Triangular ruthenium acetate clusters containing the bis(pyridyl)propane ligand and their inclusion chemistry with β-cyclodextrin

The triruthenium carboxylate cluster [Ru₃O(OAc)₆(py)₂(bpp)]⁺ (OAc = acetate) containing the bridging 1,3-bis(4-pyridyl)propane (bpp) ligand, and its dimeric species [{Ru₃O(OAc)₆(py₂)}₂(μ-bpp)]²⁺ were synthesized in order to investigate their inclusion compounds with β-cyclodextrin (β-CD). Characterization of the complexes was carried out based on spectroscopic, electrochemical and spectroelectrochemical techniques, while the formation of inclusion complexes was evaluated using ¹H NMR/NOESY spectroscopy. Since bpp is a flexible ligand, a DFT study was carried out in order to characterize its conformational isomers and their possible role in the host–guest chemistry with β-CD. Instead of observing the formation of inclusion compounds with different stoichiometries, we observed the formation of 1:1 bpp/β-CD compounds in which the bpp ligand assumes different conformations. The assembly of polymetallic rotaxane species was successfully demonstrated by monitoring the ¹H NMR spectra of the monomeric cluster species in the presence of aquapentacyanoferrate(II) ions and β-CD.     

Temperature dependent Raman scattering study of l-ascorbic acid

Temperature dependent Raman study of l-ascorbic acid has been performed from 15 to 418 K. Changes in the wavenumber vs. temperature plots for some internal modes were interpreted as conformational molecular change and the discontinuity in the wavenumber vs. temperature plots along with the appearance of a new vibrational mode in the temperature range 200-270 K suggests that l-ascorbic acid undergoes a structural phase transition. For temperatures higher than 300 K, no relevant modification was observed on the Raman spectra thus indicating a stable structure at high temperatures. Additionally, a correlation between OH stretching wavenumber and the behavior of hydrogen bond is also made.     

Adsorption of chlorhexidine on synthetic hydroxyapatite and in vitro biological activity

The kinetic of chlorhexidine digluconate (CHXDG) uptake from aqueous solution by hydroxyapatite (HA) was investigated by ultraviolet (UV) analysis performed in HA powder (UV-solid) after the CHX adsorption. Adsorption isotherm of chlorhexidine (CHX) uptake was modeled by a combination of Languimir and Langmuir-Freundlich mechanisms. Strong molecule-molecule interactions and positive cooperativity predominated in the surface when CHX concentration was above 8.6 μg(CHX)/mg(HA). UV-solid spectra (shape, intensity and band position) of CHX bound to HA revealed that long-range molecular structures, such as aggregates or micelles, started to be formed at low CHX concentrations (1.52 μg(CHX)/mg(HA)) and predominated at high concentrations. Grazing-incidence X-ray diffraction (GIXRD) analysis from synchrotron radiation discarded the formation of crystalline structures on HA surface or precipitation of CHX crystalline salts, as suggested in previous works. The effect of the HA/CHX association on HA in vitro bioactivity, cytotoxicity and CHX antimicrobial activity was evaluated. It was shown that CHX did not inhibit the precipitation of a poorly crystalline apatite at HA/CHX surface after soaking in simulating body fluid (SBF). Cell viability studies after exposure to extracts of HA and HA/CHX showed that both biomaterials did not present significant in vitro toxicity. Moreover, HA/CHX inhibited Enterococcus faecalis growth for up to 6 days, revealing that binding to HA did not affect antimicrobial activity of CHX and reduced bacterial adhesion. These results suggested that HA/CHX association could result in a potential adjuvant antimicrobial system for clinical use.     

Pendimethalin determination in natural water, baby food and river sediment samples using electroanalytical methods

This work describes the electroanalytical determination of pendimethalin herbicide levels in natural waters, river sediment and baby food samples, based on the electro-reduction of herbicide on the hanging mercury drop electrode using square wave voltammetry (SWV). A number of experimental and voltammetric conditions were evaluated and the best responses were achieved in Britton-Robinson buffer solutions at pH 8.0, using a frequency of 500 s^− 1, a scan increment of 10 mV and a square wave amplitude of 50 mV. Under these conditions, the pendimethalin is reduced in an irreversible process, with two reduction peaks at − 0.60 V and − 0.71 V, using a Ag/AgCl reference system. Analytical curves were constructed and the detection limit values were calculated to be 7.79 μg L^− 1 and 4.88 μg L^− 1, for peak 1 and peak 2, respectively. The precision and accuracy were determinate as a function of experimental repeatability and reproducibility, which showed standard relative deviation values that were lower than 2% for both voltammetric peaks. The applicability of the proposed methodology was evaluated in natural water, river sediments and baby food samples. The calculated recovery efficiencies demonstrate that the proposed methodology is suitable for determining any contamination by pendimethalin in these samples. Additionally, adsorption isotherms were used to evaluate information about the behavior of pendimethalin in river sediment samples.     

Synthesis and characterization of new porphyrin/4-quinolone conjugates

New porphyrin/4-quinolone conjugates were synthesized from the Suzuki-Miyaura coupling reaction of a β-borylated porphyrin with bromo-4-quinolones containing N-ethyl and N-d-ribofuranosyl substituents. The use of electrospray ionization tandem mass spectrometry showed important information about the fragmentation pathways of the new compounds. It was possible to distinguish between those compounds with the porphyrin moiety linked at the 6-position of the quinolone unit from their 7-substituted isomers. The new compounds showed to be good singlet oxygen generators.     

Pharmaceutical composition of hydrochlorothiazide:β-cyclo-dextrin: preparation by three different methods, physico-chemical characterization and in vivo diuretic activity evaluation

Hydrochlorothiazide is a common diuretic antihypertensive drug of the thiazide family. Its poor aqueous solubility is one of the reasons for its limited bioavailability after oral administration. This work aimed at the development of a hydrochlorothiazide:β-cyclodextrin (HTZ:β-CD) pharmaceutical composition in order to improve water solubility and bioavailability of the drug. The HTZ:β-CD complexes were prepared by three different methods: spray-drying, freeze-drying and fluid bed. Complexes were characterized by thermal analysis, Fourier transform-infrared (FTIR) spectroscopy, powder X-ray diffractometry, NMR (2D-ROESY), scanning electron microscopy (SEM), particle analysis and intrinsic dissolution. The findings reveal that three binary systems prepared presented better solubility results in comparison with free HTZ. Increased diuretic effect was observed to HTZ:β-CD obtained by fluid bed in comparison to free drug in rats. Results taken together suggest that pharmacological effect of HTZ in complex was increased by solubility improvement promoted by cyclodextrin.     

Influence of Cu(II) in the SrSnO<Subscript>3</Subscript> crystallization

Perovskite type oxides have been intensively studied due to their interesting optical, electrical, and catalytic properties. Among perovskites the alkaline earth stannates stand out, being strontium stannates (SrSnO₃) the most important material in ceramic technology among them due to their wide application as dielectric component. SrSnO₃ has also been applied as stable capacitor and humidity sensor. In the present work, SrSnO₃:Cu was synthesized by polymeric precursor method and heat treated at 700, 800, and 900 °C for 4 h. After that, the material was characterized by thermal analysis (TG/DTA), X-ray diffraction (XRD), infrared spectroscopy, and UV–vis spectroscopy. Results indicated three thermal decomposition steps and confirmed the presence of strontium carbonate and Cu²⁺ reduction to Cu⁺ at higher dopant amounts. XRD patterns indicated that the perovskite crystallization started at 700 °C with strontiatite (SrCO₃) and cassiterite (SnO₂) as intermediate phases, disappearing at higher temperatures. The amount of secondary phase was reduced with the increase in the Cu concentration.     

Influence of the incorporated metal on template removal from MCM-41 type mesoporous materials

Al-modified MCM-41, La-modified MCM-41, and Ce-modified MCM-41 mesoporous materials were prepared with different molar ratios (Si/M = 10; 25; 50; 100 and 200) at room temperature. The materials were characterized using XRD, BET–BJH, and TG–DTA. The XRD showed four peaks, due to the ordered hexagonal array of parallel silica tubes, which could be indexed as (100), (110), (200), and (210), assuming a hexagonal unit cell. The surface area decreased as the concentration of the metal incorporated in the material increased. The thermal stability of the materials was around 650 °C. The CeO₂ phase made the mass transfer process more difficult, hindering Hofmann degradation and favoring oxidation.     

Use of different techniques in the evaluation of the oxidative stability of poultry fat biodiesel

The poultry fat methylic (BMF) and ethylic (BEF) biodiesels were synthesized through transesterification by homogeneous basic catalysis. The chromatographic analyses showed the palmitic, stearic, oleic, and linoleic esters as majority components. Owing to its considerable amount of polyunsaturated fat acids, poultry fat usually leads to a biodiesel with low oxidative stability. In this study, the oxidation of their ethylic and methylic biodiesels was evaluated by Rancimat, PDSC, and PetroOxy. The OSI (Rancimat) was of 0.47 and 0.40 h for the ethylic and methylic biodiesel, respectively. In PDSC, both fuels presented an OT of about 120–123 °C. PetroOxy analysis indicated an OxyStab of 11 min for BEF and higher than 11 min for BMF. There was no correspondence among the oxidative stabilities of the employed techniques [OT(BEF) ≈ OT(BMF), OSI(BEF) > OSI(BMF), and OxyStab(BEF) < OxyStab(BMF)]. The discussion of these results was based on the indicator measured by each technique: enthalpic events are observed by PDSC; conductivity of volatile secondary oxidation products is measured by Rancimat; reduction of the oxygen pressure is determined by PetroOxy. This discussion showed that these different indicators do not reflect the same stage of the oxidative process as energy is release at the beginning of the propagation step, oxygen pressure decreases during the propagation step, and oxidation products are formed during the termination step.     

Influence of thermal degradation in the physicochemical properties of fish oil

Physicochemical and thermal analyses were undertaken to evaluate the influence of the temperature on the oxidation of sea fish oil once its polyunsaturated fatty acids deteriorate rapidly. Fish oil displayed four decomposition steps in synthetic air atmosphere and only one step in nitrogen atmosphere. The first step started at 189 and 222 °C for oxidizing and inert atmospheres, respectively. An OIT value of 53 min was measured at 100 °C. After the degradation process the peroxide index and the iodine index reduced from 35.38 to 9.85 meq × 1000 g^?1 and from 139.79 to 120.19 gI₂ × 100 g^?1, respectively. An increase of the free fatty acids amount from 0.07 to 0.17% was observed while viscosity increased from 57.2 to 58.0 cP. Absorption at 272 nm also increased. The thermogravimetric and spectroscopic techniques are reproducible and versatile being an option for characterization of edible oil oxidation.