation details and report the results of numerical experimentation on a set of large scale test problems arising from the discretization of elliptic control problems. A comparison with other interior point codes is also reported. This research was supported by the Italian Ministry for Education, University and Research (MIUR) projects: FIRB Project: “Parallel Nonlinear Numerical Optimization PN ² O” (grant n. RBAU01JYPN, ) and COFIN/PRIN04 Project “Numerical Methods and Mathematical Software for Applications” (grant n. 2004012559, ).     

On a quadratic functional occurring in a bivariate scattered data interpolation problem

Sunto L’applicazione di noti metodi che utilizzano funzioni di tipo blending per la costruzione di funzioni bivariate C¹ per l’interpolazione di dati, richiede la conoscenza delle derivate parziali del primo ordine ai vertici di una triangolazione sottostante. In questo lavoro consideriamo il metodo proposto da Nielson, che consiste nel calcolare stime delle derivate parziali del primo ordine minimizzando un opportuno funzionale quadratico, caratterizzato da parametri di tensione non negativi. Scopo del lavoro è l’analisi di alcune proprietà particolari di questo funzionale per la costruzione di algoritmi efficienti e robusti per la determinazione delle stime suddette delle derivate quando si ha a che fare con insiemi di dati di grandi dimensioni. Abstract The application of widely known blending methods for constructingC ¹ bivariate functions interpolating scattered data requires the knowledge of the partial derivatives of first order at the vertices of an underlying triangulation. In this paper we consider the method proposed by Nielson that consists in computing estimates of the first order partial derivatives by minimizing an appropriate quadratic functional, characterized by nonnegative tension parameters. The aim of the paper is to analyse some peculiar properties of this functional in order to construct robust and efficient algorithms for determining the above estimates of the derivatives when we are concerned with extremely large data sets.      

Character degree graphs that are complete graphs

Let be a finite group, and write for the set of degrees of irreducible characters of . We define to be the graph whose vertex set is , and there is an edge between and if . We prove that if is a complete graph, then is a solvable group.

     

Mean value formulas for classical solutions to uniformly parabolic equations in the divergence form with non-smooth coefficients

We prove surface and volume mean value formulas for classical solutions to uniformly parabolic equations in the divergence form with low regularity of the coefficients. We then use them to prove the parabolic strong maximum principle and the parabolic Harnack inequality. We emphasize that our results only rely on the classical theory, and our arguments follow the lines used in the original theory of harmonic functions. We provide two proofs relying on two different formulations of the divergence theorem, one stated for sets with almost C¹-boundary, the other stated for sets with finite perimeter.     

Similar Structural Dynamics for the Degradation of CH3NH3PbI3 in Air and in Vacuum

We investigate the degradation path of MAPbI₃ (MA=methylammonium) films over flat TiO₂ substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI₂. We describe how this degradation product is structurally coupled with the original MAPbI₃ lattice through the orientation of its constituent PbI₆ octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH₃NH₂ or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.     

Mechanism insights into an unexpected isomerisation reaction observed during conversion of N-benzyl piperazinones to corresponding N-benzyl thio-piperazinones

An interesting and surprising rearrangement was observed during the reaction of 4-N-benzyl piperazinone derivatives with Lawesson’s reagent as a thionating agent. Investigation into the possible mechanism responsible for these results is reported herein.     

Water-soluble peptide-coated nanoparticles: control of the helix structure and enhanced differential binding to immune cells

The stabilizing action of C(α)-tetrasubstituted α-amino acids inserted into a sequence of short peptides allowed for the first time the preparation of water-soluble nanoparticles of different materials coated with a helix-structured undecapeptide. This peptide coating strongly favors nanoparticle uptake by human immune system cells.     

Extending the applicability of pressurized hot water extraction to compounds exhibiting limited water solubility by pH control: curcumin from the turmeric rhizome

Pressurized hot water extraction (PHWE, also known as subcritical water extraction) is commonly considered to be an environmentally friendly extraction technique that could potentially replace traditional methods that use organic solvents. Unfortunately, the applicability of this technique is often limited by the very low water solubility of the target compounds, even at high temperatures. In this paper, the scope for broadening the applicability of PHWE by adjusting the pH of the water used in the extraction is demonstrated in the extraction of curcumin (which exhibits very limited water solubility) from untreated turmeric (Curcuma longa L.) rhizomes. Although poor extraction yields were obtained, even at high temperatures when using degassed water or neutral phosphate buffer as the extraction medium, yields exceeding those obtained by Soxhlet extraction were achieved using highly acidic pH buffers due to curcumin protonation. The influence of the temperature, pH, and buffer concentration on the extraction yield were investigated in detail by means of a series of designed experiments. Optimized conditions for the extraction of curcumin from turmeric by PHWE were estimated at 197 °C using 62 g/L buffer concentration at pH 1.6. The relationships between these variables were subjected to statistical analysis using response surface methodology.     

Shotgun proteomic analytical approach for studying proteins adsorbed onto liposome surface

The knowledge about the interaction between plasma proteins and nanocarriers employed for in vivo delivery is fundamental to understand their biodistribution. Protein adsorption onto nanoparticle surface (protein corona) is strongly affected by vector surface characteristics. In general, the primary interaction is thought to be electrostatic, thus surface charge of carrier is supposed to play a central role in protein adsorption. Because protein corona composition can be critical in modifying the interactive surface that is recognized by cells, characterizing its formation onto lipid particles may serve as a fundamental predictive model for the in vivo efficiency of a lipidic vector. In the present work, protein coronas adsorbed onto three differently charged cationic liposome formulations were compared by a shotgun proteomic approach based on nano-liquid chromatography–high-resolution mass spectrometry. About 130 proteins were identified in each corona, with only small differences between the different cationic liposome formulations. However, this study could be useful for the future controlled design of colloidal drug carriers and possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins into body fluids.