Ecofriendly modification of acetosolv lignin from oil palm biomass for improvement of PMMA thermo‐oxidative properties

The environmentally friendly esterification of acetosolv lignin (AL), obtained from pressed oil palm mesocarp fibers, is described, for the improvement of thermo‐oxidative properties of poly(methyl methacrylate) (PMMA) films. Acetylation of AL was performed in ecofriendly conditions using acetic anhydride in the absence of catalysts. Acetylated acetosolv lignin (AAL) was successfully obtained in only 12 min with a solvent‐free and catalyst‐free microwave‐assisted procedure. Lignins were characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), confirming the efficacy of the methodology employed. AL and AAL as fillers in different concentrations (1% and 5%) were added to PMMA films. The thermal and mechanical properties of the lignin‐incorporated films were analyzed by TGA, DSC, and dynamic mechanical analysis (DMA). The films incorporated with lignin and acetylated lignin presented initial degradation temperature (T_onset) and onset oxidative temperature (OOT) values higher than pure PMMA films, contributing thus to an enhancement of thermo‐oxidative stability of PMMA. The DMA analyses showed that incorporation of AL or AAL increased the storage modulus (E′) of PMMA films, but did not affect their glass‐transition temperatures (T_g). The results indicate the potential use of oil palm mesocarp lignin to enhance the thermo‐oxidative properties of PMMA without compromising its mechanical response. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45498.     

Technique for measuring metallic salt effects upon the indigenous heterotrophic microflora of a natural water

The effects of several concentrations of the metallic salts Ag₂SO₄, NaAsO₃, BaCl₂2H₂O, CdCl₂2.5 H₂O, CrCl₂6H₂O, CuCl₂, HgCl₂, NaCl, NiCl₂6H₂O, PbCl₂ and ZnCl₂ upon the indigenous heterotrophic microflora of a natural water were studied. Effects of these salts upon the heterotrophic activity of the microbes were assayed using the heterotrophic technique whereas lethal effects upon the heterotrophic bacteria were determined using nutrient agar plate counts. The heterotrophic activity method is based upon the uptake and mineralization of a radioactively labeled metabolite (in these experiments ¹⁴C-glucose) by the indigenous aquatic microbes and data analysis is by Michaelis—Menten enzyme kinetics equations. Concentrations of metallic salts which resulted in bacterial death also caused erratic uptake and mineralization rates of ¹⁴C-glucose whereas sub-lethal concentrations, as determined by nutrient agar plate counts, caused a non-competitive inhibition of maximum heterotrophic activity and markedly increased the turnover time of the glucose substrate.     

Validation of a simple and rapid HPLC method for determination of metronidazole in dermatological formulations

A rapid and simple method using an isocratic high-pressure liquid chromatography (HPLC) and UV detection for the determination of metronidazole in dermatological formulations is presented. Metronidazole samples were extracted with a solution composed of 60% methanol and 40% mobile phase by a procedure that can be completed in less than 10 min. Subsequent separation and quantification was accomplished in less than 20 min using reversed-phase HPLC with isocratic elution with 0.01% trifluoroacetic acid/acetonitrile (85:15%, vol/vol). Validation experiments confirmed the precision and accuracy of the method. When applied to a commercial metronidazole cream and gel formulation, recoveries of 100.4% for cream formulations and 102.3% for gel formulations were obtained. The method should facilitate studies of the formulation compatibility of metronidazole topical formulations with agents that may improve its clinical tolerability for treatment of rosacea.     

Vertical nanowire array-based light emitting diodes

Electroluminescence from a nanowire array-based light emitting diode is reported. The junction consists of a p-type GaN thin film grown by metal organic chemical vapor deposition (MOCVD) and a vertical n-type ZnO nanowire array grown epitaxially from the thin film through a simple low temperature solution method. The fabricated devices exhibit diode like current voltage behavior. Electroluminescence is visible to the human eye at a forward bias of 10 V and spectroscopy reveals that emission is dominated by acceptor to band transitions in the p-GaN thin film. It is suggested that the vertical nanowire architecture of the device leads to waveguided emission from the thin film through the nanowire array.     

Quantification of N-(deoxyguanosin-8-yl)-4-aminobiphenyl adducts in human lymphoblastoid TK6 cells dosed with N-hydroxy-4-acetylaminobiphenyl and their relationship to mutation, toxicity, and gene expression profiling

Gene expression profiles that are anchored to phenotypic endpoints may lead to the identification of signatures that predict mutagenicity or carcinogenicity. The study presented here describes the analysis of DNA adducts in the human TK6 lymphoblastoid cell line after exposure to N-hydroxy-4-aminobiphenyl, a mutagenic metabolite of 4-aminobiphenyl. A validated nano-LC microelectrospray mass spectrometry assay is reported for the detection and quantification of N-(deoxyguanosin-8-yl)-4-aminobiphenyl (dG-C8-ABP), the principal DNA adduct of 4-aminobiphenyl. Limits of quantification, based on a signal-to-noise ratio of 10:1, are determined to correspond to approximately 27 fg of dG-C8-ABP injected on-column. The assay has been used to measure the steady-state levels of the adduct in the human TK6 lymphoblastoid cell line as a function of dose (0.5, 1.0, and 10.0 microM) and time (2, 6, and 27 h) after exposure to N-hydroxy-4-aminobiphenyl. The levels of dG-C8-ABP adducts in the cells, ranging from 18 to 500 adducts in 10(9) nucleotides, were then correlated to cell toxicity, induced mutation at the TK (thymidine kinase) and HPRT loci, and gene expression profiling through microarray analysis. Cell cultures were evaluated for toxicity by growth curve extrapolation, mutation assays were performed on the HPRT and TK loci, and gene expression profiles were generated by analyses using microarray technology. In the mutation assay analysis, as the toxicant concentration increased, there was an increase in mutation fraction, indicating a direct correlation to metabolite dosing level and mutations occurring at these two loci. Statistical analysis of the gene expression data determined that a total of 2250 genes exhibited statistically significant changes in expression after treatment with N-OH-AABP (P < 0.05). Among the genes identified, 2245 were up-regulated, whereas 5 genes that had functions in cell survival and cell growth and, hence, could be indicators of toxicity, were down-regulated relative to controls. The results demonstrate the value of anchoring gene expression patterns to phenotypic markers, such as DNA adduct levels, toxicity, and mutagenicity.     

Statistical search space reduction and two-dimensional data display approaches for UPLC-MS in biomarker discovery and pathway analysis

A new analytical strategy for biomarker recovery from directly coupled ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC Tof MS) data on biofluids is presented and exemplified using a study on hydrazine-induced liver toxicity. A key step in the strategy involves a novel procedure for reducing the spectroscopic search space by differential analysis of cohorts of normal and pathological samples using an orthogonal projection to latent structures discriminant analysis (O-PLS-DA). This efficiently sorts principal discriminators of toxicity from the background of thousands of metabolic features commonly observed in data sets generated by UPLC-MS analysis of biological fluids and is thus a powerful tool for biomarker discovery.     

Robust data processing and normalization strategy for MALDI mass spectrometric imaging

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) provides localized information about the molecular content of a tissue sample. To derive reliable conclusions from MSI data, it is necessary to implement appropriate processing steps in order to compare peak intensities across the different pixels comprising the image. Here, we review commonly used normalization methods, and propose a rational data processing strategy, for robust evaluation and modeling of MSI data. The approach includes newly developed heuristic methods for selecting biologically relevant peaks and pixels to reduce the size of a data set and remove the influence of the applied MALDI matrix. The methods are demonstrated on a MALDI MSI data set of a sagittal section of rat brain (4750 bins, m/z = 50-1000, 111 × 185 pixels) and the proposed preferred normalization method uses the median intensity of selected peaks, which were determined to be independent of the MALDI matrix. This was found to effectively compensate for a range of known limitations associated with the MALDI process and irregularities in MS image sampling routines. This new approach is relevant for processing of all MALDI MSI data sets, and thus likely to have impact in biomarker profiling, preclinical drug distribution studies, and studies addressing underlying molecular mechanisms of tissue pathology.     

Detonability of natural gas–air mixtures

Direct initiation experiments were carried out in a 105 cm diameter tube to study detonation properties and evaluate the detonability limits for mixtures of natural gas (NG) with air. The natural gas was primarily methane with 1.5–1.7% of ethane. A stoichiometric methane–oxygen mixture contained in a large plastic bag was used as a detonation initiator. Self-supporting detonations with velocities and pressures close to theoretical CJ values were observed in NG–air mixtures containing from 5.3% to 15.6% of NG at atmospheric pressure. These detonability limits are wider than previously measured in smaller channels, and close to the flammability limits. Detonation cell patterns recorded near the limits vary from large cells of the size of the tube to spiral traces of spin detonations. Away from the limits, detonation cell sizes decrease to about 20 cm for 10% NG, and are consistent with existing data for methane–air mixtures obtained in smaller channels. Observed cell patterns are very irregular, and contain secondary cell structures inside primary cells and fine structures inside spin traces.