Kinetic Modeling and Parameter Estimation in a Tower Bioreactor for Bioethanol Production

In this work, a systematic method to support the building of bioprocess models through the use of different optimization techniques is presented. The method was applied to a tower bioreactor for bioethanol production with immobilized cells of Saccharomyces cerevisiae. Specifically, a step-by-step procedure to the estimation problem is proposed. As the first step, the potential of global searching of real-coded genetic algorithm (RGA) was applied for simultaneous estimation of the parameters. Subsequently, the most significant parameters were identified using the Placket–Burman (PB) design. Finally, the quasi-Newton algorithm (QN) was used for optimization of the most significant parameters, near the global optimum region, as the initial values were already determined by the RGA global-searching algorithm. The results have shown that the performance of the estimation procedure applied in a deterministic detailed model to describe the experimental data is improved using the proposed method (RGA–PB–QN) in comparison with a model whose parameters were only optimized by RGA.     

Sandwich-type aptasensor employing modified aptamers and enzyme-DNA binding protein conjugates

The use of aptamers in various analytical applications as molecular recognition elements and alternative to antibodies has led to the development of various platforms that facilitate the sensitive and specific detection of targets ranging from small molecules and proteins to whole cells. The goal of this work was to design a universal and adaptable sandwich-type aptasensor exploiting the unique properties of DNA binding proteins. Specifically, two different enzyme-DNA binding protein conjugates, GOx-dHP and HRP-scCro, were used for the direct detection of a protein using two aptamers for target capture and detection. The specific dsDNA binding sequence for each DNA binding protein tag was incorporated in the form of a hairpin at one end of each aptamer sequence during the synthesis step. Detection was accomplished by an enzymatic (GOx/HRP) cascade reaction after the binding of each enzyme conjugate to its corresponding binding sequence on each aptamer. The proposed sandwich-type aptasensor was validated for the detection of thrombin, which is one of the most commonly used model targets with known dual aptamers. The limit of detection accomplished was 0.92 nM which is comparable with other colorimetric platforms reported in the literature. The sensitivity of the aptasensor was easily modulated by changing the number of dsDNA binding sites incorporated in the aptamer sequences, thus controlling the enzyme stoichiometry. Finally, the potential use of the proposed sensing approach for real sample testing was demonstrated using spiked human plasma and no significant matrix effects were observed when up to 2% plasma was used.

     

Two new potential optical materials: Co(II) and Ni(II) 3-fluorobenzoate complexes with pyridine-3-carboxamide

Two new complexes, [Co(3-fba)₂(na)₂(H₂O)₂] (1) and [Ni(3-fba)₂(na)₂(H₂O)₂] (2) (where 3-fba = 3-fluorobenzoate and na?=?pyridine-3-carboxamide, nicotinamide), were synthesized and characterized using different techniques (elemental analysis, FT-IR, UV-Vis spectrophotometer, single-crystal X-ray diffraction, fluorescence spectroscopy, and TGA/DTA analysis). X-ray structural analysis revealed that 1 and 2 are isostructural and exhibit distorted octahedral coordination geometry. In each molecule, metal atoms (Co⁺² and Ni⁺²) are linked by two 3-fluorobenzoate anions, two pyridine-3-carboxamide ligands, and two water molecules per formula unit. The 3-fluorobenzoate and pyridine-3-carboxamide are monodentate through a carboxylate oxygen atom and the nitrogen atom of the pyridine ring, respectively. UV-Vis results showed that the studied complexes have absorption edges similar to semiconductor structures. Namely, 1 and 2 indicated emission behaviors around 370?nm and 361?nm, respectively.     

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C₆₀ was used as the complementary hydrogen bonding module (C-1), in which the C₆₀ part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C₆₀ module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C₆₀ module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C₆₀ module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion.     

5-Benzyl-5-phenyl­[1,3]­di­thiolo­[4,5-d][1,3]­di­thiole-2-thione

In the title compound, C₁₇H₁₂S₅, the di­thiole ring bearing the aryl substituents assumes an envelope conformation with the maximum deviation from planarity being −0.053 Å. The phenyl and benzyl rings are twisted by 33.0 (1) and 31.1 (1)°, respectively, out of the di­thiole plane. The crystal packing is governed by short S⃛S interactions, with the shortest being 3.550 (2) Å.     

Kinetic resolution of donor-functionalised tertiary alcohols by Cu-H-catalysed stereoselective silylation using a strained silicon-stereogenic silane

A series of propargylic tertiary alcohols decorated with an sp2-hybridised nitrogen donor were kinetically resolved by reagent-controlled dehydrogenative Si-O coupling with a strained, highly reactive silicon-stereogenic cyclic silane.     

Eupatorium capillifolium essential oil: chemical composition, antifungal activity, and insecticidal activity

Natural plant extracts often contain compounds that are useful in pest management applications. The essential oil of Eupatorium capillifolium (dog-fennel) was investigated for antifungal and insecticidal activities. Essential oil obtained by hydrodistillation of aerial parts was analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC/MS). The major components were determined to be thymol methyl ether (=methyl thymol) (36.3%), 2,5-dimethoxy-p-cymene (20.8%) and myrcene (15.7%). Antifungal activity of the essential oil was weak against the plant pathogens Colletotrichum acutatum, C. fragariae, and C. gloeosporioides in direct bioautography assay. The E. capillifolium oil showed promising repellent activity against the yellow fever mosquito Aedes aegypti, whereas the oil exhibited moderate activity against the mosquito's first instar larvae in a high throughput bioassay. Topical applications of the oil showed no activity against the blood-feeding female adults of A. aegypti. Eupatorium capillifolium essential oil showed a linear dose response between adult lace bug (Stephanitis pyrioides) mortality and increasing oil concentration in an adulticidal activity bioassay. The dog-fennel oil was more potent than the conventional insecticide malathion. In conclusion, these combined results showed Eupatorium capillifolium oil is a promising novel source of a biological insecticide with multiple modes of action.     

Essential oil composition of four endemic Ferulago species growing in Turkey

The essential oils from aerial parts of Ferulago pachyloba (Fenzl) Boiss., F. platycarpa Boiss. & Bal., F. isaurica Penmen, and F. longistylis Boiss. (Apiaceae) were obtained by hydrodistillation and analyzed by GC and GC-MS. The highest oil yield (1.50%) was obtained from F. pachyloba followed by F. longistylis (0.16%), F. isaurica (0.08%) and F. platycarpa (0.07%). Fifty-three compounds were identified in the oil of F. pachyloba with (Z)-beta-ocimene (25.7%) and alpha-pinene (9.8%) as main constituents; sixty-seven in the oil of F. platycarpa with 2,3,6-trimethylbenzaldehyde (29.8%) and cis-chrysanthenyl acetate (24.2%) as main components; seventy-eight in the oil of F. isaurica with nonacosane (25.5%) and hexadecanoic acid (14.8%) as main constituents; and fifty-nine in the oil of F. longistylis with 2,3,6-trimethylbenzaldehyde (32.7%) and bornyl acetate (12.6%) as main components. Quantitative and qualitative differences in the oil compositions of these four species were observed.     

Production of Lactic Acid from Sucrose: Strain Selection, Fermentation, and Kinetic Modeling

Lactic acid is an important product arising from the anaerobic fermentation of sugars. It is used in the pharmaceutical, cosmetic, chemical, and food industries as well as for biodegradable polymer and green solvent production. In this work, several bacterial strains were isolated from industrial ethanol fermentation, and the most efficient strain for lactic acid production was selected. The fermentation was conducted in a batch system under anaerobic conditions for 50 h at a temperature of 34 °C, a pH value of 5.0, and an initial sucrose concentration of 12 g/L using diluted sugarcane molasses. Throughout the process, pulses of molasses were added in order to avoid the cell growth inhibition due to high sugar concentration as well as increased lactic acid concentrations. At the end of the fermentation, about 90% of sucrose was consumed to produce lactic acid and cells. A kinetic model has been developed to simulate the batch lactic acid fermentation results. The data obtained from the fermentation were used for determining the kinetic parameters of the model. The developed model for lactic acid production, growth cell, and sugar consumption simulates the experimental data well.