Synthesis and evaluation of esters obtained from phenols and phenoxyacetic acid with significant phytotoxic and cytogenotoxic activities.

There is a growing demand for herbicides that are more effective than conventional ones yet less harmful to ecosystems. In light of this, this study aimed to synthesize esters from phenols and phenoxyacetic acid, using compounds with known phytotoxic potential as starting materials. Phenoxyacetic acid was first synthesized and then utilized in the synthesis of seven esters through Steglich esterification, employing N,N'-dicyclohexylcarboimide and N,N-dimethylpyridin-4-amine in the presence of phenols (thymol, vanillin, eugenol, carvacrol, guaiacol, p-cresol, and ß-naphthol), yielding esters 1-7. All synthesized compounds were characterized using mass spectrometry, 1H, and 13C NMR. These compounds were tested for phytotoxicity to evaluate their effects on the germination and root development of Sorghum bicolor and Lactuca sativa seeds, and for the induction of alterations in the mitotic cycle of meristematic cells of L. sativa roots. Esters 1, 3, 4, and 5 exhibited the most significant phytotoxic activity in both L. sativa and S. bicolor. Alterations in the mitotic index and frequency of chromosomal alterations in L. sativa roots revealed the cytotoxic, genotoxic effects, and the aneugenic mode of action of the tested molecules. These findings suggest that these compounds could serve as inspiration for the synthesis of new semi-synthetic herbicides.

ß-enaminoester derivatives exhibit promising in vitro and in silico antiviral potential against Mayaro virus.

Mayaro virus (MAYV) is the causative agent of Mayaro fever, which is characterized mainly by acute fever and long-term severe arthralgia, common manifestations of other arbovirus infections, making the correct diagnosis a challenge. Besides, MAYV infections have been reported in South America, especially in Brazil. However, the lack of vaccines or specific antiviral drugs to control these infections makes the search for new antivirals an urgent need. Herein, we evaluated the antiviral potential of synthetic ß-enaminoesters derivatives against MAYV replication and their pharmacokinetic and toxicological (ADMET) properties using in vitro and in silico strategies. For this purpose, Vero cells were infected with MAYV at an MOI of 0.1, treated with compounds (50 µM) for 24 h, and virus titers were quantified by plaque reduction assays. Compounds 2b (83.33%) and 2d (77.53%) exhibited the highest activity with inhibition rates of 83.33% and 77.53%, respectively. The most active compounds 2b (EC50 = 18.92 µM; SI > 52.85), and 2d (EC50 = 14.52 µM; SI > 68.87) exhibited higher potency and selectivity than the control drug suramin (EC50 = 38.97 µM; SI > 25.66). Then, we investigated the mechanism of action of the most active compounds. None of the compounds showed virucidal activity, neither inhibited virus adsorption, but compound 2b inhibited virus entry (62.64%). Also, compounds 2b and 2d inhibited some processes involved with the release of new virus particles. Finally, in silico results indicated good ADMET parameters of the most active compounds and reinforced their promising profile as drug candidates against MAYV.

Unveiling the crystal structure of thermostable dienelactone hydrolase exhibiting activity on terephthalate esters.

Dienelactone hydrolase (DLH) is one of numerous hydrolytic enzymes with an α/ß-hydrolase fold, which catalyze the hydrolysis of dienelactone to maleylacetate. The DLHs share remarkably similar tertiary structures and a conserved arrangement of catalytic residues. This study presents the crystal structure and comprehensive functional characterization of a novel thermostable DLH from the bacterium Hydrogenobacter thermophilus (HtDLH). The crystal structure of the HtDLH, solved at a resolution of about 1.67 Å, exhibits a canonical α/ß-hydrolase fold formed by eight ß-sheet strands in the core, with one buried α-helix and six others exposed to the solvent. The structure also confirmed the conserved catalytic triad of DHLs formed by Cys121, Asp170, and His202 residues. The HtDLH forms stable homodimers in solution. Functional studies showed that HtDLH has the expected esterase activity over esters with short carbon chains, such as p-nitrophenyl acetate, reaching optimal activity at pH 7.5 and 70 °C. Furthermore, HtDLH maintains more than 50 % of its activity even after incubation at 90 °C for 16 h. Interestingly, HtDLH exhibits catalytic activity towards polyethylene terephthalate (PET) monomers, including bis-1,2-hydroxyethyl terephthalate (BHET) and 1-(2-hydroxyethyl) 4-methyl terephthalate, as well as other aliphatic and aromatic esters. These findings associated with the lack of activity on amorphous PET indicate that HtDLH has characteristic of a BHET-degrading enzyme. This work expands our understanding of enzyme families involved in PET degradation, providing novel insights for plastic biorecycling through protein engineering, which could lead to eco-friendly solutions to reduce the accumulation of plastic in landfills and natural environments.

Discovering the volatilome fingerprint of selected traditional Cuban wines elaborated with native grapes, tropical fruits, and rice using DHS-TD-GC-MS.

Cuban wine is a traditional alcoholic beverage elaborated with a wide variety of raw materials, such as native grapes, tropical fruits, and rice, and different winemaking processes. Research on Cuban wines is almost nonexistent, and therefore, a study of these wines is necessary to improve their quality. Dynamic headspace (DHS)-TD-gas chromatography-mass spectrometry (GC-MS) analysis was carried out to establish the different aroma fingerprints of different Cuban wines. A total of 42 volatile aroma metabolites (VAMs) were identified, including esters, alcohols, aldehydes, acids, volatile phenols, terpenes, and lactones. The odorant activity values (OAV) of each VAM were obtained, and the esters were the most relevant group due to their highest OAV. Ethyl octanoate, hexanoate, and butanoate stand out and are considered key odorants in the aromatic fingerprint. The VAMs were grouped into seven aromatic series. Fruity series showed the highest OAVs due to the contribution of ethyl esters and acetates. Principal component analysis was used to identify the specific parameters most accurately reflecting the differences between the wines. Showing that fruity, spicy, and chemical aromatic series allow distinguishing the wines into three aroma types. These results may provide useful information for the selection of raw materials and optimization of the traditional winemaking processes of Cuban wines. PRACTICAL APPLICATION: This research contributes to knowledge of the aroma and the oenological parameters of traditional and selected Cuban wines (rice wine, tropical fruit wine, and native grape varieties). The establishing of the aroma fingerprint of these wines provides useful information for the industrial development of a quality product that may then be promoted in other areas of the world.

Synthesis and Cytotoxic Activity of Friedelinyl Esters.

Commonly isolated from plants of Celastraceae family, pentacyclic triterpenoids have a broad spectrum of biological activities, such as antitumor, anti-inflammatory, antinociceptive properties, among others. Structural modifications in these triterpenoids can enhance their biological activity, as well as their selectivity, while improving their physicochemical and pharmacokinetic aspects. In this study, eight novel esters were synthesized: four derivatives of 3α-friedelinol (friedelan-3α-yl p-bromobenzoate (1a); friedelan-3α-yl naproxenate (1b); friedelan-3α-yl pent-4-ynoate (1c); friedelan-3α-yl undec-10-ynoate (1d)) and four derivatives of 3ß-friedelinol (friedelan-3ß-yl p-bromobenzoate (2a); friedelan-3ß-yl naproxenate (2b); friedelan-3ß-yl pent-4-ynoate (2c); friedelan-3ß-yl undec-10-ynoate (2d)). Overall, 3α-friedelinol showed greater reactivity when compared to the ß-epimer. The esters 1b-d and 2b-c were tested for antileukemic activity against THP-1 and K-562 cells but showed low cytotoxicity for both cell lines. The most active against THP-1 cells was friedelan-3ß-yl naproxenate (2b, IC50=266±6 µM), and the most active against K-562 cells was friedelan-3α-yl pent-4-ynoate (1c, IC50=267±5 µM).

Detection of phthalate esters and targeted metabolome analysis in Franciscana dolphin (Pontoporia blainvillei) blubber in the coast of Santa Catarina, southern Brazil.

The concerning of plastic pollution in different ecosystems has been worsened by the widespread presence. Phthalate esters (PAEs), plasticizers found in everyday products, can migrate into the environment, especially into the oceans. Researches on their effects on cetaceans are still rare. Metabolomics helps assess perturbations induced by exposure to PAEs, which act as persistent endocrine disruptors. Four PAEs (dimethyl phthalate - DMP, diethyl phthalate - DEP, dibutyl phthalate - DBP, and di(2-ethylhexyl phthalate - DEHP) were analyzed, along with cholesterol and fatty acid profiles of P. blainvillei's blubber samples collected in southern Brazil. The study reveals pervasive contamination by PAEs - especially DEHP, present in all samples - with positive correlations between DEP content and animal size and weight, as well as between the DEHP amount and the C17:1 fatty acid. These findings will be relevant to conservation efforts aimed at this threatened species and overall marine ecosystems.

Evaluation of digoxin-boronate ester formation through in-capillary derivatisation-large volume sample stacking-capillary zone electrophoresis.

Determination of digoxin through in-capillary derivatisation based on the formation of o-tolyl- and 2-naphthyl-anionic boronate esters in combination with large volume sample stacking-capillary electrophoresis is proposed. The derivatisation reaction was performed at basic pH values to obtain compounds with a charge and chromophore group during the stacking process. After stacking, the species were separated and detected at 225 nm using p-nitrophenol as an internal standard. Stacking and derivatisation parameters such as pre-concentration time, preconcentration voltage and injection time (relation between the analyte and the derivatisation agent) were evaluated using a Box-Behnken design. Under optimal conditions, the proposed method exhibits a linear range of 1.08-50.00 µM with a limit of detection of 0.36 µM; additionally, adequate repeatability and reproducibility was obtained (%RSD ≤ 5.0%). The methodology was validated by comparing it to an HPLC-UV established methodology and was successfully applied for the determination of digoxin in pharmaceutical tablets and blood serum samples, showing a positive performance for these matrices.

Optoelectronic Response to the Fluor Ion Bond on 4-(4,4,5,5-Tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde.

Boronate esters are a class of compounds containing a boron atom bonded to two oxygen atoms in an ester group, often being used as precursors in the synthesis of other materials. The characterization of the structure and properties of esters is usually carried out by UV-visible, infrared, and nuclear magnetic resonance (NMR) spectroscopic techniques. With the aim to better understand our experimental data, in this article, the density functional theory (DFT) is used to analyze the UV-visible and infrared spectra, as well as the isotropic shielding and chemical shifts of the hydrogen atoms 1H, carbon 13C and boron 11B in the compound 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde. Furthermore, this study considers the change in its electronic and spectroscopic properties of this particular ester, when its boron atom is coordinated with a fluoride anion. The calculations were carried out using the LSDA and B3LYP functionals in Gaussian-16, and PBE in CASTEP. The results show that the B3LYP functional gives the best approximation to the experimental data. The formation of a coordinated covalent B-F bond highlights the remarkable sensitivity of the NMR chemical shifts of carbon, oxygen, and boron atoms and their surroundings. Furthermore, this bond also highlights the changes in the electron transitions bands n → π* and π → π* during the absorption and emission of a photon in the UV-vis, and in the stretching bands of the C=C bonds, and bending of BO2 in the infrared spectrum. This study not only contributes to the understanding of the properties of boronate esters but also provides important information on the interactions and responses optoelectronic of the compound when is bonded to a fluorine atom.

Landfill leachates as a significant source for emerging pollutants of phthalic acid esters: Identification, occurrence, characteristics, fate, and transport.

Phthalic acid esters (PAEs) are byproducts released from various sources, including microplastics, cosmetics, personal care products, pharmaceuticals, waxes, inks, detergents, and insecticides. This review article provides an overview of the literature on PAEs in landfill leachates, exploring their identification, occurrence, characteristics, fate, and transport in landfills across different countries. The study emphasizes the influence of these substances on the environment, especially on water and soil. Various analytical techniques, such as GC-MS, GC-FID, and HPLC, are commonly employed to quantify concentrations of PAEs. Studies show significant variations in levels of PAEs among different countries, with the highest concentration observed in landfill leachates in Brazil, followed by Iran. Among the different types of PAE, the survey highlights DEHP as the most concentrated PAE in the leachate, with a concentration of 89.6 µg/L. The review also discusses the levels of other types of PAEs. The data shows that DBP has the highest concentration at 6.8 mg/kg, while DOP has the lowest concentration (0.04 mg/kg). The concentration of PAEs typically decreases as the depth in the soil profile increases. In older landfills, concentrations of PAE decrease significantly, possibly due to long-term degradation and conversion of PAE into other chemical compounds. Future research should prioritize evaluating the effectiveness of landfill liners and waste management practices in preventing the release of PAE and other pollutants into the environment. It is also possible to focus on developing efficient physical, biological, and chemical methods for removing PAEs from landfill leachates. Additionally, the effectiveness of existing treatment processes in removing PAEs from landfill leachates and the necessity for new treatment processes can be considered.

Extending the computational and experimental analysis of lipase active site selectivity.

Molecular docking is an important computational analysis widely used to predict the interaction of enzymes with several starting materials for developing new valuable products from several starting materials, including oils and fats. In the present study, molecular docking was used as an efficient in silico screening tool to select biocatalysts with the highest catalytic performance in butyl esters production in a solvent-free system, an eco-friendly approach, via direct esterification of free fatty acids from Licuri oil with butanol. For such purpose, three commercial lipase preparations were used to perform molecular docking studies such as Burkholderia cepacia (BCL), Porcine pancreatic (PPL), and Candida rugosa (CRL). Concurrently, the results obtained in BCL and CRL are the most efficient in the esterification process due to their higher preference for catalyzing the esterification of lauric acid, the main fatty acid found in the licuri oil composition. Meanwhile, PPL was the least efficient because it preferentially interacts with minor fatty acids. Molecular docking with the experimental results indicated the better performance in the synthesis of esters was BCL. In conclusion, experimental results analysis shows higher enzymatic productivity in esterification reactions of 1294.83 µmol/h.mg, while the CRL and PPL demonstrated the lowest performance (189.87 µmol / h.mg and 23.96 µmol / h.mg, respectively). Thus, molecular docking and experimental results indicate that BCL is a more efficient lipase to produce fatty acids and esters from licuri oil with a high content of lauric acid. In addition, this study also demonstrates the application of molecular docking as an important tool for lipase screening to achieve more sustainable production of butyl esters with a view synthesis of biolubricants.

Protective effect of sucrose esters from cape gooseberry (Physalis peruviana L.) in TNBS-induced colitis.

Phytotherapy is an attractive strategy to treat inflammatory bowel disease (IBD) that could be especially useful in developing countries. We previously demonstrated the intestinal anti-inflammatory effect of the total ethereal extract from the Physalis peruviana (Cape gooseberry) calyces in TNBS-induced colitis. This work investigates the therapeutic potential of Peruviose A and B, two sucrose esters that constitute the major metabolites of its calyces. The effect of the Peruvioses A and B mixture on TNBS-induced colitis was studied after 3 (preventive) and 15-days (therapy set-up) of colitis induction in rats. Colonic inflammation was assessed by measuring macroscopic/histologic damage, MPO activity, and biochemical changes. Additionally, LPS-stimulated RAW 264.7 macrophages were treated with test compounds to determine the effect on cytokine imbalance in these cells. Peruvioses mixture ameliorated TNBS-induced colitis in acute (preventive) or established (therapeutic) settings. Although 3-day treatment with compounds did not produce a potent effect, it was sufficient to significantly reduce the extent/severity of tissue damage and the microscopic disturbances. Beneficial effects in the therapy set-up were substantially higher and involved the inhibition of pro-inflammatory enzymes (iNOS, COX-2), cytokines (TNF-α, IL-1ß, and IL-6), as well as epithelial regeneration with restoration of goblet cells numbers and expression of MUC-2 and TFF-3. Consistently, LPS-induced RAW 264.7 cells produced less NO, PGE2, TNF-α, IL-6, and MCP-1. These effects might be related to the inhibition of the NF-κB signaling pathway. Our results suggest that sucrose esters from P. peruviana calyces, non-edible waste from fruit production, might be useful as an alternative IBD treatment.

Cellulose esters: Synthesis for further formation of films with magnetite nanoparticles incorporated.

This study investigated the homogeneous synthesis of cellulose acetate (CA) and propionate (CP) with varying degrees of substitution (DS) from sisal cellulose in a N, N-dimethylacetamide/lithium chloride (DMAc/LiCl) solvent system. These esters were used to prepare neat (CADSF/CPDSF) and nanocomposite films (CADSFFe/CPDSFFe) from prior synthesized magnetite nanoparticles (NPs, Fe3O4, 5.1 ± 0.5 nm). Among the CA and CP series, the composite CA0.7FFe and the neat CP0.7F films exhibited the highest modulus of elasticity, 2105 MPa and 2768 MPa, respectively, probably a consequence of the continuous fibrous structures present on the surface of these films. Microsphere formation on the film's surface was observed in scanning electron microscopy micrographs. This points to applications in the controlled release of targeted substances. The VSM analysis showed that the cellulosic matrices preserved the superparamagnetic characteristics of the NPs. This study suggested a reduced coupling effect between nanoparticles inside polymeric films due to magnetic saturation at low fields. CA0.7FFe and CA1.3FFe composite films reached a saturation magnetization (MSAT) of 46 emu/g around 7 kOe field. Hosting magnetite nanoparticles in cellulose ester matrices may be an interesting way to develop new functional cellulose-based materials, which have the potential for diverse applications, including microelectromechanical systems and microsensors.

Optimizing the enzymatic production of biolubricants by the Taguchi method: Esterification of the free fatty acids from castor oil with 2-ethyl-1-hexanol catalyzed by Eversa Transform 2.0.

The solvent-free esterification of the free fatty acids (FFAs) obtained by the hydrolysis of castor oil (a non-edible vegetable oil) with 2-ethyl-1-hexanol (a branched fatty alcohol) was catalyzed by different free lipases. Eversa Transform 2.0 (ETL) features surpassed most commercial lipases. Some process parameters were optimized by the Taguchi method (L16'). As a result, a conversion over 95% of the FFAs of castor oil into esters with lubricants properties was achieved under optimized reaction conditions (15 wt% of biocatalyst content, 1:4 molar ratio (FFAs/alcohol), 30 °C, 180 rpm, 96 h). The substrates molar ratio had the highest influence on the dependent variable (conversion at 24 h). FFAs/2-ethyl-1-hexanol esters were characterized regarding the physicochemical and tribological properties. Interestingly, the modification of the FFAs with 2-ethyl-1-hexanol by ETL increased the oxidative stability of the FFAs feedstock from 0.18 h to 16.83 h. The biolubricants presented a lower friction coefficient than the reference commercial mineral lubricant (0.052 ± 0.07 against 0.078 ± 0.04). Under these conditions, ETL catalyzed the oligomerization of ricinoleic acid (a hydroxyl fatty acid) into estolides, reaching a conversion of 25.15% of the initial FFAs (for the first time).

Development and validation of a GC Orbitrap-MS method for the analysis of phthalate esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) in atmospheric particles and its application for screening PM2.5 from Curitiba, Brazil.

Phthalates or phthalic acid esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) are ubiquitous chemicals often used as plasticisers and additives in many industrial products and are classified as both persistent organic pollutants (POPs) and new emerging pollutants (NEPs). Exposure to these chemicals, especially through inhalation, is linked to a wide range of negative health effects, including endocrine disruption. Air particulate matter (PM) with an aerodynamic diameter ≤ 2.5 µm can be enriched with PAEs and DEHA and if inhaled can cause multi-system human toxicity. Therefore, proper monitoring of PAEs and DEHA in PM is required to assess human exposure to these pollutants. In this work, we developed and validated a new and sensitive gas-chromatography high-resolution mass spectrometry (GC-HRMS) method for targeted analysis of PAEs including dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl)adipate (DEHA), bis(2-ethylhexyl)phthalate (DEHP), di-n-octyl phthalate (DOP), in PM. Analytical aspects including sample preparation steps and GC-HRMS parameters, e.g., quadrupole isolation window, to enhance method sensitivity have been assessed. The estimated limit of detection (LODs) of target PAEs and DEHA ranged from 5.5 to 17 pg µL-1, allowing their trace-level detection in PM. Extraction efficiencies of 78-101% were obtained for the target compounds. Low DMP and DEP extraction efficiencies from the spiked filter substrates indicated that significant losses of higher volatility PAEs can occur during the sample collection when filter-based techniques are used. This work is the first targeted method based on GC-Orbitrap MS for PAEs and DEHA in environmental samples. The validated method was successfully applied for the targeted analysis of PAEs and DEHA in PM2.5 samples from the eighth most populous city in Brazil, Curitiba. This work is the first to report DBP, DEHA, DEHP, and DOP in urban PM from Brazil. The observed concentrations of PAEs (up to 29 ng m-3) in PM2.5 from Curitiba may not represent the extent of pollution by these toxic compounds since the analysed samples were collected during a COVID-19 restriction when anthropogenic activities were reduced.

Chemical characterization, antioxidant activity, and cytotoxicity of fatty acids methyl esters from Handroanthus impetiginosus (Mart. ex DC.) Mattos (Bignoniaceae) seeds.

Handroanthus impetiginosus, popularly known as "ipê-roxo", is used in folk medicine to treat skin inflammations, infections, stomach diseases, and cancer. Fatty acid methyl esters (FAMEs) obtained from the esterification reaction of fatty acids (FA) found in the hexane extract (HE) of seeds of H. impetiginosus were identified by gas chromatography-mass spectrometry (GC-MS). The antioxidant and cytotoxic activities of the HE and FAMEs were evaluated. Methyl palmitate, methyl linoleate, methyl oleate, and methyl stearate were the major FAMEs obtained from the HE. The samples, especially the HE, exhibited a significant antioxidant potential analyzed by ferric reducing ability power (FRAP) assay. In the A. salina larvae bioassay, the HE showed no cytotoxic effects, but the FAMEs exhibited a high toxicity. This study reported, for the first time, the antioxidant and cytotoxic activities of the HE and FAMEs obtained from H. impetiginosus seeds.

Grouping of esters of 4-hydroxybenzoic acid for hazard assessment.

Hazardous properties of a large number of esters of 4-hydroxybenzoic acid (parabens) have been proposed by ECHA to be assessed as a group. We recommend to restrict the grouping approach to short chain esters, i.e. methyl, ethyl, propyl and butyl paraben which are very similar in chemical structures, physicochemical properties, toxicokinetics, and hazardous properties. While these parabens show a weak estrogenicity in some in vitro or in vivo screening assays, they do not induce estrogen-receptor-mediated adverse effects in intact animals. Therefore, there is no support regarding classification and labeling of endocrine disruption or reproductive toxicity of these parabens.

Functionalized Biochar from the Amazonian Residual Biomass Murici Seed: An Effective and Low-Cost Basic Heterogeneous Catalyst for Biodiesel Synthesis.

This study presents the synthesis of a basic heterogeneous catalyst based on sodium functionalized biochar. The murici biochar (BCAM) support used in the process was obtained through the pyrolysis of the murici seed (Byrsonimia crassifolia), followed by impregnation of the active phase in amounts that made it possible to obtain concentrations of 6, 9, 12, 15 and 18% of sodium in the final composition of the catalyst. The best-performing 15Na/BCAM catalyst was characterized by Elemental Composition (CHNS), Thermogravimetric Analysis (TG/DTG), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Energy Dispersion X-ray Spectroscopy (EDS). The catalyst 15Na/BCAM was applied under optimal reaction conditions: temperature of 75 °C, reaction time of 1.5 h, catalyst concentration of 5% (w/w) and MeOH:oil molar ratio of 20:1, resulting in a biodiesel with ester content of 97.20% ± 0.31 in the first reaction cycle, and maintenance of catalytic activity for five reaction cycles with ester content above 65%. Furthermore, the study demonstrated an effective catalyst regeneration process, with the synthesized biodiesels maintaining ester content above 75% for another five reaction cycles. Thus, the data indicate a promising alternative to low-cost residual raw materials for the synthesis of basic heterogeneous catalysts.

Hydroxy esters atmospheric degradation: OH and Cl reactivity, products distribution and fate of the alkoxy radicals formed.

Kinetic studies of the reaction of ethyl glycolate HOCH2C(O)OCH2CH3 with OH radicals (kOH) and Cl atoms (kCl) have been conducted by the relative method using a glass atmospheric reactor by "in situ" Fourier Transform Infrared (FTIR) and Gas Chromatography equipped with flame ionization detection by Solid Phase Micro Extraction (GC-FID/SPME) at room temperature and atmospheric pressure. The following relative rate coefficients were determined using several reference compounds and two different techniques: kEG + OH-FTIR = (4.36 ± 1.21) × 10-12; kEG + OH-GC-FID= (3.90 ± 0.74) × 10-12; and kEG + Cl-GC-FID= (6.40 ± 0.72) × 10-11 all values in units of cm3.molecule-1.s-1. Complementary product studies were performed under comparable conditions to the kinetic tests, in order to identify the reaction products and to postulate their tropospheric oxidation mechanisms. The reaction of OH radicals and Cl atoms with ethyl glycolate initiates via H-atom abstraction from alkyl groups of the molecule. Formic acid was positively identified as a reaction product by FTIR. On the other hand, formaldehyde, acetaldehyde, glycolic acid; and formic acid were identified by the GC-MS technique. The Structure-Activity Relationship, (SAR) calculations were also implemented to estimate the more favorable reaction pathways and compare them with the products identified. Tropospheric lifetimes of τOH = 34 h and τCl = 5.5 days were estimated to determine how these investigated reactions might affect the air quality. In this sense, average ozone production of [O3] = 0.75 and a Photochemical Ozone Creation Potential, POCP, of 38 were calculated for the hydroxyl ester studied.

Growth Behavior, Biomass Composition and Fatty Acid Methyl Esters (FAMEs) Production Potential of Chlamydomonas reinhardtii, and Chlorella vulgaris Cultures.

The production of biomolecules by microalgae has a wide range of applications in the development of various materials and products, such as biodiesel, food supplements, and cosmetics. Microalgae biomass can be produced using waste and in a smaller space than other types of crops (e.g., soja, corn), which shows microalgae's great potential as a source of biomass. Among the produced biomolecules of greatest interest are carbohydrates, proteins, lipids, and fatty acids. In this study, the production of these biomolecules was determined in two strains of microalgae (Chlamydomonas reinhardtii and Chlorella vulgaris) when exposed to different concentrations of nitrogen, phosphorus, and sulfur. Results show a significant microalgal growth (3.69 g L-1) and carbohydrates (163 mg g-1) increase in C. reinhardtii under low nitrogen concentration. Also, higher lipids content was produced under low sulfur concentration (246 mg g-1). It was observed that sulfur variation could affect in a negative way proteins production in C. reinhardtii culture. In the case of C. vulgaris, a higher biomass production was obtained in the standard culture medium (1.37 g L-1), and under a low-phosphorus condition, C. vulgaris produced a higher lipids concentration (248 mg g-1). It was observed that a low concentration of nitrogen had a better effect on the accumulation of fatty acid methyl esters (FAMEs) (C16-C18) in both microalgae. These results lead us to visualize the effects that the variation in macronutrients can have on the growth of microalgae and their possible utility for the production of microalgae-based subproducts.

High wax ester and triacylglycerol biosynthesis potential in coastal sediments of Antarctic and Subantarctic environments.

The wax ester (WE) and triacylglycerol (TAG) biosynthetic potential of marine microorganisms is poorly understood at the microbial community level. The goal of this work was to uncover the prevalence and diversity of bacteria with the potential to synthesize these neutral lipids in coastal sediments of two high latitude environments, and to characterize the gene clusters related to this process. Homolog sequences of the key enzyme, the wax ester synthase/acyl-CoA:diacylglycerol acyltransferase (WS/DGAT) were retrieved from 13 metagenomes, including subtidal and intertidal sediments of a Subantarctic environment (Ushuaia Bay, Argentina), and subtidal sediments of an Antarctic environment (Potter Cove, Antarctica). The abundance of WS/DGAT homolog sequences in the sediment metagenomes was 1.23 ± 0.42 times the abundance of 12 single-copy genes encoding ribosomal proteins, higher than in seawater (0.13 ± 0.31 times in 338 metagenomes). Homolog sequences were highly diverse, and were assigned to the Pseudomonadota, Actinomycetota, Bacteroidota and Acidobacteriota phyla. The genomic context of WS/DGAT homologs included sequences related to WE and TAG biosynthesis pathways, as well as to other related pathways such as fatty-acid metabolism, suggesting carbon recycling might drive the flux to neutral lipid synthesis. These results indicate the presence of abundant and taxonomically diverse bacterial populations with the potential to synthesize lipid storage compounds in marine sediments, relating this metabolic process to bacterial survival.