Numerical differentiation on scattered data through multivariate polynomial interpolation

BIT Numerical Mathematics - We discuss a pointwise numerical differentiation formula on multivariate scattered data, based on the coefficients of local polynomial interpolation at Discrete Leja...     

Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

1,3‐Benzothiazoles as Antimicrobial Agents

Starting from 2‐amino‐1,3‐mercaptobenzothiazoles recently reported ( 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h ), a series of the corresponding 2‐mercapto‐1,3‐benzothiazole isosters ( 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h ) were screened for their in vitro antibacterial and antifungal activities. Results underline that the presence of the mercapto moiety at the 2‐position of the heterocyclic nucleus is crucial for activity against bacteria. The biological screening against Candida spp. identified commercial 2f as the most promising compound as antifungal against Candida albicans and tropicalis. Molecular modeling studies supported these results. Then, to enlarge structure‐activity relationship (SAR) studies on series 1 , newly synthesized compounds ( 1k , 1l , 1m , 1n , 1o , 1p ) were reported. All the compounds belonging to this series and bearing a bulky substituent at the 6‐position of the aryl moiety showed high antifungal activity.     

Phase segregation of metastable quenched liquid mixtures and the effect of the quenching rate

The effect of the quenching rate on the phase separation of partially miscible liquid mixtures is studied, showing that it may influence the growth rate of single-phase domains. In particular, the phase separation of metastable binary mixtures in the presence of strong emulsifiers appears to be heavily retarded. These effects constitute an important limitation to the phase transition extraction process introduced by the authors in previous works, which is based on the fact that phase separation of unstable mixtures is rapid, even in the presence of surface active compounds.     

Profiling and quantifying polar lipids in milk by hydrophilic interaction liquid chromatography coupled with evaporative light-scattering and mass spectrometry detection

In this work, a high-performance liquid chromatography with evaporative light scattering detection method has been developed and applied for quantification of the polar content of the lipid fraction in milk samples of different origin. From a chromatographic stand-point, a 4.6-mm I.D. hydrophilic interaction liquid chromatography column was employed to attain a baseline separation of major phospholipid classes contained in the various milk samples tested. Quantitative analysis was performed by the external calibration method using reference material solutions in the 5–100 mg/L concentration range. Analytical recoveries ranging from 57 to 100 %, and repeatability data lower than 8.04 % were obtained on a skimmed cow’s milk sample. The crude cow milk was the most abundant (0.04 %) in phospholipids and donkey milk was the poorest (0.004 %). Quantitative differences were determined in the phospholipid content of the milk samples tested. Finally, characterization of phospholipid profile and fatty acid composition of the different samples was carried out by an ion trap-time of flight mass spectrometer and gas chromatography coupled to flame ionization and mass spectrometry detection. A thorough screening of the polar lipid composition of milk samples of different origin is here outlined, for the first time.     

Revenue Models and Policies for the Car Rental Industry

In this paper, we consider the application of revenue management techniques in the context of the car rental industry. In particular, the paper presents a dynamic programming formulation for the problem of assigning cars of several categories to different segments of customers, with rental requests arising dynamically and randomly with time. Customers make a rental request for a given type of car, for a given number of days at a given pickup time. The rental firm can satisfy the demand for a given product with either the product requested or with a car of at most one category superior to that initially required, in this case an “upgrade” can take place. The one-way rental scenario, which allows the possibility of the rental starting and ending at different locations, is also addressed. In the framework considered, the logistic operator has to decide whether to accept or reject a rental request. Since the proposed dynamic programming formulations are impractical due to the curse of dimensionality, linear programming approximations are used to derive revenue management decision policies for the operator. Indeed, primal and dual acceptance policies are developed (i.e. booking limits, bid prices) and their effectiveness is assessed on the basis of an extensive computational phase.     

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.     

Supercritical CO2 Assisted Impregnation of Ibuprofen on Medium-Chain-Length Polyhydroxyalkanoates (mcl-PHA)

In this work, we propose the utilization of scCO₂ to impregnate ibuprofen into the mcl-PHA matrix produced by Pseudomonas chlororaphis subs. aurantiaca (DSM 19603). The biopolymer has adhesive properties, is biocompatible and has a melting temperature of 45 °C. Several conditions, namely, pressure (15 and 20 MPa) and impregnation time (30 min, 1 h and 3 h) were tested. The highest ibuprofen content (90.8 ± 6.5 mg of ibuprofen/g_PHA) was obtained at 20 MPa and 40 °C, for 1 h, with an impregnation rate of 89 mg/(g·h). The processed mcl-PHA samples suffered a plasticization, as shown by the decrease of 6.5 °C in the T_g, at 20 MPa. The polymer’s crystallinity was also affected concomitantly with the matrices’ ibuprofen content. For all the impregnation conditions tested the release of ibuprofen from the biopolymer followed a type II release profile. This study has demonstrated that the mcl-PHA produced by P. chlororaphis has a great potential for the development of novel topical drug delivery systems.     

Evaluation of sample processing and sub-sampling performance

A methodology for the estimation of sample processing and sub-sampling performance based on the comparison of the global method experimental dispersion of results with the uncertainty estimated from developed models for the subsequent analytical steps is presented. This approach is a valuable alternative to the evaluation of adequate experimental information using a classical ANOVA, since the significance of the sample processing and sub-sampling is evaluated with a higher number of degrees of freedom for the same number of experimental assays, due to the high number of degrees of freedom associated with the uncertainty estimated for the subsequent analytical steps from the combination of the involved sources of uncertainty.Considering the construction of a model to describe the performance of the analytical steps following sample processing and sub-sampling over a broad concentration range, the experimental assays involved at the evaluation of the sample processing and sub-sampling can be performed at any concentration meeting the previously validated range and several months after the development of that model once its adequacy has been proven over time.This approach, which also allows the construction of a detailed performance model for the global analytical method over a broad concentration range, was applied to the determination of pesticide residues in apples by gas-chromatography with electron capture detector.Considering that no information was available regarding the samples heterogeneity, sub-sampling performance was evaluated considering a sample representing the worst expectable homogeneity. This was accomplished by spiking just one out of the 10 halves of apples processed in each sample.The developed model for the performance of the analytical method was successfully and easily applied to routine analysis through an automated link between the information generated by the chromatograph software with a file containing the model.