Surface viscosity and reorientation process in an asymmetric nematic cell

The influence of surface viscosity and anchoring energy on the reorientation process of a nematic liquid crystal cell is theoretically investigated. The cell is a slab of thickness, d, whose limiting surfaces are characterised by different anchoring strengths and present easy directions parallel to the bounding surfaces, changing with time due to some external action. The exact space-time profile of the director angle is obtained by means of integral transform techniques and a Green function approach. From this formalism, the time dependence of the optical path difference is exactly determined and its behaviour is analysed in connection with the presence of surface viscosity and different anchoring energies. The problem is also exactly solved in the presence of a constant electric field. It is shown that the compatibility problem between the time derivative of the director field on the surface and in the bulk can be avoided.     

Morphology and properties of waterborne adhesives made from hybrid polyacrylic/montmorillonite clay colloidal dispersions showing improved tack and shear resistance

The morphology and adhesive properties of waterborne films from n-butyl acrylate/methyl methacrylate/montmorillonite clay hybrid polymer latexes which were synthesized by miniemulsion polymerization in the presence of a reactive organoclay ((2-methacryloylethyl) hexadecyldimethylammonium modified montmorillonite, CMA16) were investigated. It was found by cryo-TEM analysis that the hybrid dispersions were a mixture of colloidal particles composed of a small fraction of free montmorillonite clay platelets, polymer latex particles, polymer particles to which one or more clay platelets where adhered onto its surface and a fraction of colloidal material consisted of a clay platelet with a polymer lob adhered to either side, in other words hybrid particles with a dumbbell-like morphology. The films made from these waterborne hybrid dispersions presented a homogeneous dispersion of the clay platelets and exfoliated morphology. The shear adhesion failure temperature (SAFT) and shear resistance of the hybrid latex films synthesized with CMA16 were better than those prepared with a commercial clay (Cloisite 30B), but presented a liquid-like probe-tack performance. When allyl methacrylate (AMA) was added in the formulation, SAFT and shear resistance improved, but the film had a very low energy of adhesion due to the excessively crosslinked matrix. In order to reduce crosslink density and thus improve the adhesion energy, small amounts of chain transfer agent, in this case n-dodecyl mercaptan (n-DDM), were used in the miniemulsion polymerization process. Adhesive films made from these waterborne hybrid dispersions showed excellent SAFT and shear resistance, and good energy of adhesion.      

Simultaneous Square‐Wave Voltammetric Determination of Paracetamol,Caffeine and Orphenadrine in Pharmaceutical Formulations Using a Cathodically Pretreated Boron‐Doped Diamond Electrode

An electroanalytical method for the simultaneous determination of paracetamol (PAR), caffeine (CAF), and orphenadrine (ORPH) using the square‐wave voltammetry (SWV) and a cathodically pretreated boron‐doped diamond electrode was developed. The method exhibits linear responses to PAR, CAF, and ORPH in the concentration ranges 5.4×10^?7–6.1×10^?5 M, 7.8×10^?7–3.5×10^?5 M, and 7.8×10^?7–3.5×10^?5 M, respectively, with detection limits of 2.3×10^?7 M, 9.6×10^?8 M, and 8.4×10^?8 M, respectively. The proposed method was successfully applied in the simultaneous determination of these analytes in pharmaceutical formulations.     

Improved Solvent‐Free Dakin Oxidation Protocol

A solvent‐free Dakin reaction with mCPBA was accomplished with various aromatic aldehydes, resulting in an easy and improved methodology for the preparation of corresponding phenols. 3,4‐Methylenedioxyphenol, 3,4‐dimethoxyphenol, 4‐methoxyphenol, 4‐chlorophenol, and other functionalized phenols were obtained in high yields from the corresponding aromatic aldehydes in a few minutes. This new methodology represents an efficient alternative for this important synthetic conversion.     

Optimization of the extraction conditions of the volatile compounds from chili peppers by headspace solid phase micro-extraction

A method involving headspace-solid phase micro-extraction (HS-SPME), gas chromatography with flame ionization detection (GC-FID) and gas chromatography with mass spectrometry (GC-MS) was developed and optimized to investigate the volatile composition of Capsicum chili peppers. Five SPME fibers were tested for extraction: carboxen/polydimethylsiloxane (CAR/PDMS-75μm), polydimethylsiloxane (PDMS-100μm), divinylbenzene/polydimethylsiloxane (DVB/PDMS-65μm), carbowax/divinylbenzene (CW/DVB-70μm), and divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS-50/30μm), the last of which was shown to be the most efficient fiber to trap the volatile compounds. Optimization of the extraction conditions was carried out using multivariate strategies such as factorial design and response surface methodology. Eighty three compounds were identified by GC-MS when using the optimized extraction conditions, the majority of which were esters.     

Enlightening the influence of mordant, dyeing technique and photodegradation on the colour hue of textiles dyed with madder - A chromatographic and spectrometric approach

Wool samples were dyed with madder and alum, copper, and iron salts at different concentration by pre-mordanting (MD) and simultaneous mordanting (M + D) procedures. Samples were artificially aged to identify the influence of the mordant on the madder chromophores photodegradation. A set of analytical techniques was used for complete characterisation of the dyed fibres before and after light exposure, which included colour and chromophore analysis (colourimetry and LC-ESI-MS/MS analysis), determination of mordant ions amounts in the fibres (FAAS and ICP-OES analysis), morphological characterisation of the fibres and punctual chemical analysis (SEM-EDS studies).Fibre colour hue was found to be dependent on the mordant ion nature, mordant bath concentration and dyeing procedure. Mordant ion quantification showed that the uptake of metal ion by the fibres is relatively small, with the Cu ion presenting the highest affinity for the fibre. MD method yields fibres with higher amounts of metal ions and larger chromophore chromatographic peak areas corresponding, in general, to stronger colour hues. Photodegradation was more severe in alum mordant samples and in the first 480 h of light exposure. Chromophore degradation rates are unequal and dependent on the mordant nature, contributing for colour changes observed after light exposure.     

Infrared (810 nm) low-level laser therapy in rat achilles tendinitis: a consistent alternative to drugs

Nonsteroidal anti-inflammatory drugs (NSAIDs) are widely used and can reduce musculoskeletal pain in spite of the cost of adverse reactions like gastrointestinal ulcers or cardiovascular events. The current study investigates if a safer treatment such as low-level laser therapy (LLLT) could reduce tendinitis inflammation, and whether a possible pathway could be through inhibition of either of the two-cyclooxygenase (COX) isoforms in inflammation. Wistar rats (six animals per group) were injected with saline (control) or collagenase in their Achilles tendons. Then, we treated them with three different doses of IR LLLT (810 nm; 100 mW; 10 s, 30 s and 60 s; 3.57 W cm(-2); 1 J, 3 J, 6 J) at the sites of the injections, or intramuscular diclofenac, a nonselective COX inhibitor/NSAID. We found that LLLT dose of 3 J significantly reduced inflammation through less COX-2-derived gene expression and PGE(2) production, and less edema formation compared to nonirradiated controls. Diclofenac controls exhibited significantly lower PGE(2) cytokine levels at 6 h than collagenase control, but COX isoform 1-derived gene expression and cytokine PGE(2) levels were not affected by treatments. As LLLT seems to act on inflammation through a selective inhibition of the COX-2 isoform in collagenase-induced tendinitis, LLLT may have potential to become a new and safer nondrug alternative to coxibs.     

Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb2+ determination by flow-injection thermospray flame furnace atomic absorption spectrometry

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb(2+) ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb(2+) ions as template, tetraethoxysilane as reticulating agent and 2,2'-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L(-1)), eluent (HNO(3)) concentration (0.5 mol L(-1)) and preconcentration flow rate (4.0 mL min(-1)), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L(-1) (r=0.999) with limit of detection of 0.75 μg L(-1); the precision (repeatability) calculated as relative standard deviation (n=10) was 5.0 and 3.6% for Pb(2+) concentration of 10.0 and 60.0 μg L(-1), respectively. From on-line breakthrough curve, column capacity was 3.5 mg g(-1). Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min(-1), respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb(2+)/Cd(2+), Pb(2+)/Cu(2+) and Pb(2+)/Zn(2+). The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb(2+) than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb(2+) determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.     

Water-in-Oil-in-Water Double Emulsions as Protective Carriers for Sambucus nigra L. Coloring Systems

The use of natural colorants is needed to overcome consumer concerns regarding synthetic food colorants′ safety. However, natural pigments have, in general, poor stability against environmental stresses such as temperature, ionic strength, moisture, light, and pH, among others. In this work, water-in-oil-in-water (W₁/O/W₂) emulsions were used as protective carriers to improve color stability of a hydrophilic Sambucus nigra L. extract against pH changes. The chemical system comprised water and corn oil as the aqueous and oil phases, respectively, and polyglycerol polyricinoleate (PGPR), Tween 80, and gum Arabic as stabilizers. The primary emulsion was prepared using a W₁/O ratio of 40/60 (v/v). For the secondary emulsion, W₁/O/W₂, different (W₁/O)/W₂ ratios were tested with the 50/50 (v/v) formulation presenting the best stability, being selected as the coloring system to test in food matrices of different pH: natural yogurt (pH 4.65), rice drink (pH 6.01), cow milk (pH 6.47), and soy drink (pH 7.92). Compared to the direct use of the extract, the double emulsion solution gave rise to higher color stability with pH change and storage time, as corroborated by visual and statistical analysis.     

Structural Design,Synthesis and Antioxidant,Antileishmania, Anti-Inflammatory and Anticancer Activities of a Novel Quercetin Acetylated Derivative

Quercetin (Q) is a bioflavonoid with biological potential; however, poor solubility in water, extensive enzymatic metabolism and a reduced bioavailability limit its biopharmacological use. The aim of this study was to perform structural modification in Q by acetylation, thus, obtaining the quercetin pentaacetate (Q5) analogue, in order to investigate the biological potentials (antioxidant, antileishmania, anti-inflammatory and cytotoxicity activities) in cell cultures. Q5 was characterized by FTIR, ¹H and ¹³C NMR spectra. The antioxidant potential was evaluated against the radical ABTS^•+. The anti-inflammatory potential was evaluated by measuring the pro-inflammatory cytokine tumor necrosis factor (TNF) and the production of nitric oxide (NO) in peritoneal macrophages from BALB/c mice. Cytotoxicity tests were performed using the AlamarBlue method in cancer cells HepG2 (human hepatocarcinoma), HL-60 (promyelocytic leukemia) and MCR-5 (healthy human lung fibroblasts) as well as the MTT method for C6 cell cultures (rat glioma). Q and Q5 showed antioxidant activity of 29% and 18%, respectively, which is justified by the replacement of hydroxyls by acetyl groups. Q and Q5 showed concentration-dependent reductions in NO and TNF production (p < 0.05); Q and Q5 showed higher activity at concentrations > 40µM when compared to dexamethasone (20 µM). For the HL-60 lineage, Q5 demonstrated selectivity, inducing death in cancer cells, when compared to the healthy cell line MRC-5 (IC₅₀ > 80 µM). Finally, the cytotoxic superiority of Q5 was verified (IC₅₀ = 11 µM), which, at 50 µM for 24 h, induced changes in the morphology of C6 glioma cells characterized by a round body shape (not yet reported in the literature). The analogue Q5 had potential biological effects and may be promising for further investigations against other cell cultures, particularly neural ones.