Detection of Organic Matter and Biosignatures in Space Missions.

Carbon-based compounds are widespread throughout the Universe, including abiotic molecules that are the components of the life as we know it. This article reviews the space missions that have aimed to detect organic matter and biosignatures in planetary bodies of our solar system. While to date there was only one life-detection space mission, i.e., the Viking mission to Mars, several past and present space missions have searched for organic matter, paving the way for the future detection of signatures of extra-terrestrial life. This review also reports on the in-situ analysis of organic matter and sample-return missions from primitive bodies, i.e. comets and asteroids, providing crucial information on the conditions of the early solar system as well as on the building blocks of life delivered to the primitive Earth.

Interaction of organic compounds with chondritic silicate surfaces. Atomistic insights from quantum chemical periodic simulations.

The interaction of 14 different probe organic molecules with the crystalline (010) forsterite Mg2SiO4 surface has been studied at quantum chemical level by means of B3LYP-D2* periodic simulations. The probe molecules are representatives of the class of soluble organic compounds found in carbonaceous meteorites, namely: aliphatic and aromatic hydrocarbons, alcohols, carbonyl compounds, amines, amides, nitrogen heterocycles, carboxylic and hydroxycarboxylic acids, sulfonic and phosphonic acids, amino acids, and carbohydrates. With the exception of the aliphatic and aromatic hydrocarbons, the interaction takes place mainly between the O and N electron donor atoms of the molecules and the outermost Mg surface cations, and/or by hydrogen bonds of H atoms of the molecules with O surface atoms. Dispersion also contributes to the final interaction energies. Each surface/molecule complex has also been characterized by computing its harmonic vibrational spectrum, in which the most significant frequency perturbations caused by the surface interaction are described. With the calculated interaction energies, a trend of the intrinsic affinity of the probe molecules with the silicate surface has been obtained. However, this affinity scale does not correlate with the experimental abundances of the class of compounds found in the Murchison meteorite. A brief discussion of this lack of correlation and the factors that can help us to understand the abundances is provided.

Molecular chirality in meteorites and interstellar ices, and the chirality experiment on board the ESA cometary Rosetta mission.

Life, as it is known to us, uses exclusively L-amino acid and D-sugar enantiomers for the molecular architecture of proteins and nucleic acids. This Minireview explores current models of the original symmetry-breaking influence that led to the exogenic delivery to Earth of prebiotic molecules with a slight enantiomeric excess. We provide a short overview of enantiomeric enhancements detected in bodies of extraterrestrial origin, such as meteorites, and interstellar ices simulated in the laboratory. Data are interpreted from different points of view, namely, photochirogenesis, parity violation in the weak nuclear interaction, and enantioenrichment through phase transitions. Photochemically induced enantiomeric imbalances are discussed more specifically in the topical context of the "chirality module" on board the cometary Rosetta spacecraft of the ESA. This device will perform the first enantioselective in situ analyses of samples taken from a cometary nucleus.

Variations of organic functional chemistry in carbonaceous matter from the asteroid 162173 Ryugu.

Primordial carbon delivered to the early earth by asteroids and meteorites provided a diverse source of extraterrestrial organics from pre-existing simple organic compounds, complex solar-irradiated macromolecules, and macromolecules from extended hydrothermal processing. Surface regolith collected by the Hayabusa2 spacecraft from the carbon-rich asteroid 162173 Ryugu present a unique opportunity to untangle the sources and processing history of carbonaceous matter. Here we show carbonaceous grains in Ryugu can be classified into three main populations defined by spectral shape: Highly aromatic (HA), Alkyl-Aromatic (AA), and IOM-like (IL). These carbon populations may be related to primordial chemistry, since C and N isotopic compositions vary between the three groups. Diffuse carbon is occasionally dominated by molecular carbonate preferentially associated with coarse-grained phyllosilicate minerals. Compared to related carbonaceous meteorites, the greater diversity of organic functional chemistry in Ryugu indicate the pristine condition of these asteroid samples.

Spectroscopic Detection of Biosignatures in Natural Ice Samples as a Proxy for Icy Moons.

Some of the icy moons of the solar system with a subsurface ocean, such as Europa and Enceladus, are the targets of future space missions that search for potential extraterrestrial life forms. While the ice shells that envelop these moons have been studied by several spacecrafts, the oceans beneath them remain unreachable. To better constrain the habitability conditions of these moons, we must understand the interactions between their frozen crusts, liquid layers, and silicate mantles. To that end, astrobiologists rely on planetary field analogues, for which the polar regions of Earth have proven to be great candidates. This review shows how spectroscopy is a powerful tool in space missions to detect potential biosignatures, in particular on the aforementioned moons, and how the polar regions of the Earth are being used as planetary field analogues for these extra-terrestrial environments.

Mycotoxins' Prevalence in Food Industry By-Products: A Systematic Review.

The recovery of biomolecules from food industry by-products is of major relevance for a circular economy strategy. However, by-products' contamination with mycotoxins represents a drawback for their reliable valorization for food and feed, hampering their application range, especially as food ingredients. Mycotoxin contamination occurs even in dried matrices. There is a need for the implantation of monitoring programs, even for by-products used as animal feed, since very high levels can be reached. This systematic review aims to identify the food by-products that have been studied from 2000 until 2022 (22 years) concerning mycotoxins' contamination, distribution, and prevalence in those by-products. PRISMA ("Preferred Reporting Items for Systematic Reviews and MetaAnalyses") protocol was performed via two databases (PubMed and SCOPUS) to summarize the research findings. After the screening and selection process, the full texts of eligible articles (32 studies) were evaluated, and data from 16 studies were considered. A total of 6 by-products were assessed concerning mycotoxin content; these include distiller dried grain with solubles, brewer's spent grain, brewer's spent yeast, cocoa shell, grape pomace, and sugar beet pulp. Frequent mycotoxins in these by-products are AFB1, OTA, FBs, DON, and ZEA. The high prevalence of contaminated samples, which surpasses the limits established for human consumption, thus limiting their valorization as ingredients in the food industry. Co-contamination is frequent, which can cause synergistic interactions and amplify their toxicity.

From data to insight: Exploring contaminants in different food groups with literature mining and machine learning techniques.

Food remains a major source of human exposure to chemical contaminants that are unintentionally present in commodities globally, despite strict regulation. Scientific literature is a valuable source of quantification data on those contaminants in various foods, but manually summarizing the information is not practicable. In this review, literature mining and machine learning techniques were applied in 72 foods to obtain relevant information on 96 contaminants, including heavy metals, polychlorinated biphenyls, dioxins, furans, polycyclic aromatic hydrocarbons (PAHs), pesticides, mycotoxins, and heterocyclic aromatic amines (HAAs). The 11,723 data points collected from 254 papers from the last two decades were then used to identify the patterns of contaminants distribution. Considering contaminant categories, metals were the most studied globally, followed by PAHs, mycotoxins, pesticides, and HAAs. As for geographical region, the distribution was uneven, with Europe and Asia having the highest number of studies, followed by North and South America, Africa and Oceania. Regarding food groups, all contained metals, while PAHs were found in seven out of 12 groups. Mycotoxins were found in six groups, and pesticides in almost all except meat, eggs, and vegetable oils. HAAs appeared in only three food groups, with fish and seafood reporting the highest levels. The median concentrations of contaminants varied across food groups, with citrinin having the highest median value. The information gathered is highly relevant to explore, establish connections, and identify patterns between diverse datasets, aiming at a comprehensive view of food contamination.

Macromolecular organic matter in samples of the asteroid (162173) Ryugu.

Samples of the carbonaceous asteroid (162173) Ryugu were collected and brought to Earth by the Hayabusa2 spacecraft. We investigated the macromolecular organic matter in Ryugu samples and found that it contains aromatic and aliphatic carbon, ketone, and carboxyl functional groups. The spectroscopic features of the organic matter are consistent with those in chemically primitive carbonaceous chondrite meteorites that experienced parent-body aqueous alteration (reactions with liquid water). The morphology of the organic carbon includes nanoglobules and diffuse carbon associated with phyllosilicate and carbonate minerals. Deuterium and/or nitrogen-15 enrichments indicate that the organic matter formed in a cold molecular cloud or the presolar nebula. The diversity of the organic matter indicates variable levels of aqueous alteration on Ryugu's parent body.

Size exclusion and reversed-phase high-performance liquid chromatography/UV for routine control of thermal processing of cows' and donkey milk major proteins.

Cows' and donkey milks (raw and thermally processed) and respective whey were analysed for quantification of major proteins. Two different chromatographic approaches, size exclusion (SE-HPLC) and reversed-phase high performance liquid chromatography (RP-HPLC) both coupled to UV detection were used. Usefulness of these methods for routine control of the effect of thermal processing was evaluated. The external standard method was used to calibrate the SE-HPLC and RP-HPLC systems. Concerning quantification of ß-lactoglobulin (ß-lg), α-lactalbumin (α-la), lysozyme (lys), and total casein (cn), no significant differences between results obtained by SE-HPLC and by RP-HPLC (t-test, P>0·05) were observed for raw milks and whey. Heating of cows' milk promoted aggregation of denatured proteins as observed by SE-HPLC, whereas α-la and ß-lg from donkey milk were stable to thermal processing at 100 °C (5 min). Lys was quantified in donkey raw milk and whey however, in thermally processed donkey milk lys was denatured and could not be quantified by HPLC.

Color Catalogue of Life in Ice: Surface Biosignatures on Icy Worlds.

With thousands of discovered planets orbiting other stars and new missions that will explore our solar system, the search for life in the universe has entered a new era. However, a reference database to enable our search for life on the surface of icy exoplanets and exomoons by using records from Earth's icy biota is missing. Therefore, we developed a spectra catalogue of life in ice to facilitate the search for extraterrestrial signs of life. We measured the reflection spectra of 80 microorganisms-with a wide range of pigments-isolated from ice and water. We show that carotenoid signatures are wide-ranged and intriguing signs of life. Our measurements allow for the identification of such surface life on icy extraterrestrial environments in preparation for observations with the upcoming ground- and space-based telescopes. Dried samples reveal even higher reflectance, which suggests that signatures of surface biota could be more intense on exoplanets and moons that are drier than Earth or on environments like Titan where potential life-forms may use a different solvent. Our spectra library covers the visible to near-infrared and is available online. It provides a guide for the search for surface life on icy worlds based on biota from Earth's icy environments.

Contamination analysis of Arctic ice samples as planetary field analogs and implications for future life-detection missions to Europa and Enceladus.

Missions to detect extraterrestrial life are being designed to visit Europa and Enceladus in the next decades. The contact between the mission payload and the habitable subsurface of these satellites involves significant risk of forward contamination. The standardization of protocols to decontaminate ice cores from planetary field analogs of icy moons, and monitor the contamination in downstream analysis, has a direct application for developing clean approaches crucial to life detection missions in these satellites. Here we developed a comprehensive protocol that can be used to monitor and minimize the contamination of Arctic ice cores in processing and downstream analysis. We physically removed the exterior layers of ice cores to minimize bioburden from sampling. To monitor contamination, we constructed artificial controls and applied culture-dependent and culture-independent techniques such as 16S rRNA amplicon sequencing. We identified 13 bacterial contaminants, including a radioresistant species. This protocol decreases the contamination risk, provides quantitative and qualitative information about contamination agents, and allows validation of the results obtained. This study highlights the importance of decreasing and evaluating prokaryotic contamination in the processing of polar ice cores, including in their use as analogs of Europa and Enceladus.

Protein Hydrolysates from Brewing By-Products as Natural Alternatives to ACE-Inhibitory Drugs for Hypertension Management.

The treatment of hypertension is of major importance to reduce the risk of cardiovascular disease, the leading cause of death worldwide. Angiotensin-converting enzyme (ACE) inhibitors are anti-hypertensive drugs associated with several side effects. Natural products, namely bioactive peptides from brewing by-products, brewers' spent grain (BSG), and yeast (BSY), are promising alternatives since they can inhibit ACE in vitro. However, the oral intake of these peptides may modify their expected inhibitory effect owing to possible changes in active peptides' bioavailability, which have not been assessed so far. The goal of this study was to simulate oral administration to evaluate BSG/BSY peptides' effectiveness by submitting protein hydrolysates sequentially to simulated gastrointestinal digestion, intestinal absorption (Caco-2 cells), and liver metabolism (HepG2 cells). MTT assay was used to assess BSG/BSY protein hydrolysates safeness. The ACE-inhibitory potential of initial and final protein hydrolysates (BSY, BSG, and a new product, MIX) were tested using a fluorometric assay and compared with captopril (1 µM, an ACE-inhibitory drug). Simulation of oral administration greatly increased BSY and MIX protein hydrolysates' ACE-inhibitory capacity, though final MIX and BSG revealed greater ACE-inhibitory potential than captopril. Notwithstanding, all final protein hydrolysates presented ACE-inhibitory capacity, thus being promising compounds to manage hypertension.

Mycotoxin Interactions along the Gastrointestinal Tract: In Vitro Semi-Dynamic Digestion and Static Colonic Fermentation of a Contaminated Meal.

Aflatoxin B1 (AFB1) and ochratoxin A (OTA) naturally co-occur in several foods, but no studies have followed the fate of mycotoxins' interactions along the gastrointestinal tract using in vitro digestion models. This study used a novel semi-dynamic model that mimics gradual acidification and gastric emptying, coupled with a static colonic fermentation phase, in order to monitor mycotoxins' bioaccessibility by the oral route. AFB1 and OTA bioaccessibility patterns differed in single or co-exposed scenarios. When co-exposed (MIX meal), AFB1 bioaccessibility at the intestinal level increased by ~16%, while OTA bioaccessibility decreased by ~20%. Additionally, a significant increase was observed in both intestinal cell viability and NO production. With regard to mycotoxin-probiotic interactions, the MIX meal showed a null effect on Lactobacillus and Bifidobacterium strain growth, while isolated AFB1 reduced bacterial growth parameters. These results were confirmed at phylum and family levels using a gut microbiota approach. After colonic fermentation, the fecal supernatant did not trigger the NF-kB activation pathway, indicating reduced toxicity of mycotoxins. In conclusion, if single exposed, AFB1 will have a significant impact on intestinal viability and probiotic growth, while OTA will mostly trigger NO production; in a co-exposure situation, both intestinal viability and inflammation will be affected, but the impact on probiotic growth will be neglected.

Nutritional Characterization of Strychnos madagascariensis Fruit Flour Produced by Mozambican Communities and Evaluation of Its Contribution to Nutrient Adequacy.

The indigenous fruit Strychnos madagascariensis is usually processed to flour, called nfuma, being highly consumed during staple food shortage. This study aimed to evaluate the nutritional composition of nfuma and its nutrient adequacy. Flours from four districts of Mozambique were analyzed using AOAC methods for proximate composition, HPLC for sugar, amino acids (AA), vitamin E and carotenoids and ICP-MS and FAAS for minerals. The results showed that nfuma stands out for its high content of fat (26.3-27.8%), mainly oleic acid, fiber (>6%), vitamin E (6.7 to 8.0 mg/100 g) and carotenes (2.2 to 2.6 mg/100 g). The main amino acids of nfuma protein were Arg, Asp and Glu, and Lys was the limiting one. The mineral composition reveals K (~1200 to 1700 mg/100 g) as the main macromineral followed by Mg > Ca > Na. The main trace element was Mn (~4 mg/100 g) followed by Fe > Zn > Cu > Cr > Co. Aluminum (~3 mg/100 g) was the main non-essential element and Rb, Ni, Sr, Ba, V, Cd were also quantified. Assuming the daily consumption of 50 g, nfuma provides 82% of Vitamin A dietary reference value for toddlers, while the consumption of 100 g contributes to 132% and 60% of Mn and vitamin A DRV for adults, respectively. Despite the nutritional advantages of nfuma, this flour can be a source of Ni, highlighting the importance of the study of good practices in its preparation to decrease the exposure to non-essential elements.

Structural shifts in sea ice prokaryotic communities across a salinity gradient in the subarctic.

Current knowledge of the processes that shape prokaryotic community assembly in sea ice across polar ecosystems is scarce. Here, we coupled culture-dependent (bacterial isolation on R2A medium) and culture-independent (high-throughput 16S rRNA gene sequencing) approaches to provide the first comprehensive assessment of prokaryotic communities in the late winter ice and its underlying water along a natural salinity gradient in coastal Hudson Bay, an iconic cryo-environment that marks the ecological transition between Canadian Subarctic and Arctic biomes. We found that prokaryotic community assembly processes in the ice were less selective at low salinity since typical freshwater taxa such as Frankiales, Burkholderiales, and Chitinophagales dominated both the ice and its underlying water. In contrast, there were sharp shifts in community structure between the ice and underlying water samples at sites with higher salinity, with the orders Alteromonadales and Flavobacteriales dominating the ice, while the abovementioned freshwater taxa dominated the underlying water communities. Moreover, primary producers including Cyanobium (Cyanobacteria, Synechococcales) may play a role in shaping the ice communities and were accompanied by known Planctomycetes and Verrucomicrobiae taxa. Culture-dependent analyses showed that the ice contained pigment-producing psychrotolerant or psychrophilic bacteria from the phyla Proteobacteria, Actinobacteriota, and Bacteroidota, likely favored by the combination of low temperatures and the seasonal increase in sunlight. Our findings suggest that salinity, photosynthesis and dissolved organic matter are the main drivers of prokaryotic community structure in the late winter ice of coastal Hudson Bay, the ecosystem with the fastest sea ice loss rate in the Canadian North.

Insoluble organic matter in chondrites: Archetypal melanin-like PAH-based multifunctionality at the origin of life?

An interdisciplinary review of the chemical literature that points to a unifying scenario for the origin of life, referred to as the Primordial Multifunctional organic Entity (PriME) scenario, is provided herein. In the PriME scenario it is suggested that the Insoluble Organic Matter (IOM) in carbonaceous chondrites, as well as interplanetary dust particles from meteorites and comets may have played an important role in the three most critical processes involved in the origin of life, namely 1) metabolism, via a) the provision and accumulation of molecules that are the building blocks of life, b) catalysis (e.g., by templation), and c) protection of developing life molecules against radiation by excited state deactivation; 2) compartmentalization, via adsorption of compounds on the exposed organic surfaces in fractured meteorites, and 3) replication, via deaggregation, desorption and related physical phenomena. This scenario is based on the hitherto overlooked structural and physicochemical similarities between the IOM and the dark, insoluble, multifunctional melanin polymers found in bacteria and fungi and associated with the ability of these microorganisms to survive extreme conditions, including ionizing radiation. The underlying conceptual link between these two materials is strengthened by the fact that primary precursors of bacterial and fungal melanins (collectively referred to herein as allomelanins) are hydroxylated aromatic compounds like homogentisic acid and 1,8-dihydroxynaphthalene, and that similar hydroxylated aromatic compounds, including hydroxynaphthalenes, figure prominently among possible components of the organic materials on dust grains and ices in the interstellar matter, and may be involved in the formation of IOM in meteorites. Inspired by this rationale, a vis-à-vis review of the properties of IOM from various chondrites and non-nitrogenous allomelanin pigments from bacteria and fungi is provided herein. The unrecognized similarities between these materials may pave the way for a novel scenario at the origin of life, in which IOM-related complex organic polymers delivered to the early Earth are proposed to serve as PriME and were preserved and transformed in those primitive forms of life that shared the ability to synthesize melanin polymers playing an important role in the critical processes underlying the establishment of terrestrial eukaryotes.

Headspace volatolome of peel flours from citrus fruits grown in Brazil.

Citrus fruit peel comprises a pleasant mix of volatile compounds together with fibers, nutrients, and bioactive compounds. Therefore, it has great potential for use as a food ingredient. Studies evaluating the volatile composition of citrus peel flours are limited for most citruses. The goal of this study was to characterize, by HS-SPME/GC-MS, the volatile profile of citrus peel flours made from fruits commonly grown in Brazil. Two composite samples of ten types of citrus peel flours from consecutive harvests were evaluated. 69 volatile compounds were assigned, 49 in Tahiti acid lime, 49 in Sicilian lemon, 37 in Persian lime, 34 in Italian tangerine and oval kumquat, 33 in Valencia orange, 32 in Baia orange and round kumquat, 28 in Blood-of-Mombuca orange and 26 in Lima orange. 26 major compounds represented 93-99% of the total chromatogram peak area. Terpenic compounds were predominant in all samples, especially monoterpenes (about 48-97% of the total chromatogram peak area), while lower proportions of aldehydes (0.2-16.1%), monoterpene alcohols (0.4-11.8%) and esters (0.0-7.7%) were observed. Even though a few compounds like limonene, ß-myrcene, linalool, α-pinene and valencene were detected in all citrus, volatile compounds followed specific patterns in the different citruses, with a clear distinction among them, especially between lemon flours and the remaining flours. The variety of volatile profiles and singular specific volatolomic signatures in citrus peels can be explored for different applications related to food flavoring and preservation, and promotion of good health. These aspects should be thoroughly investigated in future studies.

Nutritional quality of protein concentrates from Moringa Oleifera leaves and in vitro digestibility.

The nutritional value and digestibility of leaf proteins is still a major issue. Therefore, the goal of this work was to optimize the production of a protein concentrate (PC) from Moringa Oleifera defatted leaves (MODL) by enzymatic extraction using Viscozyme L and evaluate its nutritional quality and digestibility. Protein extraction conditions were screened using a factorial design. Enzyme/Substrate ratio and pH had no significant effect, whereas, the significant variables, temperature (°C), enzyme concentration and incubation time (h) were optimized by central composite design (CCD). PC contained 55.7% of proteins with a balanced amino acid profile when compared with MODL and higher content of essential amino acids (EAAs) (488.6-402.9 mg/g of protein respectively). Improvement on protein digestibility was observed for MODL compared to PC (64.75-99.86% respectively) and higher protein digestibility corrected amino acid score (PDCAAS) (62.10-91.41% respectively). PC meets FAO protein quality expectations.

Sensory and Olfactometry Chemometrics as Valuable Tools for Assessing Hops' Aroma Impact on Dry-Hopped Beers: A Study with Wild Portuguese Genotypes.

Sensory, olfactometry (using the sums of odour intensities for each class of compounds) and chemometric analyses were used to evaluate Portuguese wild hops' sensory characteristics and the aroma that those hops impart to dry-hopped beer. CATA analysis and agglomerative hierarchical clustering was applied for the sensory characterization of 15 wild hops of Portuguese genotypes, clustering them in two groups: one more sulphurous, floral, and fruity, and another more earthy, resinous, floral, and non-citrus fruits. Two hops representative of each group were selected for the production of four dry-hopped beers using the same base beer style (Munich Helles). Beers were analysed by quantitative descriptive analyses and quantification of hop-derived key volatile compounds. Multivariate statistical treatment of the data was performed. Results indicate significant differences (p < 0.05) in fruity, resinous, earthy, floral, and sulphurous attributes of hops, but the dry-hopped beers only have a significant increase (p < 0.05) in fruity and spicy notes when compared with non-dry-hopped Munich-style Helles beer. Hop olfactometry explained the sensory perception that the 11 hops not used for brewing (employed as supplementary observations) are placed into the space of the odour-active compounds profile of the four hops selected for brewing. These 11 hop samples have more spiciness than fruitiness potential.