Synthesis of non-agglomerated Ba<Subscript>0.77</Subscript>Ca<Subscript>0.23</Subscript>TiO<Subscript>3</Subscript> nanopowders by a modified polymeric precursor method

In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba_0.77Ca_0.23TiO₃ nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba_0.77Ca_0.23TiO₃ nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.     

Preparation of optically pure fused polycyclic scaffolds by Ugi reaction followed by olefin and enyne metathesis

Optically pure fused polycyclic scaffolds containing up to eight stereocentres have been synthesised by olefin metathesis and tandem enyne metathesis/Diels-Alder addition of Ugi multicomponent reaction adducts generated from 7-oxa-[2.2.1]-bicyclic amino acid derivatives.     

U-4C-3CR versus U-5C-4CR and stereochemical outcomes using suitable bicyclic β-amino acid derivatives as bifunctional components in the Ugi reaction

Intramolecular Ugi reactions with bicyclic β-amino acids have been performed and the effects of the configuration and N-alkylation have been studied. We have proven that preferential ring contraction or nucleophilic attack by the solvent depend not only on the presence of N-alkylation but also on the relative disposition of the carboxyl group and the amine. Excellent results in terms of stereoselectivity have been obtained in the case of N-alkyl-3-exo-amino-7-oxabicyclo[2.2.1]-2-endo-carboxylic acids.     

Electrochromic properties of poly(alkoxy-terthiophenes): an experimental and theoretical investigation

Much effort has been made to synthesize novel compounds and enhance the optical properties of poly(terthiophenes). The electrochromic properties of poly(4,4′′-dimetoxy-3′-methyl-2′-5′,2′′-terthiophene) (PDMMT) and poly(4,4′′-dipentoxy-3′-methyl-2′-5′,2′′-terthiophene) (PDPMT) have been studied focusing on the differences in the alkoxy-group length. Theoretical calculations were employed to elucidate the structural and thermodynamic stability of the monomers and dimmers. The results showed that in this type of thiophenes large alkoxy chains assist positive charge dispersion through hyperconjugative effect. Thus, PDPMT is thermodynamically more stable than PDMMT in the oxidized state, leading to better electrochromic stability and optical memory.     

A novel highly selective chiral auxiliary for the asymmetric synthesis of L- and D-alpha-amino acid derivatives via a multicomponent Ugi reaction

This paper describes the synthesis of a bicyclic beta-amino acid scaffold in both pure enantiomeric forms and its application as chiral auxiliary in an intramolecular version of the Ugi multicomponent reaction (U-5C-4CR) to prepare alpha-amino acid derivatives of both D- and L-series in a straightforward and very stereoselective manner. The mild conditions required for the Ugi condensation and for the removal of the chiral auxiliary make this method very attractive to prepare a wide range of differently structured N-alkylated and unalkylated amino acid derivatives.     

One-pot synthesis of α-acyloxyaminoamides via nitrones as imine surrogates in the Ugi MCR

α-acyloxyaminoamides can be prepared, with yields ranging from fair to very good (up to 89%), through an Ugi four component reaction by mixing a carbonyl component, a carboxylic acid, an isocyanide and an N-alkylated hydroxylamine in methanol. Preformed nitrones furnish the same final compounds with comparable yields.     

Further studies on the rotational barriers of Carbamates. An NMR and DFT analysis of the solvent effect for Cyclohexyl N,N-dimethylcarbamate

The solvent effect on the Gibbs energy of activation for rotation around the (C=O)–N bond in cyclohexyl N,N-dimethylcarbamate was investigated by dynamic NMR spectroscopy and density-functional theory at the B3LYP/6-311+G^** level. The experimental barriers were about 15 kcal mol⁻¹ with no appreciable variation when the solvent polarity was changed. A reaction field model was applied to theoretically mediate the solvent effect and the results were comparable to the experimental data. An analysis, based on the Onsager solvation theory, showed that the solvent effect on rotational barriers can be understood employing the total molecular dipole moment, the difference between the dipole moments of the ground and the transition state structures, or both, as appropriate.     

Development and full validation of an HPLC methodology to quantify atorvastatin and curcumin after their intranasal co‐delivery to mice

There is increasing interest in atorvastatin and curcumin owing to their potential anticancer activity. A new, accurate and sensitive HPLC method was developed, for the first time, to simultaneously quantify atorvastatin and curcumin in mouse plasma and brain, liver, lung and spleen tissues following protein precipitation sample preparation. The chromatographic separation was achieved in 13 min on a C₁₈ column, at 35°C, using a mobile phase composed of acetonitrile–methanol–2% (v/v) acetic acid (37.5:2.5:60, v/v/v) at a flow rate of 1.0 mL/min. The detection of analytes and internal standard was carried out at 247, 425 and 250 nm, respectively. According to international guidelines, the method was shown to be selective, with lower limits of quantification ranging from 10 to 500 ng/mL for curcumin, and from 100 to 600 ng/mL for atorvastatin, linear over a wide concentration range (r² ≥ 0.9971) and with acceptable accuracy (bias ± 12.29%) and precision (coefficient of variation ≤13.15%). The analytes were reproducibly recovered at a percentage >81.10% and demonstrated to be stable under various experimental conditions in all biological matrices. This method can be easily applied to in vivo biodistribution studies related to the intranasal administration of atorvastatin and curcumin, separately or simultaneously.     

Pseudo-orthogonality for graph 1-Laplacian eigenvectors and applications to higher Cheeger constants and data clustering

The data clustering problem consists in dividing a data set into prescribed groups of homogeneous data. This is an NP-hard problem that can be relaxed in the spectral graph theory, where the optimal cuts of a graph are related to the eigenvalues of graph 1-Laplacian. In this paper, we first give new notations to describe the paths, among critical eigenvectors of the graph 1-Laplacian, realizing sets with prescribed genus. We introduce the pseudo-orthogonality to characterize m₃(G), a special eigenvalue for the graph 1-Laplacian. Furthermore, we use it to give an upper bound for the third graph Cheeger constant h₃(G), that is, h₃(G) 6 m₃(G). This is a first step for proving that the k-th Cheeger constant is the minimum of the 1-Laplacian Raylegh quotient among vectors that are pseudo-orthogonal to the vectors realizing the previous k - 1 Cheeger constants. Eventually, we apply these results to give a method and a numerical algorithm to compute m₃(G), based on a generalized inverse power method.