Thermal analysis: an effective characterization method of polyvinyl acetate films applied in corrosion inhibition field

Journal of Thermal Analysis and Calorimetry - To prepare a commercial product with economic and technical relevance, polyvinyl acetate (PVAc) was synthesized, under our laboratory conditions,...     

Studies on thermal,spectral, magnetic and biological properties of new Ni(II), Cu(II) and Zn(II) complexes with a bismacrocyclic ligand bearing an aromatic linker

Novel complexes of M₂LCl₄·nH₂O type (M:Ni, n = 4; M:Cu, n = 3 and M:Zn, n = 0; L: ligand resulted from 1,4-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde one-pot condensation) were synthesized and characterised by microanalytical, ESI–MS, IR, UV–Vis, ¹H NMR and EPR spectra, magnetic data at room temperature and molar conductivities as well. The electrochemical behaviour of complexes was investigated by cyclic voltammetry. Simultaneous TG/DTA measurements were performed in order to evidence the thermal behaviour of the obtained complexes. Processes such as water elimination, fragmentation and oxidative degradation of the organic ligand as well as chloride elimination occurred during thermal decomposition. The antimicrobial assays demonstrate that the compounds exhibited good antibacterial activity, especially against S. aureus and E. coli strains, the most active being the copper(II) complex, which also exhibited the most prominent anti-biofilm effect, suggesting its potential use for the development of new antimicrobial agents. The biological activity was correlated with log P _ow values. All complexes disrupt the membrane integrity of HCT 8 tumour cells.     

Synthesis and thermal behavior of new ambazone complexes with some transitional cations

Ambazone is a pharmaceutical compound that possesses antiseptic activity and tested as well for anti-tumor properties. Metal complexes of Zn(II), Fe(III), and Cu(II) containing ambazone as ligand were synthesized using a molar ratio salt:ligand of 1:1, heating the mixture up to 50 °C for 6 h. Coordination compounds were characterized by thin-layer chromatography, FT-IR spectroscopy, elemental analysis, and thermal behavior. The non-isothermal experiments were carried out in order to investigate the thermal degradation process of these complexes and were performed in a dynamic air atmosphere at a heating rate β = 10 °C min^?1 from ambient temperature, up to 500 °C. It was revealed that decomposition process is a multistadial one.     

Cauliflower-like CdS microspheres composed of nanocrystals and their physicochemical properties

Cauliflower-like cadmium sulfide (CdS) microspheres composed of nanocrystals have been successfully synthesized by a hydrothermal method using poly(ethylene glycol) (PEG) as the template coordination agent and characterized by a variety of methods. Our experiments confirmed that the size of the CdS microspheres could be easily modified by controlling the chain length of PEG. Powder X-ray diffraction and Raman spectroscopy measurements revealed the cubic structure of the CdS microspheres; morphological studies performed by HR-SEM and HR-TEM methods showed the cauliflower-like structure of the synthesized CdS microspheres. Each microsphere was identified to be created by the self-assembly of CdS nanocrystals and is attributed to the oriented aggregation of the CdS nanocrystals around a polymer-Cd(2+) complex spherical framework structure. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) analysis confirmed the stoichiometries of the CdS microspheres. Diffuse reflectance spectrum (DRS) measurements showed that increasing the PEG chain length increased the band gap value of the CdS microspheres slightly, from 1.99 to 2.06 eV. The cauliflower-like CdS microspheres could be applied to photocatalytic degradation studies.     

Linear and nonlinear optical properties of cationic bipyridyl iridium(III) complexes: tunable and photoswitchable?

A series of cationic Ir(III) substituted bipyridyl ()(N(∧)N (N(∧)N-bpy) complexes incorporating electron-donor and -acceptor substituents, [Ir(C(∧)N-ppy-R')(2)(N(∧)N-bpy-CH═CH-C(6)H(4)-R)][X] (X(-) = PF(6)(-) or C(12)H(25)SO(3)(-)), 2 (a, R = NEt(2) and R' = Me; b, R = O-Oct and R' = Me; c, R = NO(2) and R' = C(6)H(13); C(∧)N-ppy = cyclometalated 2-phenylpyridine, [Ir(C(∧)N-ppy-Me)(2)(N(∧)N-bpy-CH═CH-thienyl-Me)][PF(6)], 2d, and the dithienylethene (DTE)-containing complex 2e have been synthesized and characterized, and their absorption, luminescence, and quadratic nonlinear optical (NLO) properties are reported. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations on the complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes. All five complexes are luminescent in a rigid glass at 77 K, displaying vibronically structured spectra with long lifetimes (14-90 μs), attributed to triplet states localized on the styryl-appended bipyridines. The second-order NLO properties of 2a-d and related complexes 1a-d with 1,10-phenanthrolines have been investigated by both electric field induced second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques. They are characterized by high negative EFISH μβ values which decrease when the ion pair strength between the cation and the counterion (PF(6)(-), C(12)H(25)SO(3)(-)) increases. The EFISH response is mainly controlled by metal-to-ligand charge-transfer/ligand-to-ligand charge-transfer (MLCT/L'LCT) processes. A combination of HLS and EFISH techniques is used to evaluate both the dipolar and octupolar contributions to the total quadratic hyperpolarizability, demonstrating that the major contribution is controlled by the octupolar part. The incorporation of a photochromic DTE unit into the N(∧)N-bpy ligand (complex 2e) allows the luminescence to be switched ON or OFF. The photocyclisation of the DTE unit can be triggered by using either UV (365 nm) or visible light (430 nm), leading to an efficient quenching of the ligand-based 77 K luminescence, which can be restored upon irradiation of the closed form at 715 nm. In contrast, no significant modification of the EFISH μβ value is observed upon photocyclization, suggesting that the quadratic NLO response is dominated by the MLCT/L'LCT processes, rather than by the intraligand excited states localized on the substituted bipyridine ligand.     

A New Sulfur‐containing Schiff‐Base Ligand and Binding to Copper(II) and Cobalt(II)

A new Schiff‐base ligand having a potentially coordinating thioether group (2‐quinoline‐N‐(2′‐methylthiophenyl)methyleneimine, qmtpm ) has been prepared. The synthesis, structure, UV‐Vis and EPR studies of one copper(II) and two cobalt(II) complexes from this ligand is reported. The X‐ray structures of the Cu^II and Co^II chlorido complexes 1 and 2 reveal the metal atoms in highly distorted square‐pyramidal environments constituted of one tridentate ligand and two anions. On the other hand, the thiocyanato Co^II compound 3 exhibits a distorted trigonal‐bipyramidal structure. These structural variations are apparently due to the different counter‐ions which leads to distinct lattice interactions. The spectroscopic data obtained by EPR and UV‐Vis investigations are in agreement with the solid‐state structures of the coordination compounds.     

Natural glycoconjugates with antitumor activity

Cancer is one of the major causes of death worldwide. As a consequence, many different therapeutic approaches, including the use of glycosides as anticancer agents, have been developed. Various glycosylated natural products exhibit high activity against a variety of microbes and human tumors. In this review we classify glycosides according to the nature of their aglycone (non-saccharidic) part. Among them, we describe anthracyclines, aureolic acids, enediyne antibiotics, macrolide and glycopeptides presenting different strengths and mechanisms of action against human cancers. In some cases, the glycosidic residue is crucial for their activity, such as in anthracycline, aureolic acid and enediyne antibiotics; in other cases, Nature has exploited glycosylation to improve solubility or pharmacokinetic properties, as in the glycopeptides. In this review we focus our attention on natural glycoconjugates with anticancer properties. The structure of several of the carbohydrate moieties found in these conjugates and their role are described. The structure–activity relationship of some of these compounds, together with the structural features of their interaction with the biological targets, are also reported. Taken together, all this information is useful for the design of new potential anti-tumor drugs.     

Direct chlorine determination in crude oils by energy dispersive X-ray fluorescence spectrometry: An improved method based on a proper strategy for sample homogenization and calibration with inorganic standards

Official guidelines to perform chlorine determination in crude oil are (i) American Society for Testing and Materials (ASTM) D6470, which is based on the extraction of water from the oil and subsequent determination of the chloride by potentiometry, (ii) ASTM D3230, that measures the conductivity of a solution of crude oil in a mixture of organic solvents and (iii) US Environmental Protection Agency (EPA) 9075 that uses energy dispersive X-ray fluorescence spectrometry to quantify chlorine and it is applicable for the range from 200 μg g^− 1 to percent levels of the analyte. The goal of this work is to propose method to quantify lower amounts of chlorine in crude oil using energy dispersive X-ray fluorescence spectrometry using a simple calibration strategy. Sample homogenization procedure was carefully studied in order to enable accurate results. The calibration curve was made with standards prepared by diluting aqueous NaCl standard in glycerin. The method presented a linear response that covers the range from 8 to at least 100 μg g^− 1 of chlorine. Chlorine in crude oil samples from Campos Basin - Brazil were quantified by the proposed method and by potentiometry after extraction of chlorine from the oil. Results achieved using both methods were statistically the same at 95% confidence level.     

A multi-analytical approach for the identification of aloe as a colorant in oil–resin varnishes

Aloe plants have been widely documented in artists’ treatises dating from the sixteenth to the nineteenth century as a source of colorant to achieve lustrous golden glazes on tin- and silver-foiled objects and warm-toned finishes on musical instruments, such as violins. Aloe extracts contain characteristic anthraquinone and phenolic components which impart a distinctive orange tone and fluorescence to mixtures containing them. Because of the low concentration of colorant in the coatings and its probable degradation by high temperature during manufacture, the identification of aloe in heated oil–resin mixtures represents an analytical challenge. For this reason, the possible presence of aloe in glazes and coatings has been largely overlooked. This paper describes various analytical approaches to the identification of aloe in historic samples, from comparison with results obtained from reference standards and mock-up samples. Complementary analytical techniques including thermally assisted hydrolysis and methylation–gas chromatography–mass spectrometry, high-performance liquid chromatography, laser desorption–mass spectrometry, matrix-assisted laser desorption-ionization-mass spectrometry and surface-enhanced Raman scattering were used. Different chemical markers were identified by the individual methods and the advantages and limitations of each technique for the identification of aloe in oil–resin varnishes are discussed.     

Development and validation of an HPLC-MS/MS method to quantify clopidogrel acyl glucuronide, clopidogrel acid metabolite, and clopidogrel in plasma samples avoiding analyte back-conversion

A new sensitive and fast quantitative analytical method for the simultaneous determination of clopidogrel, its main metabolite clopidogrel carboxylic acid, and the newly described acyl glucuronide metabolite, in human plasma samples, is presented. The analytical procedures (plasma storage, handling, and extract storage in the autosampler) were optimized in order to avoid back-conversion; a known drawback in measurements of clopidogrel. Clopidogrel acyl glucuronide was confirmed as a major source of back-conversion to the parent drug in the presence of methanol, and thorough stability experiments were carried out to find the most appropriate conditions for an accurate analysis of clopidogrel and the two metabolites. The method was validated by assessing selectivity, sensitivity, linearity, accuracy, and precision for all three analytes, in accordance to Food and Drug Administration guidelines. Spiked quality controls in plasma as well as incurred samples were used to verify back-conversion in the selected conditions, with results meeting European Medicines Agency acceptance criteria (concentrations within 80–120% of the first reading). The method was then applied to a pharmacokinetic study, and for the first time, a pharmacokinetic curve of clopidogrel acyl glucuronide in human plasma is presented. The concentrations ranged up to 1,048.684 ng/mL, with a mean of 470.268 ng/mL, while clopidogrel had a mean C _max of 1.348 ng/mL; these orders of magnitude show how much the back-conversion of this metabolite may influence clopidogrel quantification if it is not properly controlled.