Low Molecular Weight Organic Compounds Research Articles

RESEARCH OF THE COMPOSITION OF PRODUCTS OF MICROWAVE PYROLYSIS OF WOOD

A method of microwave action on wood of various species was developed, as a result of which the pyrolysis process was carried out. Allocated solid, gaseous fractions, as well as as a result of condensation of a vapor-gas mixture, pyrolysate, which is a raw material for the production of low molecular weight organic compounds of various classes. Gas chromatography-mass spectroscopic analysis of the liquid fraction was carried out, the components included in its composition were identified. The proposed method allows liquefaction of wood for 20-30 minutes in the temperature range from 230 to 423 °С.

Cellular immunity indexes after therapeutic use of immunoactive and anti-inflammatory agents in patients with orthodontically induced gingival hyperplasia

Orthodontic treatment with fixed appliances that is mediated by the power forces of the apparatus might lead to changes in the blood circulation, predispose to a number of complications such as tooth movement and contributes to the morphological bone tissue remodeling. We have investigated 126 patients aged 16–35 years after appliance bracket therapy that has caused orthodontically induced gingival hyperplasia. Immunological investigation which comprised the study of the cellular immune system in patients with orthodontically induced gingival hyperplasia suggested that there were significant disorders of the cellular immune system that correspond to the T-suppressor type of the secondary immunodeficiency state. Endogenous interferon composed of a low molecular weight organic compounds and an interferon-inducing agent (isonicotinic acid derivative) was used in the treatment of the patients with orthodontically induced gingival hyperplasia. Interferon provides restoration of functional activity in T-lymphocytes, enhances the functional capacity of the macrophages, provides normalization of the cell immunity, contributes to the elimination of secondary immunodeficiency and restoration of immunological homeostasis in individuals with orthodontically induced gingival hyperplasia caused by fixed appliances.

Ефекти вітамінів А, Е, D, порушення їх обміну та оцінка рівня вітамінної забезпеченості в дітей (огляд літератури)

Vitamins are a group of biologically highly active, low molecular weight organic compounds of various chemical nature, which are practically not synthesized in the human body or are synthesized in insufficient quantities, mainly income with food, and are vital to ensure for the flow and regulation of metabolic processes in the body. Vitamins are micronutrients that are among the essential (essential) factors of nutrition, their content in food is small, usually in the range from 10 to 100 mg/100 g. Vitamins have an exceptional property — the ability to high biological activity in small doses, without being a source of energy or plastic material, act as biological catalysts for vital body functions. According to physicochemical properties and solubility, vitamins A, E, D belong to fat-soluble, are characterized by thermal stability, resistant to cysts and alkalis, their main characteristic is the ability to promote the assimilation of mаcro- and microelements. Vitamins A, E, D are needed at all stages of growth and development of the child's body, the processes of adaptation. The main types of vitamins metabolism disorders are vitamin deficiency, hypo-, hyper- and dysvitaminosis, polyvitaminosis. It is important to constantly monitor the sufficient content of each vitamins in the daily diet of children. The following methods of assessing vitamin supply are known: clinical, biochemical, calculation of vitamin content. Purpose — to increase knowledgment about the effects of vitamins A, E, D, their importance in metabolism, to analyze the main types of their metabolism disorders, to present possible methods for assessing the supply of vitamins in children. Conclusions. The child's body needs a constant supply of vitamins to maintain their amount at the required level. All vital processes take place in the body during the direct participation of vitamins. Future research in the field of the vitamins A, E, D effects will contribute to a better understanding of their role in ensuring the optimal functioning in a human body. Screening and elimination of vitamin A, E, D deficiency in children can not only improve health, but also help increase the life quality. No conflict of interest was declared by the authors. Key words: vitamins A, E, D, vitamin deficiency, hypovitaminosis, hypervitaminosis, dysvitaminosis, polyvitaminosis, children.

Persistent Free Radicals from Low-Molecular-Weight Organic Compounds Enhance Cross-Coupling Reactions and Toxicity of Anthracene on Amorphous Silica Surfaces under Light.

Polycyclic aromatic hydrocarbon (PAH) contamination has raised great environmental concerns, while the effects of low-molecular-weight organic compounds (LMWOCs) on PAH photodegradation at amorphous silica (AS)/air interfaces have been largely ignored. In this study, the phototransformation of anthracene (ANT) at amorphous silica (AS)/air interfaces was investigated with the addition of LMWOCs. ANT removal was attributed to •OH attacking and the energy transfer process via 3ANT*. Light irradiation induced the fractured ≡SiO• or ≡Si• generation on AS surfaces, which could react with absorbed H2O and O2 to generate •OH and further yield a series of hydroxylated products of ANT. The presence of citric acid and oxalic acid improved •OH generation and enhanced ANT removal by 1.0- and 2.2-fold, respectively. For comparison, the presence of catechol and hydroquinone significantly decreased ANT removal and produced coupling products. The results of density functional theory calculations suggest that persistent free radicals (PFRs) on AS surfaces from catechol or hydroquinone after •OH attacking prefer to cross-couple with ANT via C-C bonding rather than self-couple. Dianthrone and cross-coupling products might possess higher ecotoxicity, while hydroxylated products were less ecotoxic than their parent compounds based on Ecological Structure Activity Relationships (ECOSAR) estimation. The results of this study revealed the potential ecotoxicity of PAH-adsorbed particulates coexisting with LMWOCs and also provided a new insight into PAH transformation through PFR pathways.

1,2,4-Trimethoxybenzene selectively inhibits NLRP3 inflammasome activation and attenuates experimental autoimmune encephalomyelitis.

NOD-like receptor (NLR) family pyrin domain-containing-3 (NLRP3) inflammasome is implicated in inflammation-associated diseases such as multiple sclerosis, Parkinson's disease, and stroke. Targeting the NLRP3 inflammasome is beneficial to these diseases, but few NLRP3 inflammasome-selective inhibitors are identified to date. Essential oils (EOs) are liquid mixtures of volatile and low molecular-weight organic compounds extracted from aromatic plants, which show various pharmacological activities, including antibacterial, antifungal, antiviral, antioxidant, and anti-inflammatory properties. In this study we screened active ingredients from essential oils, and identified 1,2,4-trimethoxybenzene (1,2,4-TTB) as a selective NLRP3 inflammasome inhibitor. We showed that 1,2,4-TTB (1 mM) markedly suppressed nigericin- or ATP-induced NLRP3 inflammasome activation, thus decreased caspase-1 activation and IL-1β secretion in immortalized murine bone marrow-derived macrophages (iBMDMs) and in primary mouse microglia. Moreover, 1,2,4-TTB specifically inhibited the activation of NLRP3 inflammasome without affecting absent in melanoma 2 (AIM2) inflammasome activation. We further demonstrated that 1,2,4-TTB inhibited oligomerization of the apoptosis-associated speck-like protein containing a CARD (ASC) and protein-protein interaction between NLRP3 and ASC, thus blocking NLRP3 inflammasome assembly in iBMDMs and in primary mouse macrophages. In mice with experimental autoimmune encephalomyelitis (EAE), administration of 1,2,4-TTB (200 mg · kg-1 · d-1, i.g. for 17 days) significantly ameliorated EAE progression and demyelination. In conclusion, our results demonstrate that 1,2,4-TTB is an NLRP3 inflammasome inhibitor and attenuates the clinical symptom and inflammation of EAE, suggesting that 1,2,4-TTB is a potential candidate compound for treating NLRP3 inflammasome-driven diseases, such as multiple sclerosis.

Comparison of the performance of atmospheric pressure glow discharges operated between a flowing liquid cathode and either a pin-type anode or a helium jet anode for the Ga and In determination by the optical emission spectrometry

Novel atmospheric pressure glow discharge (APGD) microplasma systems, sustained between a miniaturized flowing liquid cathode (FLC) and either a pin-type anode or a He nozzle jet were investigated for the determination of Ga and In by the optical emission spectrometry (OES). The most influential working parameters, i.e., solution flow rate, acid concentration, discharge current, and He flow rate, were optimized for both studied systems. Furthermore, the effect of the addition of low molecular weight organic compounds (LMWOCs) into the FLC solution on the signals intensity of Ga and In was investigated. Subsequently, the impact of concomitant ions on the signals intensity of Ga and In was thoroughly studied and it was established that both studied methods are relatively resistant to matrix effects. Under the optimized conditions, the detection limits (DLs, assessed on the basis of the 3σ criterion) of the studied elements were similar for both discharges and ranged between 1.8 and 2.3 μg L−1 for Ga and 0.37–0.40 μg L−1 for In. The received DLs were therefore better than those obtained for other spectrometric methods being premised upon microplasma systems and comparable with those obtained by currently employed large-scale instrumentation. The system with the pin-type anode was successfully applied for the Ga and In determination in four leachates of solders and electronic scrap as well as river water, using external calibration with simple standard solutions. The received results were compared to those obtained from ICP-OES or ICP-MS measurements and their recoveries were fallen within the range of 98–114%, confirming the excellent accuracy and reliability of the developed FLC-APGD-OES method.

Small molecule-based treatment approaches for intervertebral disc degeneration: Current options and future directions.

Low back pain (LBP) is a major reason for disability, and symptomatic intervertebral disc (IVD) degeneration (IDD) contributes to roughly 40% of all LBP cases. Current treatment modalities for IDD include conservative and surgical strategies. Unfortunately, there is a significant number of patients in which conventional therapies fail with the result that these patients remain suffering from chronic pain and disability. Furthermore, none of the current therapies successfully address the underlying biological problem - the symptomatic degenerated disc. Both spinal fusion as well as total disc replacement devices reduce spinal motion and are associated with adjacent segment disease. Thus, there is an unmet need for novel and stage-adjusted therapies to combat IDD. Several new treatment options aiming to regenerate the IVD are currently under investigation. The most common approaches include tissue engineering, growth factor therapy, gene therapy, and cell-based treatments according to the stage of degeneration. Recently, the regenerative activity of small molecules (low molecular weight organic compounds with less than 900 daltons) on IDD was demonstrated. However, small molecule-based therapy in IDD is still in its infancy due to limited knowledge about the mechanisms that control different cell signaling pathways of IVD homeostasis. Small molecules can act as anti-inflammatory, anti-apoptotic, anti-oxidative, and anabolic agents, which can prevent further degeneration of disc cells and enhance their regeneration. This review pursues to give a comprehensive overview of small molecules, focusing on low molecular weight organic compounds, and their potential utilization in patients with IDD based on recent in vitro, in vivo, and pre-clinical studies.

Compositional differences of fluorescent dissolved organic matter in Arctic Ocean spring sea ice and surface waters north of Svalbard

We assessed the qualitative composition of fluorescent dissolved organic matter (FDOM) in Arctic Ocean surface water and in sea ice north of the Svalbard Archipelago (in the Sophia Basin, the Yermak Plateau and the north Spitsbergen shelf) in May and June 2015, during the “TRANSSIZ” expedition (Transitions in the Arctic Seasonal Sea Ice Zone). Samples collected in open lead waters (OW), under-ice waters (UIW) and from the sea ice (ICE) were analyzed by fluorescence spectroscopy and subsequently by multivariate statistical methods using Parallel Factor Analysis (PARAFAC). Statistical analyses of all measured DOM fluorescence excitation and emission matrices (EEMs) enabled four components to be identified and validated. The spectral characteristics of the first component C1 (λEx/λEm 282(270)/335) corresponded to those of tryptophan. The spectral properties of the other three components corresponded to those of humic-like substances: components two (C2 − λEx/λEm 315(252)/395) and three (C3 − λEx/λEm 357(258)/446) corresponded to humic-like substances of marine origin, whereas component four (C4 − λEx/λEm 261(399)/492) resembled terrestrial humic-like substances. Changes in FDOM composition were recorded in OW, in contrast to UIW and sea ice. In the OW the sum of fluorescence intensities of humic-like components (C2, C3 and C4) was two times higher than the fluorescence intensity of protein-like component (C1). Component C2 exhibited the highest fluorescence intensity. In the UIW and particularly in the sea ice the fluorescence intensity of the protein-like component, IC1, was the highest. The IC1 in the sea ice increased toward the sea ice bottom, reaching maximum values at the sea ice-water interface. The calculated spectral indices (SUVA(254) and HIX) and ratios of fluorescence intensities of protein-like to humic-like components, Ip/Ih, suggested that FDOM in water and sea ice was predominantly autochthonous, characterized by low molecular weight organic compounds and low aromatic ring saturation. Enrichment factors Dc, calculated from salinity-normalized values of the optical DOM properties and dissolved organic carbon concentrations, indicated the significant fractionation of FDOM in the sea ice relative to the parent open waters. The humic-like terrestrial component C4 was enriched the least, whereas the protein-like component C1 was enriched the most. A statistically significant (p < 0.0001) and relatively strong (R = 63) correlation between IC1 and the total chlorophyll a concentration Tchla was found in the sea ice, which suggests that sympagic algal communities were producers of the protein-like FDOM fraction.

In Search of Non-covalent Inhibitors of SARS-CoV-2 Main Protease: Computer Aided Drug Design Using Docking and Quantum Chemistry

Two stages virtual screening of a database containing several thousand low molecular weight organic compounds is performed with the goal to find inhibitors of SARS-CoV-2 main protease. Overall near 41000 different 3D molecular structures have been generated from the initial molecules taking into account several conformers of most molecules. At the first stage the classical SOL docking program is used to determine most promising candidates to become inhibitors. SOL employs the MMFF94 force field, the genetic algorithm (GA) of the global energy optimization, takes into account the desolvation effect arising upon protein-ligand binding and the internal stress energy of the ligand. Parameters of GA are selected to perform the meticulous global optimization, and for docking of one ligand several hours on one computing core are needed on the average. The main protease model is constructed on the base of the protein structure from the Protein Data Bank complex 6W63. More than 1000 ligands structures have been selected for further postprocessing. The SOL score values of these ligands are more negative than the threshold of –6.3 kcal/mol obtained for the native X77 ligand docking. Subsequent calculation of the protein-ligand binding enthalpy by the PM7 quantum-chemical semiempirical method with COSMO solvent model have narrowed down the number of best candidates. Finally, the diverse set of 20 most perspective candidates for the in vitro validation are selected.

Plant Secondary Metabolites as Defenses, Regulators, and Primary Metabolites: The Blurred Functional Trichotomy.

The plant kingdom produces hundreds of thousands of low molecular weight organic compounds. Based on the assumed functions of these compounds, the research community has classified them into three overarching groups: primary metabolites, which are directly required for plant growth; secondary (or specialized) metabolites, which mediate plant-environment interactions; and hormones, which regulate organismal processes and metabolism. For decades, this functional trichotomy of plant metabolism has shaped theory and experimentation in plant biology. However, exact biochemical boundaries between these different metabolite classes were never fully established. A new wave of genetic and chemical studies now further blurs these boundaries by demonstrating that secondary metabolites are multifunctional; they can function as potent regulators of plant growth and defense as well as primary metabolites sensu lato. Several adaptive scenarios may have favored this functional diversity for secondary metabolites, including signaling robustness and cost-effective storage and recycling. Secondary metabolite multifunctionality can provide new explanations for ontogenetic patterns of defense production and can refine our understanding of plant-herbivore interactions, in particular by accounting for the discovery that adapted herbivores misuse plant secondary metabolites for multiple purposes, some of which mirror their functions in plants. In conclusion, recent work unveils the limits of our current functional classification system for plant metabolites. Viewing secondary metabolites as integrated components of metabolic networks that are dynamically shaped by environmental selection pressures and transcend multiple trophic levels can improve our understanding of plant metabolism and plant-environment interactions.

Photodegradation of low molecular weight organic compounds by 185-nm UV light in ultrapure water production system

The photodegradation of low molecular weight organic compounds by 185-nm UV light was studied using a continuously operated column reactor which can be simulated the TOC reduction UV unit in ultrapure water production (UPW) process. Six chemicals (methanol, ethanol, acetaldehyde, isopropyl alcohol (IPA), acetone, and methyl ethyl ketone (MEK)) were chosen as target compounds, because they are frequently observed in influent of a total organic carbon (TOC) reduction UV unit in UPW production process. The degradation efficiency of each chemical and the proportions of intermediate byproducts and the final product (CO2) were measured by TOC and gas chromatography mass spectrometry (GC–MS). The degradation efficiency by 185-nm UV based on GC–MS analysis was as follows, from highest to lowest: acetaldehyde, IPA, ethanol, MEK, methanol, and acetone. The fastest oxidation to CO2 was observed in methanol degradation in which 13 % of methanol was transformed to CO2 which was 6 times higher than that of ethanol, the slowest one. In the analysis of the intermediate byproducts of chemical degradation, except for IPA, the percentage of charged byproduct was higher than that of uncharged byproduct. These findings constitute a theoretical basis for placement of ion exchange (IX) resin behind a TOC reduction UV unit to increase the TOC removal efficiency because charged organic materials are removed by IX resin.

Electro-oxidation of secondary effluents from various wastewater plants for the removal of acetaminophen and dissolved organic matter

Electro-oxidation of acetaminophen (ACT) in three different doped secondary effluents collected from a conventional Municipal Waste Water Treatment Plant (MWWTP), a MWWTP using a membrane bioreactor (WWTP MBR) and a lab-scale MBR treating source-separated urine (Urine MBR) was investigated by electro-Fenton (EF) coupled with anodic oxidation (AO) using sub-stoichiometric titanium oxide anode (Ti4O7). After 8 h of treatment, 90 ± 15%, 76 ± 3.8% and 46 ± 1.3% of total organic carbon removal was obtained for MWWTP, MWWTP-MBR and Urine-MBR respectively, at a current intensity of 250 mA, pH of 3 and [Fe2+] = 0.2 mM. Faster degradation of ACT was observed in the WWTP MBR because of the lower amount of competitive organic matter, however, >99% degradation of ACT was obtained after 20 min for all effluents. The acute toxicity of the treated effluent was measured using Microtox® tests. Results showed an initial increase in toxicity, which could be assigned to formation of more toxic by-products than parent compounds. From 3D excitation and emission matrix fluorescence (3DEEM), different reactivity was observed according to the nature of the organic matter. Particularly, an increase of low molecular weight organic compounds fluorescence was observed during Urine MBR treatment. This could be linked to the slow decrease of the acute toxicity during Urine MBR treatment and ascribed to the formation and recalcitrance of toxic organic nitrogen and chlorinated organic by-products. By comparison, the acute toxicity of other effluents decreased much more rapidly. Finally, energy consumption was calculated according to the objective to achieve (degradation, absence of toxicity, mineralization).

Characterization of 10 Biogenic Amines in Male Silkworm Moth by HPLC with Precolumn Derivatization

Background: Biogenic Amines (BAs) are biologically active nitrogenous organic compounds of low molecular weight, which are frequently found in a wide variety of foods, beverages and herbs due to their toxic potential in humans. Male Silkworm Moth (MSM), a Traditional Chinese Medicine (TCM), has been exploited and utilized as nutritious liquor based on its traditional effects in the Chinese community. Objective: The objective of this study was to develop an HPLC with Dns-Cl derivatization method for characterizing overall BAs in MSM and providing data for further evaluating its activities and safety profiles. Methods: The method has acceptable sensitivity, precision, accuracy, selectivity and recovery, and was successfully applied to the determination of the BAs contents in MSM for the first time. Results: In the analysis of 10 batches of MSM samples, serotonin and dopamine were not found in detectable concentrations in any samples, and the most abundant amine found was putrescine. The mean values of tryptamine, phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine, and spermine determined in the samples were found to be 34.7 mg/ kg, 16.1 mg/ kg, 218.3 mg/ kg, 37.9 mg/ kg, 12.1 mg/ kg, 18.2 mg/ kg, 4.5mg/ kg, and 0.9 mg/ kg, respectively. Conclusion: The contents of BAs in 10 batches of MSM were below the maximum recommended limits, and MSM can be used safely.

Processes of catalytic oxidation for the production of chemicals from softwood biomass

Two alternative routes of softwood catalytic oxidative fractionation to cellulose products and fine chemicals are assessed.Wesuggested to use the process of larch wood peroxide oxidation in the medium acetic acid – water at temperatures 70–100 °C in the presence of soluble catalyst (NH4)6Mo7O24 to produce microcrystalline cellulose (35.0 wt% on wood), microfibrillated cellulose (7.5 wt% on wood) or nanocrystalline cellulose (3.7 wt% on wood) and low molecular weight organic compounds (20 wt% on wood). The developed process reduces the number of technological stages and increase an environmentally safety of nanocelluloses production from wood, compared to traditional technologies.Another suggested process of softwood (pine and larch) fractionation to vanillin (up to 4.7 wt% on wood) and cellulose (up to 34.6 wt% on wood) is based on wood oxidation by oxygen in water–alkaline medium at temperatures 160–180 °C in the presence of suspended catalyst Cu(OH)2. The further acid conversion of cellulose by 2 % H2SO4at 180 °C produces levulinic acid with the yield up to 9.7 wt % on wood.The integration of the processes of dihydroquercetin and arabinogalactan extraction isolation from larch wood, oxidation of extracted wood by oxygen to vanillin and cellulose in the presence of catalyst Cu(OH)2, acid catalyzed conversion of cellulose to levulinic acid and arabinogalactan hydrolysis over solid acid catalyst to arabinose and galactose leads to an increase in the number of target products.FTIR, XRD, SEM, AFM, solid state 13C CP/MAS and chemical methods were used for characterization of cellulose products. Organic compounds were identified by GC, HPLC and GC-MS methods.The two alternative schemes of larch wood catalytic oxidative biorefinery to produce nanocelluloses and fine chemicals have been developed.

Exploring ovarian cancer screening using a combined sensor approach: A pilot study

All cells release low molecular weight organic compounds that possess finite vapor pressures at body and/or ambient temperatures. These volatile organic compounds (VOCs) may possess an odor and can be found emanating from all body fluids. As cells turn malignant, analysis of changes in these VOCs can provide insight into cancer onset and diagnosis. Previous studies have demonstrated that dogs can be trained to distinguish ovarian cancer tissues of various stages and grades from normal ovarian tissue and other gynecological malignancies with sensitivity and specificity over 95%. When trained on biopsied tissue, dogs were able to detect the VOC disturbances in peripheral blood samples with the same accuracy. Building on these earlier studies, we examined the VOCs emanating from plasma samples from primary ovarian cancer patients, patients with benign reproductive tract growths, and healthy controls. We used a three-pronged sensor approach to analyze the VOCs from plasma: canines trained on tissue and plasma samples, analysis using solid phase microextraction gas chromatography–mass spectrometry, and novel single stranded DNA-coated carbon nanotube sensor field effect transistors. Each of the three experimental approaches used in this study provided preliminary evidence that plasma from ovarian cancer patients emits a volatile odor signature that can be distinguished from the VOCs of patients with benign ovarian tumors and controls. Our results provide optimism that a diagnostic approach based on the analysis of the VOC odor signature of ovarian cancer is achievable.

The effect of soil and climatic conditions on the distribution of nutrients in Actinidia arguta leaves

The patterns of the distribution of nutrients in kiwiberry (Actinidia arguta (Siebold &amp; Zucc.) Planch. ex Miq.), family Actinidiaceae (Gilg &amp; Werderm), leaves growing under different soil and climatic conditions (Ukraine and China) were studied. Using scanning electron microscopy, significant differences were shown in the distribution of assimilates and mineral nutrients in the leaves of kiwiberry cultivated under different climate and soil conditions (Kyiv city, Ukraine and Jiamusi, China). The leaves of plants grown in China have higher concentration of all of the studied nutrients exception for silicon. The differences found in the content of macro- and microelements in plant tissues are consistent with their total content in the soil, and depend on the synthesis of low molecular weight organic compounds, namely, hydroxybenzoic, benzoic and triterpene acids. An increase in the silicon content in the leaves of kiwiberry plants grown in Ukraine indicates the moisture deficit in the soil. This conclusion is confirmed by the anatomical differences viz. the presence of additional integumentary formations and fewer stomata number per 1 mm2 of leaf surface. The specific feature of ‘Perlyna sadu’ cultivar was high concentrations of sodium and aluminum in the foliar tissues, regardless of the place of growth. The analysis of the distribution of nutrients in the leaves located along the stem showed remobilization of the former within the three layers: the lower one nourishes the roots, the upper one nourishes the leaves in the active growth phase and the middle one allocates the assimilates in both directions. A significant positive relationship was found between the biosynthesis of photosynthetic pigments and electrophysiological activity, especially for the leaves of the lower zone. The revealed differentiation into layers differing in polarity of bioelectric potentials and the distribution of assimilates suggests functional differentiation of the kiwiberry leaves. In particular, the leaves of the lower layer perform a storage function. The middle part is less conservative and characterized by higher sensitivity to environmental factors performs a mainly synthetic function. The upper layer performs an active growth function. The results of the comparative analysis of the indicators of the number of chloroplasts in the mesophyll cells proved that the obtained dependence can be used as a diagnostic criterion in assessing the predicted plant productivity at the early stages of their development.

Use of untargeted metabolomics for assessing soil quality and microbial function

Soils support a wide range of ecosystem services that underpin Earth system functioning. It is therefore essential that we have robust approaches to evaluate how anthropogenic perturbation affects soil quality and the delivery of these services. Metabolomics, the large-scale study of low molecular weight organic compounds in soil, offers one potential approach to characterise soils and evaluate the metabolic status of the soil biological community. The aims of the present study were to 1) characterise the soil metabolome across a contrasting range of soil types, 2) understand the relationships between common chemical and physical soil quality indicators and its metabolome, and 3) evaluate the discriminatory power of soil metabolomics and its potential use as a soil quality indicator. Nine different topsoils with 5 replications were collected along an altitudinal primary productivity gradient encompassing a wide range of soil types and land uses. Metabolites were extracted from soil using 3:3:2 (v/v/v) acetonitrile:isopropanol:water and individual compounds identified using a gas chromatography-mass spectrometry (GC-MS) platform. Overall, 405 individual compounds were detected, of which 146 were positively identified, including sugars, amino acids, organic acids, nucleobases, sugar alcohols, lipids and a range of secondary metabolites. The concentration and profile of metabolites was found to vary greatly between the soil types. Further, the soils’ metabolomic fingerprints correlated to a number of environmental factors, including pH, land-use, moisture and salinity. We also tentatively attributed soil-specific metabolites to potential functional pathways, although complementary proteomic, genomic and transcriptomic approaches would be needed to provide definitive supporting evidence. In conclusion, soil metabolomics offers the potential to reveal the complex molecular networks and metabolic pathways operating in the soil microbial community and a means of evaluating soil function. Further work is now required to benchmark soil metabolomes under a wide range of management regimes so that they can be used for the quantitative assessment of soil quality.

Profiling low molecular weight organic compounds from naphthenic acids, acid extractable organic mixtures, and oil sands process-affected water by SPME-GC-EIMS

Naphthenic acids (NAs) are complex mixtures of carboxylic acids from petroleum that have industrial applications and that may be released to the environment after oil spills. There is significant research on the chemical composition and toxicity of water-soluble NAs derived from oil sands mining in Alberta, Canada. Yet, little is known about low molecular weight organic compounds (LMWOC) from these sources. Headspace solid-phase microextraction coupled to gas chromatography-electron impact mass spectrometry was used for LMWOC profiling of commercial NA blends, and an acid-extractable organics (AEOs) mixture from a tailings pond. From Sigma 1, Sigma 2, Merichem NAs and the AEO extract, 54, 56, 40 and 4 compounds were identified, respectively. These include aliphatic and cyclic hydrocarbons, carboxylic acids, alkylbenzenes, phenols, naphthalene and alkyl-naphthalene, and decalin compounds. A sample of oil sands process-affected water (OSPW) and aqueous solutions of the NA blends were evaluated for matrix effects on LMWOC profiles. Principal component and clustering analyses revealed that LMWOC profiles of commercial extracts were closely related but distinct from the AEO and OSPW samples. Some of the identified LMWOC are reported to be genotoxic or carcinogenic, and therefore the NA mixtures and AEOs should be considered hazardous materials and further evaluated.

Advanced biofilm analysis in streams receiving organic deicer runoff.

Prolific heterotrophic biofilm growth is a common occurrence in airport receiving streams containing deicers and anti-icers, which are composed of low-molecular weight organic compounds. This study investigated biofilm spatiotemporal patterns and responses to concurrent and antecedent (i.e., preceding biofilm sampling) environmental conditions at stream sites upstream and downstream from Milwaukee Mitchell International Airport in Milwaukee, Wisconsin, during two deicing seasons (2009-2010; 2010-2011). Biofilm abundance and community composition were investigated along spatial and temporal gradients using field surveys and microarray analyses, respectively. Given the recognized role of Sphaerotilus in organically enriched environments, additional analyses were pursued to specifically characterize its abundance: a consensus sthA sequence was determined via comparison of whole metagenome sequences with a previously identified sthA sequence, the primers developed for this gene were used to characterize relative Sphaerotilus abundance using quantitative real-time PCR, and a Sphaerotilus strain was isolated to validate the determined sthA sequence. Results indicated that biofilm abundance was stimulated by elevated antecedent chemical oxygen demand concentrations, a surrogate for deicer concentrations, with minimal biofilm volumes observed when antecedent chemical oxygen demand concentrations remained below 48 mg/L. Biofilms were composed of diverse communities (including sheathed bacterium Thiothrix) whose composition appeared to shift in relation to antecedent temperature and chemical oxygen demand. The relative abundance of sthA correlated most strongly with heterotrophic biofilm volume (positive) and dissolved oxygen (negative), indicating that Sphaerotilus was likely a consistent biofilm member and thrived under low oxygen conditions. Additional investigations identified the isolate as a new strain of Sphaerotilus montanus (strain KMKE) able to use deicer components as carbon sources and found that stream dissolved oxygen concentrations related inversely to biofilm volume as well as to antecedent temperature and chemical oxygen demand. The airport setting provides insight into potential consequences of widescale adoption of organic deicers for roadway deicing.

Construction of Plasma Ion Sources to be Applied in Analysis of Small Organic Compounds Using Mass Spectrometry

The application of an independent source of ions working with mass spectrometers and permitting generation of ions at atmospheric pressure from samples of different types is a very attractive solution allowing construction of small portable mass spectrometers. In our study two types of plasma source were used as external sources of ions to analyze the low molecular weight organic compounds by mass spectrometry. Small organic compounds and analytes on solid materials were analyzed. The application of plasma torches for analysis of organic compounds was tested by the methods of mass spectra (MS) and ion fragmentation analysis (MS2).