Specific Compound Classes Research Articles

Temperature and moisture alter organic matter composition across soil fractions

Understanding the complex interplay of biotic and abiotic controls on soil organic carbon (SOC) stabilization and aggregate formation is a vital and evolving research field, with implications for C and climate change modeling. Here, we delve into the effects of temperature and moisture treatments on aggregate SOC composition. Aggregate fractions representing different levels of physical protection for SOC were isolated three times during a 6-month incubation with 2x2 factorial temperature and moisture treatments (22 or 30 °C, 45% or 65% water-filled pore space). The chemical composition within each fraction was analyzed using high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) to evaluate the prevalence of different classes of C compounds by fraction and temperature and moisture treatments. In addition, a partial least square regression (PLSR) was used to explore potential correlations between relative abundance of C compound classes and C content within aggregate fractions. We found that organic matter in the macro- (>250 µm) and micro-aggregates (53 to 250 µm) was relatively enriched in lipid-, carbohydrates-, and protein--like compounds compared to silt and clay fractions (<53 µm). Organic matter in silt and clay was, on the other hand, relatively enriched in compounds with no specific classification, with overall high aromaticity. Broadly, simpler, low-molecular-weight C storage was altered by both temperature and moisture, while complex C storage was especially altered by moisture, within aggregates. Univariate effects of temperature and moisture on specific compound classes varied by soil fraction, but across fractions temperature increased the relative abundance of condensed- and unsaturated hydrocarbon-, tannin-, and amino sugar-like compounds and decreased the relative abundance of protein-like compounds. Moisture increased tannin-, condensed hydrocarbon-like compounds, and the overall aromaticity, and had the most pronounced effect in fractions occluded within macroaggregates, suggesting that substrate diffusion and pore connectivity within the aggregate environment drive the composition of C protected within aggregates. The PLSR indicated that treatments promoted different compounds to contribute to C accrual. Under dry conditions, condensed hydrocarbon-like compounds were associated with microaggregates, while amino sugar-like compounds were associated with macroaggregates and coarse particulate organic matter (POM), and lipid-like and aliphatic compounds were associated with silt and clay. Temperature effects on PLSR results were most visible in silt and clay fractions, where carbohydrate- and tannin-like compounds were associated with C content. This suggests that warmer conditions under climate change may more substantially alter mineral-associated C content, while changing water regimes will alter C content in physically protected environments, with the most significant changes under cool and moist conditions. Overall, our data reveal distinct resource pools in different climate and aggregate environments, a baseline for our understanding of SOC accrual and soil structure under different conditions. More research into how microbes process physically protected SOC under altered environments may fine-tune our ability to predict soil functions including water behavior and nutrient release.

Extraction Kinetics of Total Polyphenols, Flavonoids, and Condensed Tannins of Lentil Seed Coat: Comparison of Solvent and Extraction Methods.

The lentil seed coat is a waste by-product still rich in phenolic compounds, specifically condensed tannins. The effect of different solvents, as well as different processes, namely conventional solid–liquid extraction (CSLE) and ultrasound-assisted extraction (UAE), on the extraction yield of specific phenolic compound classes was studied. Four empirical two-parameter models were examined to select the one that better fit the experimental data obtained under different operating conditions. Additionally, ultra-high-pressure liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UHPLC-ESI/QTOF-MS) was employed to profile the phenolic compounds obtained under distinct extraction conditions. In the operative conditions adopted here, the bioactive compounds yield achieved using UAE was lower than that obtained with CSLE. The kinetics of polyphenols, flavonoids, and condensed tannins extraction from the lentil seed coat were successfully fitted to the power-law models, yielding mean values of the root mean square < 5.4%, standard error of estimation < 0.53, and coefficient of determination > 0.8. In addition, the UHPLC-ESI/QTOF-MS of the lentil seed coat extracts allowed the putative recognition of nearly 500 compounds, mainly flavonoids and phenolic acids.

An approach to fast 2D nuclear magnetic resonance at low concentration based on p-H2 -induced polarization and nonuniform sampling.

Recent developments in para-hydrogen-induced polarization (PHIP) methods allow the nuclear magnetic resonance (NMR) detection of specific classes of compounds, down to sub-micromolar concentration in solution. However, when dealing with complex mixtures, signal resolution requires the acquisition of 2D PHIP-NMR spectra, which often results in long experimental times. This strongly limits the applicability of these 2D PHIP-NMR techniques in areas in which high-throughput analysis is required. Here, we present a combination of fast acquisition and nonuniform sampling that can afford a 10-fold reduction in measuring time without compromising the spectral quality. This approach was tested on a mixture of substrates at micromolar concentration, for which a resolved 2D PHIP spectrum was acquired in less than 3min.

Specific and conserved patterns of microbiota-structuring by maize benzoxazinoids in the field

BackgroundPlants influence their root and rhizosphere microbial communities through the secretion of root exudates. However, how specific classes of root exudate compounds impact the assembly of root-associated microbiotas is not well understood, especially not under realistic field conditions. Maize roots secrete benzoxazinoids (BXs), a class of indole-derived defense compounds, and thereby impact the assembly of their microbiota. Here, we investigated the broader impacts of BX exudation on root and rhizosphere microbiotas of adult maize plants grown under natural conditions at different field locations in Europe and the USA. We examined the microbiotas of BX-producing and multiple BX-defective lines in two genetic backgrounds across three soils with different properties.ResultsOur analysis showed that BX secretion affected the community composition of the rhizosphere and root microbiota, with the most pronounced effects observed for root fungi. The impact of BX exudation was at least as strong as the genetic background, suggesting that BX exudation is a key trait by which maize structures its associated microbiota. BX-producing plants were not consistently enriching microbial lineages across the three field experiments. However, BX exudation consistently depleted Flavobacteriaceae and Comamonadaceae and enriched various potential plant pathogenic fungi in the roots across the different environments.ConclusionsThese findings reveal that BXs have a selective impact on root and rhizosphere microbiota composition across different conditions. Taken together, this study identifies the BX pathway as an interesting breeding target to manipulate plant-microbiome interactions.4atbM_n1-Xmh1rBaQ1rPHqVideo

The effect of community‐wide phytochemical diversity on herbivory reverses from low to high elevation

Abstract Theory predicts that a large fraction of phytochemical diversity—the richness of individual chemical compounds produced by plants—governs the complexity of interactions between plants and their herbivores. While the effect of specific classes of chemical compounds on plant resistance against herbivores has been largely documented, the effect of community‐level variation in phytochemical diversity on plant–herbivore interactions has so far received minimal consideration. We hypothesized that plant communities bearing on average higher levels of phytochemical diversity should sustain lower herbivory rates, overall. Yet, the magnitude of this effect could vary across different environmental conditions, potentially because of climate‐mediated effects on phytochemical production and changes in herbivore community richness and composition. To address these hypotheses, we used previous knowledge of species‐level phytochemical make‐up for more than 400 plant species of the Swiss Alps. Using common garden experiments, we estimated season‐wide herbivore damage on low (average 3,500 unique molecules) and high (average 4,500 unique molecules) phytochemical diversity plant communities that were planted in the colline, mountain and alpine vegetation sites along two elevation transects in the Alps. We found that high phytochemical diversity plant communities showed reduced levels of herbivore damage in the colline (low elevation) sites, but this pattern reversed in the alpine (high elevation) sites. Our results suggest that the outcome of phytochemical diversity on plant–herbivore interactions depends on the characteristics of the local herbivore communities, together with trade‐offs between chemical defences and other plant traits (i.e. physical defences and plant palatability). Synthesis. Phytochemical diversity is a key component of functional diversity, influencing community composition and dynamics. We show that the effect of phytochemical diversity on herbivory is environmental‐dependent, generating ecological switches when moving from low to high elevation. Through upward movement of plants under climate change, phytochemical community structure will be likely modified, ultimately disrupting local community assembly processes.

Improved nutritional quality in fruit tree species through traditional and biotechnological approaches

The increasing evidences on the relation between diet and human health are driving the consumers toward the choice of foods with high amount of nutrients, considered the molecules responsible for the regulation of several metabolic and biochemical processes, and for the prevention of many chronic diseases. Among food products, fruits represent a natural source of many different nutrients and possess much importance in a balanced diet. The increase of the micro/macronutrient levels and the decrease of antinutrients amount are considered main objectives for the improvement of fruit trees nutritional value. This review summarizes many of the attempts made to increase the nutritional quality of fruit tree species during the last decades through the application of traditional and molecular breeding technologies, and the most recent New breeding techniques (NBTs). New genotypes with improved nutritional quality have been obtained for different fruit tree species, either by increasing the content of well-known beneficial molecules, such as phenolic compounds, vitamins, and carotenoids, or by decreasing the levels of specific antinutrients. The development of molecular techniques and biotechnological tools allowed the identification and validation of candidate genes involved in the regulation of specific classes of nutritional compounds in fruit trees, and useful to obtain nutritionally improved products. NBTs represent alternative tools to classical breeding techniques, to regulate one or more fruit trees key nutrients in a more quick and precise manner. However, genetic engineering approaches still present public and regulatory concerns that strongly limit their exploitation. • Fruit consumption provides essential macro and micronutrients for human health • Conventional breeding is widely used, but presents several limitations • Molecular techniques can be applied to assist and optimize conventional breeding • New biotechnological tools allow the engineered introduction of quality traits • Genetic engineering approaches still present public and regulatory concerns

Comparison of Thermal and Flow-Based Modulation in Comprehensive Two-Dimensional Gas Chromatography—Time-of-Flight Mass Spectrometry (GC × GC-TOFMS) for the Analysis of Base Oils

Base oils are produced by refining crude oil or through chemical synthesis. They are a key component of engine oils. With an immense range of carbon numbers and boiling points, analyzing such complex mixtures is very difficult. The need to monitor industrial petroleum processing steps, as well as to identify petrochemical environmental pollutants, drives the search for improved characterization methods. Comprehensive two-dimensional gas chromatography (GC × GC) is one of the best tools for that. The modulator used in GC × GC is responsible for trapping/sampling the first dimension (1D) column analytes, then reinjecting them in the form of narrow bands onto the second dimension (2D) column for further separation. Modulators used today generally fall into two categories, thermal and flow ones. Heater-based thermal modulators trap the 1D column effluent at or above ambient temperatures. Flow-based modulators utilize storage loop(s) to collect the 1D effluent, which is subsequently flushed into the second-dimension column for further separation. A single-stage, consumable-free thermal modulator and a reverse fill/flush flow modulator were compared for the characterization of base oils. Both were evaluated on their ability to achieve separation of several conventional and synthetic engine oils components. A reverse column set, polar 1D and nonpolar 2D, allowed group-type analysis of all classes, including linear, branched, and aromatic species. The results show the ability to achieve a comprehensive separation of specific compound classes and the differentiation of engine oil types and manufacturers. Soft ionization assisted in tentative identification of two alkylated diphenylamines in each sample. The advantages and limitations of both thermal and flow modulation are presented.

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

AbstractEvaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.

Concentration of meteoritic free organic matter by fluid transport and adsorption

Carbonaceous chondrites contain many abiotic organic compounds, some of which are found in life on Earth. Both the mineral and organic matter phases, of these meteorites, have been affected by aqueous alteration processes. Whilst organic matter is known to be associated with phyllosilicate phases, no such relationship has yet been identified for specific organic compound classes. Furthermore, ongoing sample return missions, Hyabusa 2 and OSIRIS-Rex, are set to return potentially organic rich C-type asteroid samples to the Earth. Consequently, strategies to investigate organic-mineral relationships are required. Here we report spatial data for free/soluble organic matter (FOM/SOM) components (akylimidazole and alkylpyridine homologues) and mineral phases. Low and intermediate molecular weight alkylimidazole homologues are more widely distributed than higher molecular weight members, likely due to their affinity for the aqueous phase. On aqueous alteration of anhydrous mineral phases, transported FOM is adsorbed onto the surface or into the interlayers of the resulting phyllosilicates and thus concentrated and protected from oxidising fluids. Therefore, aiding the delivery of biologically relevant molecules to earth, shortly preceding the origin of life.

Digging deeper - A new data mining workflow for improved processing and interpretation of high resolution GC-Q-TOF MS data in archaeological research

Gas chromatography-mass spectrometry profiling is the most established method for the analysis of organic residues, particularly lipids, from archaeological contexts. This technique allows the decryption of hidden chemical information associated with archaeological artefacts, such as ceramic pottery fragments. The molecular and isotopic compositions of such residues can be used to reconstruct past resource use, and hence address major questions relating to patterns of subsistence, diet and ritual practices in the past. A targeted data analysis approach, based on previous findings reported in the literature is common but greatly depends on the investigator’s prior knowledge of specific compound classes and their mass spectrometric behaviour, and poses the risk of missing unknown, potentially diagnostic compounds. Organic residues from post-prehistoric archaeological samples often lead to highly complex chromatograms, which makes manual chromatogram inspection very tedious and time consuming, especially for large datasets. This poses a significant limitation regarding the scale and interpretative scopes of such projects. Therefore, we have developed a non-targeted data mining workflow to extract a higher number of known and unknown compounds from the raw data to reduce investigator’s bias and to vastly accelerate overall analysis time. The workflow covers all steps from raw data handling, feature selection, and compound identification up to statistical interpretation.

Improving glycan isomeric separation via metal ion incorporation for drift tube ion mobility-mass spectrometry

Glycosylated proteins are an essential class of molecules playing critical roles in complex biological systems. Understanding their biological functions remains extremely difficult due to the extremely broad compositions and structure variations of glycans. Although the combination of ion mobility spectrometry and mass spectrometry (IMS-MS) has become a promising technique in glycan structure characterization and composition identification, the insufficient resolving power of most IMS-MS instruments has limited its utility in performing the comprehensive structure characterization of glycans. To mitigate the low IMS resolving power, metal ion incorporation has been employed to enhance the separation of isomeric glycans. Here, we present a systematic investigation of many different glycan-metal ion complexes in an attempt to optimize the IMS separation of different isomeric glycans. By selecting optimum glycan-metal ion complexes, partial IMS separation was realized for all the 21 isomeric glycan pairs used in the experimental study. Baseline IMS separation was achieved for 76% of these isomeric glycan pairs. The best IMS separation of isomeric glycans was achieved in some cases by incorporating multiple ions with a glycan, such as the complex [glycan + Ca + Cl]+. In addition, the well-known IMS-MS measurement trendlines, often used to identify specific compound classes, were preserved for glycans even for all the 270 glycan-metal ion complexes observed in IMS-MS spectra.

Temporal Dynamics of the Soil Metabolome and Microbiome During Simulated Anaerobic Soil Disinfestation.

Significant interest exists in engineering the soil microbiome to attain suppression of soil-borne plant diseases. Anaerobic soil disinfestation (ASD) has potential as a biologically regulated disease control method; however, the role of specific metabolites and microbial community dynamics contributing to ASD mediated disease control is mostly uncharacterized. Understanding the trajectory of co-evolutionary processes leading to syntrophic generation of functional metabolites during ASD is a necessary prelude to the predictive utilization of this disease management approach. Consequently, metabolic and microbial community profiling were used to generate highly dimensional datasets and network analysis to identify sequential transformations through aerobic, facultatively anaerobic, and anaerobic soil phases of the ASD process and distinct groups of metabolites and microorganisms linked with those stages. Transient alterations in abundance of specific microbial groups, not consistently accounted for in previous studies of the ASD process, were documented in this time-course study. Such events initially were associated with increases and subsequent diminution in highly labile metabolites conferred by the carbon input. Proliferation and dynamic compositional changes in the Firmicutes community continued throughout the anaerobic phase and was linked to temporal changes in metabolite abundance including accumulation of small chain organic acids, methyl sulfide compounds, hydrocarbons, and p-cresol with antimicrobial properties. Novel potential modes of disease control during ASD were identified and the importance of the amendment and “community metabolism” for temporally supplying specific classes of labile compounds were revealed.

Molecular characterization of organic matter in two calcareous soils: the effects of an acid decarbonation treatment.

The molecular composition of soil organic matter (SOM) of two calcareous soils highly rich in carbonates was assessed before and after decarbonation by acid washing with HCl through 13C-CPMAS-NMR spectroscopy and off-line thermochemolysis coupled with gas chromatography and mass spectrometry (THM-GC-MS). The acidic treatment promoted a considerable concentration of organic matter in both soils, thus improving the identification of molecules otherwise not easily detectable. Decarbonation induced only a slight loss of soil organic carbon (SOC), corresponding to 1.4 and 2.7% for A and B soils respectively. The acidic treatment also led to an increase in the organic carbon/total nitrogen (OC/N) ratio in soil A, while an opposite variation was found for the second soil. Moreover, variations in the concentration and molecular distribution of specific compound classes present in SOM were caused by the acid washing of soils. As confirmed by both 13C-CPMAS-NMR and thermochemolysis results, the molecules most susceptible to the acid treatment were the carbohydrates, lignin monomers (G14 and G15), fatty acids (C18 saturated and unsaturated), fatty acids of microbial origin (C15, C17, and C19), hydroxy acids (C16, C18), and dioic acids (C18) which represent the components weakly bound to the organic matrix. Our findings not only showed the efficacy of the decarbonation treatment of calcareous soils with 3N HCl, but also indicated how the acidic washing can improve the differentiation of soils on the basis of SOM molecular characteristics. Graphical abstract.

The non-destructive separation of diverse astrobiologically relevant organic molecules by customizable capillary zone electrophoresis and monolithic capillary electrochromatography

AbstractThein situdetection of organic molecules in space is key to understanding the variety and the distribution of the building blocks of life, and possibly the detection of extraterrestrial life itself. Gas chromatography mass spectrometry (GC-MS) has been the most sensitive analytical strategy for organic analyses in flight, and was used on missions from NASA's Viking, Phoenix, Curiosity missions to ESA's Rosetta space probe. While pyrolysis GC-MS revealed the first organics on Mars, this step alters or degrades certain fragile molecules that are excellent biosignatures including polypeptides, oligonucleotides and polysaccharides, rendering the intact precursors undetectable. We have identified a solution tailored to the detection of biopolymers and other biomarkers by the use of liquid-based capillary electrophoresis and electrochromatography. In this study, we show that a capillary electrochromatography approach using monolithic stationary phases with tailor-made surface chemistry can separate and identify various polycyclic aromatic hydrocarbons, nucleobases and aromatic acids that could be formed under astrophysically relevant conditions. In order to simulate flyby organic sample capture, we conducted hypervelocity impact experiments which consisted of accelerating peptide-soaked montmorillonite particles to a speed of 5.6 km s−1, and capturing them in an amorphous silica aerogel of 10 mg cm−3bulk density. Bulk peptide extraction from aerogel followed by capillary zone electrophoresis led to the detection of only two stereoisomeric peptide peaks. The recovery rates of each step of the extraction procedure after the hypervelocity impact suggest that major peptide loss occurred during the impact. Our study provides initial exploration of feasibility of this approach for capturing intact peptides, and subsequently detecting candidate biomolecules during flight missions that would be missed by GC-MS alone. As the monolith-based electrochromatography technology could be customized to detect specific classes of compounds as well as miniaturized, these results demonstrate the potential of the instrumentation for future astrobiology-related spaceflight missions.

Effect of passive oxygen exposure during pressing and handling on the chemical and sensory attributes of Chardonnay wine

Background and Aims The significance of oxygen in winemaking has been well established, but knowledge gaps exist regarding the extent and impact passive oxygenation has on chemical and sensory properties during the initial stages. Methods and Results Using in-press oxygen monitors, controlling oxygen exposure during the earliest stages of grape processing was shown to be highly effective. This work demonstrated that pressing management has far more impact on wine composition than handling management; the earliest and highest exposure to oxygen has the most profound impact on the composition of the resulting wine compared to the lower levels of repeated exposure typical of normal handling procedures. Furthermore, control of oxygen exposure during post-pressing operations offers the possibility of modulating specific classes of compounds, described in sensory analysis as floral and confection. Conclusions Significant modulation of aromatic, phenolic and protein profiles of wine occurred through controlling oxygen exposure during the earliest stages of grape processing. Significance of the Study This work shows the possible stylistic potential and limitations of oxygen control, albeit with investment in press technology. The understanding of the relative influence of processing variables assessed in this work can be immediately applied by winemakers.

Composition of heterotrophic specialized sub-guilds defined by a positive RNA and polyhydroxyalkanoate correlation in activated sludge

Microbial heterotrophic guilds in activated sludge wastewater treatment systems have complex population structures and functions. A previously proposed heterotrophic-specialist model states that heterotrophs consist of sub-guilds specialized in consuming specific classes of compounds, either readily degradable substrate (RDS) or slowly degradable substrate (SDS) according to current mathematical modeling practices for wastewater treatment processes. It follows from metabolic considerations that the levels of RNA and polyhydroxyalkanoate (PHA) are correlated for strains of the same species growing in different environments; a conjecture previously tested. The proposed classification of heterotrophs into RDS or SDS consumers predicts that the same correlation would also be found across heterotrophic species in conventional activated sludge systems; this prediction was tested in the current study. The positive correlation between the RNA and PHA levels was observed in 9 conventional activated sludge plants in two independent sampling times and it was also found stable over a 6-month regular sampling period at one of these plants. Together, these results imply that the levels of RNA and PHA can be used to define heterotrophic-specialist sub-guilds. In order to gain insight in the species composition of the defined sub-guilds, flow cytometry cell sorting was used to further analyze one of the activated sludge samples. Four sorted sub-samples were obtained (high-RNA/high-PHA, low-RNA/high-PHA, high-RNA/low-PHA, and low-RNA/low-PHA), and the phylogenetic composition of each was determined using 16S rRNA gene amplicon pyrosequencing. Heterotrophic genera were identified across 12 phyla, and their representation in each sorted sub-sample showed that the high-RNA/high-PHA and low-RNA/low-PHA groups were most dissimilar. The enriched genera in these sorted sub-samples are suggested to represent the composition of heterotrophic-specialized sub-guilds defined by the kinetics of substrate consumption.

Sequential Hybrid Three-Dimensional Gas Chromatography with Accurate Mass Spectrometry: A Novel Tool for High-Resolution Characterization of Multicomponent Samples

A novel sequential three-dimensional gas chromatography-high-resolution time-of-flight mass spectrometry (3D GC-accTOFMS) approach for profiling secondary metabolites in complex plant extracts is described. This integrated system incorporates a nonpolar first-dimension (1Dnp) separation step, prior to a microfluidic heart-cut (H/C) of a targeted region(s) to a cryogenic trapping device, directly followed by the rapid reinjection of a trapped solute into a polar second-dimension (2DPEG) column for multidimensional separation (GCnp-GCPEG). For additional separation, the effluent from 2DPEG can then be modulated according to a comprehensive 2D GC process (GC×GC), using an ionic liquid phase as a third-dimension (3DIL) column, to produce a sequential GCnp-GCPEG×GCIL separation. Thus, the unresolved or poorly resolved components, or regions that require further separation, can be precisely selected and rapidly transferred for additional separation on 2D or 3D columns, based on the greater separation realized by these steps. The described integrated system can be used in a number of modes, but one useful approach is to target specific classes of compounds for improved resolution. This is demonstrated through the separation and detection of the oxygenated sesquiterpenes in hop ( Humulus lupulus L.) essential oil and agarwood ( Aquilaria malaccensis) oleoresin. Improved resolution and peak capacity were illustrated through the progressive comparison of the tentatively identified components for GCnp-GCPEG and GCnp-GCPEG×GCIL methods. Relative standard deviations of intraday retentions (1 tR, 2 tR,, and 3 tR) and peak areas of ≤0.01, 0.07, 0.71, and 7.5% were achieved. This analytical approach comprising three GC column selectivities, hyphenated with high-resolution TOFMS detection, should be a valuable adjunct for the improved characterization of complex plant samples, particularly in the area of plant metabolomics.

The Composition and Stability of Clay-Associated Organic Matter along a Soil Profile

Organic carbon in subsoil generally has longer turnover times than that in surface soil, but little is known about how the stability of the specific organic compound classes changes with soil depth. The objective of this study was to analyze the composition and thermal stability of clay-associated organic matter (OM) at varying soil depths in the summit and footslope of a pasture hillslope using C X-ray absorption near edge structure (XANES) and pyrolysis-field ionization mass spectrometry (Py-FIMS). C XANES showed aromatic C was relatively enriched in the subsoil, relative to the surface soil. Py-FIMS demonstrated a relative enrichment of phenols/lignin monomers and alkylaromatics with increasing profile depth in the summit soil, and to a greater extent in the footslope soil, followed by a decreasing abundance of sterols. In surface soil, the thermostability of clay-associated OM increases in the order: carbohydrates and N compounds &lt; phenols/lignin monomers &lt; lignin dimers and alkylaromatics, suggesting the intrinsic chemical nature of OM as a major driver for OM persistent in surface soil. The thermal stability of clay-associated carbohydrates, N compounds, and phenols/lignin monomers increased with profile depth, likely due to stronger organic-organic/organic-mineral binding. In subsoil, the thermal stability of clay-associated carbohydrates and N compounds can be as high as that of alkylaromatic and lignin dimers, implying that persistent subsoil OM could be composed of organic compound classes, like carbohydrates, that were traditionally considered as biochemically labile compounds. In contrast, the thermally-stable compound classes, like lignin dimers and alkylaromatics, showed no changes in the thermal stability with soil depth. This study suggests that stability of the more labile OM compounds may be more strongly influenced by the change in environmental conditions, relative to the more stable forms.

Trace analysis in water-alcohol mixtures by continuous p-H2 hyperpolarization at high magnetic field.

Nuclear magnetic resonance (NMR) studies of complex mixtures are often limited by the low sensitivity of the technique and by spectral overlap. We have recently reported on an NMR chemosensor on the basis of para-Hydrogen Induced Polarization that potentially addresses both these issues, albeit for specific classes of compounds. This approach makes use of Signal Amplification By Reversible Exchange (SABRE) catalysts in methanol and allows selective detection and quantification of dilute analytes in complex mixtures. Herein, we demonstrate that, despite a large decrease in attained hyperpolarization, this method can be extended to water-alcohol mixtures. Our approach was tested on whisky, where nitrogenous heterocyclic flavor components at low-micromolar concentration could be detected and quantified.

Solvent selection for efficient extraction of bioactive compounds from grape pomace

Pomace is a winemaking by-product, rich in bioactive compounds which exert various health benefits and are used as dietary supplements, cosmetic ingredients, food colorants and preservatives. Isolation and further utilization of these compounds is an important issue in pomace waste management. Different industries have different requirements for specific classes of compounds and thus, selective extraction methods for isolation of these classes should be developed. In this work, the efficacy of six solvents (80% MeOH, 80% EtOH, EtOAc, acetone, acidified 50% and 80% MeOH) for the extraction of polyphenolic and triterpenoid compounds was examined. Pomaces of different grape varieties from Fruška Gora winery region in Serbia were used for extraction. 47 phenolics and 3 triterpenoids were analyzed by LC–MS/MS and 5 anthocyanin glucosides by LC-UV/VIS, while contents of total phenols and flavonoids were determined spectrophotometrically in obtained extracts. The most efficient solvent for each class and each compound was defined: EtOAc was the best for obtaining an extract rich in polyphenols, acidified 50% MeOH for isolation of anthocyanins, and acetone for ursolic acid. For industries that work on a large scale and aim at the highest utilization of raw material, 80% MeOH was found to be a solvent of choice, providing the highest yield of all polyphenols. This study confirmed that pomaces from Fruška Gora vineyards are a promising source of bioactive compounds, suggesting that their utilization could be very attractive for pharmaceutical, food and cosmetic industries.