Obtaining and studying the properties of cobalt- and nickel-containing nanocomposites by thermolysis, using saturated carboxylates as precedors

Nickel (II) and cobalt (II) salts were synthesized with saturated monocarboxylic acids: butyric, valeric, nylon,enanthic, and caprylic. The obtained compounds were characterized by elemental analysis, IR spectroscopy,and differential scanning calorimetry. As a result of thermolysis of the synthesized carboxylates, nanocomposites were obtained, which were studied by scanning and transmission electron microscopy, elemental analysis, IR spectroscopy, energy dispersive X-ray spectroscopy, and X-ray phase analysis. The magnetic properties of the obtained nanocomposites have been studied.

Total organic carbon and the contribution from speciated organics in cloud water: airborne data analysis from the CAMP²Ex field campaign

This work focuses on total organic carbon (TOC) and contributing species in cloud water over Southeast Asia using a rare airborne dataset collected during NASA's Cloud, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex), in which a wide variety of maritime clouds were studied, including cumulus congestus, altocumulus, altostratus, and cumulus. Knowledge of TOC masses and their contributing species is needed for improved modeling of cloud processing of organics and to understand how aerosols and gases impact and are impacted by clouds. This work relies on 159 samples collected with an axial cyclone cloud-water collector at altitudes of 0.2–6.8 km that had sufficient volume for both TOC and speciated organic composition analysis. Species included monocarboxylic acids (glycolate, acetate, formate, and pyruvate), dicarboxylic acids (glutarate, adipate, succinate, maleate, and oxalate), methanesulfonic acid (MSA), and dimethylamine (DMA). TOC values range between 0.018 and 13.66 ppm C with a mean of 0.902 ppm C. The highest TOC values are observed below 2 km with a general reduction aloft. An exception is samples impacted by biomass burning for which TOC remains enhanced at altitudes as high as 6.5 km (7.048 ppm C). Estimated total organic matter derived from TOC contributes a mean of 30.7 % to total measured mass (inorganics + organics). Speciated organics contribute (on a carbon mass basis) an average of 30.0 % to TOC in the study region and account for an average of 10.3 % to total measured mass. The order of the average contribution of species to TOC, in decreasing contribution of carbon mass, is as follows (±1 standard deviation): acetate (14.7 ± 20.5 %), formate (5.4 ± 9.3 %), oxalate (2.8 ± 4.3 %), DMA (1.7 ± 6.3 %), succinate (1.6 ± 2.4 %), pyruvate (1.3 ± 4.5 %), glycolate (1.3 ± 3.7 %), adipate (1.0 ± 3.6 %), MSA (0.1 ± 0.1 %), glutarate (0.1 ± 0.2 %), and maleate (< 0.1 ± 0.1 %). Approximately 70 % of TOC remains unaccounted for, highlighting the complex nature of organics in the study region; in samples collected in biomass burning plumes, up to 95.6 % of TOC mass is unaccounted for based on the species detected. Consistent with other regions, monocarboxylic acids dominate the speciated organic mass (∼ 75 %) and are about 4 times more abundant than dicarboxylic acids. Samples are categorized into four cases based on back-trajectory history, revealing source-independent similarity between the bulk contributions of monocarboxylic and dicarboxylic acids to TOC (16.03 %–23.66 % and 3.70 %–8.75 %, respectively). Furthermore, acetate, formate, succinate, glutarate, pyruvate, oxalate, and MSA are especially enhanced during biomass burning periods, which is attributed to peat emissions transported from Sumatra and Borneo. Lastly, dust (Ca2+) and sea salt (Na+/Cl-) tracers exhibit strong correlations with speciated organics, supporting how coarse aerosol surfaces interact with these water-soluble organics.

Chiroptical activity of hydroxycarboxylic acids with implications for the origin of biological homochirality

Circularly polarised light (CPL) interacting with interstellar organic molecules might have imparted chiral bias and hence preluded prebiotic evolution of biomolecular homochirality. The l-enrichment of extra-terrestrial amino acids in meteorites, as opposed to no detectable excess in monocarboxylic acids and amines, has previously been attributed to their intrinsic interaction with stellar CPL revealed by substantial differences in their chiroptical signals. Recent analyses of meteoritic hydroxycarboxylic acids (HCAs) – potential co-building blocks of ancestral proto-peptides – indicated a chiral bias toward the l-enantiomer of lactic acid. Here we report on novel anisotropy spectra of several HCAs using a synchrotron radiation electronic circular dichroism spectrophotometer to support the re-evaluation of chiral biomarkers of extra-terrestrial origin in the context of absolute photochirogenesis. We found that irradiation by CPL which would yield l-excess in amino acids would also yield l-excess in aliphatic chain HCAs, including lactic acid and mandelic acid, in the examined conditions. Only tartaric acid would show “unnatural” d-enrichment, which makes it a suitable target compound for further assessing the relevance of the CPL scenario.

Total organic carbon and contribution from speciated organics in cloud water: Airborne data analysis from the CAMP²Ex field campaign

This work focuses on total organic carbon (TOC) and contributing species in cloud water over Southeast Asia using a rare airborne dataset collected during NASA’s Cloud, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex), in which a wide variety of maritime clouds were studied, including cumulus congestus, altocumulus, altostratus, and cumulus. Knowledge of TOC levels and their contributing species is needed for improved modeling of cloud processing of organics and to understand how aerosols and gases impact and are impacted by clouds. This work relies on 159 samples collected with an Axial Cyclone Cloud water Collector at altitudes of 0.2–6.8 km that had sufficient volume for both TOC and speciated organic composition analysis. Species included monocarboxylic acids (glycolate, acetate, formate, and pyruvate), dicarboxylic acids (glutarate, adipate, succinate, maleate, and oxalate), methanesulfonate (MSA), and dimethylamine (DMA). TOC values range between 0.018–13.660 ppm C with a mean of 0.902 ppm C. The highest TOC values are observed below 2 km with a general reduction aloft. An exception is samples impacted by biomass burning for which TOC remains enhanced as high as 6.5 km (7.048 ppm C). Estimated total organic matter derived from TOC contributes a mean of 30.7 % to total measured mass (inorganics + organics). Speciated organics contribute (on carbon mass basis) an average of 30.0 % to TOC in the study region, and account for an average of 10.3 % to total measured mass. The order of the average contribution of species to TOC, in decreasing contribution of carbon mass, is as follows: acetate (14.7 ± 20.5 %), formate (5.4 ± 9.3 %), oxalate (2.8 ± 4.3 %), DMA (1.7 ± 6.3 %), succinate (1.6 ± 2.4 %), pyruvate (1.3 ± 4.5 %), glycolate (1.3 ± 3.7 %), adipate (1.0 ± 3.6 %), MSA (0.1 ± 0.1 %), glutarate (0.1 ± 0.2 %), maleate (< 0.1 ± 0.1 %). Approximately 70 % of TOC remains unaccounted for, thus highlighting the complex nature of organics in the study region; samples collected in biomass burning plumes have up to 95.6 % of unaccounted TOC mass based on the species detected. Consistent with other regions, monocarboxylic acids dominate the speciated organic mass (~75 %) and are about four times in greater abundance than dicarboxylic acids. Samples are categorized into four cases based on back-trajectory history revealing source-independent similarity between the bulk contributions of monocarboxylic and dicarboxylic acids to TOC (16.03 %–23.66 % and 3.70 %–8.75 %, respectively). Furthermore, acetate, formate, succinate, glutarate, pyruvate, oxalate, and MSA are especially enhanced during biomass burning periods, attributed to peat emissions transported from Sumatra and Borneo. Lastly, dust (Ca2+) and sea salt (Na+/Cl−) tracers exhibit strong correlations with speciated organics, thus supporting how coarse aerosol surfaces interact with these water-soluble organics.

Screening and characterization of a novel reversible 4-hydroxyisophthalic acid decarboxylase from Cystobasidium slooffiae HTK3

Owing to carboxylation activity, reversible decarboxylases can use CO2 as a C1-building block to produce useful carboxylic acids. Although many reversible decarboxylases can synthesize aromatic monocarboxylic acids, only a few reversible decarboxylases have been reported to date that catalyze the synthesis of aromatic dicarboxylic acids. In the present study, a reversible 4-hydroxyisophthalic acid decarboxylase was identified in Cystobasidium slooffiae HTK3. Furthermore, recombinant 4-hydroxyisophthalic acid decarboxylase was prepared, characterized, and used for 4-hydroxyisophthalic acid production from 4-hydroxybenzoic acid.

Chiroptical activity of hydroxycarboxylic acids: implications for the origin of biological homochirality

Circularly polarised light (CPL) interacting with interstellar organic molecules might have imparted chiral bias and hence preluded prebiotic evolution of biomolecular homochirality. The l-enrichment of extra-terrestrial amino acids in meteorites, as opposed to no detectable excess in monocarboxylic acids and amines, has previously been attributed to their intrinsic interaction with stellar CPL revealed by substantial differences in their chiroptical signals. Recent analyses of meteoritic hydroxycarboxylic acids (HCAs) – potential co-building blocks of ancestral proto-peptides – showed an enantiomeric excess in l-lactic acid. Here we report on novel anisotropy spectra of several HCAs using a synchrotron radiation electronic circular dichroism spectrophotometer to support the re-evaluation of chiral biomarkers of extra-terrestrial origin in the context of absolute photochirogenesis. We found that irradiation by CPL which would yield l-excess in amino acids would also yield lexcess in aliphatic chain HCAs including lactic acid as well as mandelic acid in the examined conditions. Only tartaric acid would show “unnatural” d-enrichment, which makes it a suitable target compound for further assessing the relevance of the CPL scenario.

Garlic greening: Pigments biosynthesis and control strategies

Greening is a major problem for garlic’s quality. This phenomenon leads to discoloration of the product and is directly related to the alliinase-catalyzed conversion of isoalliin into 1-propenyl-containing thiosulfates. Garlic crushing, refrigeration, and storage in normal atmosphere, as well as in the presence of monocarboxylic acids, are established the main factors that promote its greening. In last decades, the study of biochemical pathway of this phenomenon has allowed to effectively understand the main steps and key enzymes involved, and to identify optimum conditions for chemical and enzymatic reactions leading to discoloration. These findings have, in some cases, determined the development of new tools for the control of garlic greening on large scale. After providing an updated description of the biochemistry of green pigments produced in garlic, this review reports an overview on the strategies for controlling discoloration of garlic at industrial level.