Co-Fermentation of Cheese Whey and Crude Glycerol in EGSB Reactor as a Strategy to Enhance Continuous Hydrogen and Propionic Acid Production

This study evaluated the production of hydrogen and propionic acid in an expanded granular sludge bed (EGSB) reactor by co-fermentation of cheese whey (CW) and crude glycerol (CG). The reactor was operated at hydraulic retention time (HRT) of 8 h by changing the CW/CG ratio from 5:1 to 5:2, 5:3, 5:4, and 5:5. At the ratio of 5:5, HRT was reduced from 8 to 0.5 h. The maximum hydrogen yield of 0.120 mmol H₂ g COD^?1 was observed at the CW/CG ratio of 5:1. Increasing the CG concentration repressed hydrogen production in favor of propionic acid, with a maximum yield of 6.19 mmol HPr g COD^?1 at the CW/CG ratio of 5:3. Moreover, by reducing HRT of 8 to 0.5 h, the hydrogen production rate was increased to a maximum value of 42.5 mL H₂ h^?1 L^?1at HRT of 0.5 h. The major metabolites were propionate, 1,3-propanediol, acetate, butyrate, and lactate.     

Synthesis and Characterization of Triphenylphosphine Oxide-Containing Poly(Aryl Imide)-Poly(Dimethyl Siloxane) Randomly Segmented Copolymers

Abstract

Poly(aryl imide)-poly(dimethyl siloxane) randomly segmented copolymers were synthesized by essentially a one-step solution imidization process in a solvent system consisting of predominately o-dichlorobenzene with a small amount of n-methylpyrolidone. This solvent combination was selected because of its ability to afford homogeneous solutions throughout the polymerization process. This enabled copolymers of any desired poly(dimethyl siloxane) composition to be prepared. A hydrolytically stable triphenylphosphine oxide containing diamine, bis(3-amino-phenoxy-4′-phenyl)phenylphosphine oxide, was utilized as a chain extender and together with oxydiphthalic anhydride formed the hard segment in these copolymers. The soft segment was formed from α,ω-aminopropyl poly(dimethyl siloxane) oligomers of controlled molecular weight. The presence of phosphorus and silicon contributes several unique properties to the system, including enhanced solubility, thermal stability, and flame resistance. High molecular weight copolymers containing up to 60% (w/w) of the poly(dimethyl siloxane) segments were successfully prepared using this method. Gel permeation chromatography analysis, based on a universal calibration curve in CHCl₃, was performed to determine the molecular weights and distribution. These copolymers with 40-60% (w/w) poly(dimethyl siloxane) exhibited upper T_g values ranging from 130 to 180°C and showed substantial char yields at 750°C in air, which increased with siloxane content. Dynamic mechanical analysis confirmed the anticipated microphase behavior by the presence of two separate glass-transition regions. Both small angle x-ray scattering and transmission electron microscopy measurements determined on well-characterized transparent cast films were used to better demonstrate the multiphase nature of these copolymers.     

Comparative study of the oxidative and thermal stability of vegetable oils to be used as lubricant bases

Demand for lubricating oils is increasing in the growing Brazilian economy. The use of vegetable bases in exchange of minerals can bring socio-economic and environmental benefits for Brazil. The purpose of this study is to compare the thermal and oxidative stability of vegetable oils related to the bases commonly used as lubricants. In this study, thermogravimetric analysis of castor oil, cotton oil, macauba’s almond oil, passion oil, paraffinic mineral oil, naphthenic oil (NH-140) and synthetic oil (Etro) was performed in inert and oxidative atmosphere to study the thermal and oxidative degradation of the vegetable oils related to the most common lubricants’ oils base. These oils’ oxidation stability were determined by standard procedures (ISO 6886). The use of mineral oil’s additives in these vegetable oils was tested to verify the viability of these additives to improve the oxidative stability of the vegetable oils. The castor oil and the cotton oil presented results of thermal analysis similar to the mineral and synthetic bases values. The castor oil was the only vegetable oil that showed a great oxidative stability. All other vegetable oils had their oxidative stability significantly increased by the additives.     

Chemometric Strategies to Develop a Nanocomposite Electrode for Simultaneous Determination of Ascorbic Acid,Dopamine, and Uric Acid

A simple and sensitive method for simultaneously measuring dopamine (DA), ascorbic acid (AA), and uric acid (UA) using a poly(1‐aminoanthracene) and carbon nanotubes nanocomposite electrode is presented. The experimental parameters for composite film synthesis as well as the variables related to simultaneous determination of DA, AA, and UA were optimized at the same time using fractional factorial and Doehlert designs. The use of carbon nanotubes and poly(1‐aminoanthracene) in association with a cathodic pretreatment led to three well‐defined oxidation peaks at potentials around ?0.039, 0.180 and 0.351 V (vs. Ag/AgCl) for AA, DA, and UA, respectively. Using differential pulse voltammetry, calibration curves for AA, DA, and UA were obtained over the range of 0.16–3.12×10^?3 mol L^?1, 3.54–136×10^?6 mol L^?1, and 0.76–2.92×10^?3 mol L^?1, with detection limits of 3.95×10^?5 mol L^?1, 2.90×10^?7 mol L^?1, and 4.22×10^?5 mol L^?1, respectively. The proposed method was successfully applied to determine DA, AA, and UA in biological samples with good results.     

Development and validation studies for determination of phenylpropanoid‐substituted flavan‐3‐ols in semipurified extract of Trichilia catigua by high‐performance liquid chromatography with photodiode array detection

The phenolic compounds are the main phytochemical constituents of the bark of Trichilia catigua and are commonly used for medicinal purposes. An HPLC method for the simultaneous quantification of phenolic compounds (procyanidin B2 (PB2), epicatechin (EPC), chinchonains Ia, Ib, IIa, IIb, catechin, and chrologenic acid) in T. catigua extract was developed and validated. A suitable chromatographic system was selected, which uses a gradient elution with methanol/ACN (75:25), and water both with 0.05% TFA, as mobile phase, column Luna, 280 nm, and flow 0.4 mL/min. Validation of the analytical method was based on the parameters: linearity, precision, LODs and LOQs, accuracy, robustness, and stability. The method showed linearity for PB2 and EPC, in the range 10–120 μg/mL with good correlation coefficients (>0.996). For precision, the repeatability ranged from 1.89 to 3.23%, and the values for accuracy for PB2 and EPC were 95 and 89%, respectively. The LODs and LOQs for PB2 were 1.36 and 4.12 μg/mL, and for EPC were 2.18 and 6.61 μg/mL, respectively. The method was robust under the conditions employed. The proposed method could be employed for quality assessment of T. catigua, as well as pharmaceutical products.     

Microwave Synthesis of 5-Substituted 1H-Tetrazoles Catalyzed by Bismuth Chloride in Water

Bismuth chloride was used to catalyze the [2 + 3] cycloaddition between sodium azide with aryl nitriles, aliphatic nitriles, and vinyl nitriles. A number of 5-substituted 1H-tetrazoles were synthesized in water or isopropanol/water mixtures using microwave heating. Good yields were obtained for these reactions when heated for 1 h at 120–160 °C in a 3:1 isopropanol/water mixture. A few of the less reactive nitriles required longer reaction times for good yields.     

Selenides and diselenides containing oxadiazoles: a new class of functionalised materials

A simple and efficient procedure for the synthesis of a new class of organoselenium liquid crystal compounds was developed. The coupling of aryl bromides with elemental selenium was catalysed using copper oxide nanopowder in the presence of potassium hydroxide employing dimethyl sulfoxide as the solvent. This is the first report of the synthesis and characterisation of liquid crystal-based diselenides. Their mesophases were characterised by polarising optical microscopy and differential scanning calorimetry. Compounds 1, 2 and 4b exhibited the smectic A phase. In addition, these compounds showed weak blue fluorescence in solution (λ_{max. em.} 350–405 nm) and a Stokes shift of around 90 nm.     

Hydrophobic Derivatives of Dextran Polysaccharide: Characterization and Properties

This study reports the synthesis and characterization of hydrophobic derivatives of dextran in which long alkyl chains substituted a proportion of the hydroxyl groups. These derivatives were characterized by ¹³C and ¹H NMR and infrared spectroscopy. Information about hydrophobic associations in aqueous solutions was obtained by fluorescence spectroscopy in the presence of pyrene and nabumetone probes. These results, in addition to the swelling‐index data of derivatives, showed that there are perspectives of using them as a starting point for models of drug delivery.     

Cinnamic acid hydrogen bonds to isoniazid and N′‐(propan‐2‐ylidene)isonicotinohydrazide,an in situ reaction product of isoniazid and acetone

A new polymorph of the cinnamic acid–isoniazid cocrystal has been prepared by slow evaporation, namely cinnamic acid–pyridine‐4‐carbohydrazide (1/1), C₉H₈O₂·C₆H₇N₃O. The crystal structure is characterized by a hydrogen‐bonded tetrameric arrangement of two molecules of isoniazid and two of cinnamic acid. Possible modification of the hydrogen bonding was investigated by changing the hydrazide group of isoniazid via an in situ reaction with acetone and cocrystallization with cinnamic acid. In the structure of cinnamic acid–N′‐(propan‐2‐ylidene)isonicotinohydrazide (1/1), C₉H₈O₂·C₉H₁₁N₃O, carboxylic acid–pyridine O—H...N and hydrazide–hydrazide N—H...O hydrogen bonds are formed.