Fourier Transform Cyclotron Resonance Mass Research Articles

The unique biogeochemical role of carbonate-associated organic matter in a subtropical seagrass meadow

The particulate organic matter buried in carbonate-rich seagrass ecosystems is an important blue carbon reservoir. While carbonate sediments are affected by alkalinity produced or consumed in seagrass-mediated biogeochemical processes, little is known about the corresponding impact on organic matter. A portion of particulate organic matter is carbonate-associated organic matter. Here, we explore its biogeochemistry in a carbonate seagrass meadow in central Florida Bay, USA. We couple inorganic stable isotope analyses (δ34S, δ18O) with a molecular characterization of dissolved and carbonate associated organic matter (21 tesla Fourier-transform ion cyclotron resonance mass spectrometry). We find that carbonate-associated molecular formulas are highly sulfurized compared to surface water dissolved organic matter, with multiple sulfurization pathways at play. Furthermore, 97% of the formula abundance of surface water dissolved organic matter is shared with carbonate-associated organic matter, indicating connectivity between these two pools. We estimate that 9.2% of the particulate organic matter is carbonate-associated, and readily exchangeable with the broader aquatic system as the sediment dissolves and reprecipitates.

A fast solid-phase microextraction scheme for in vivo monitoring of bio-accumulation and bio-transformation of arbidol in living plants

Large quantity of the antiviral drug arbidol is used for resisting virus infection like the Corona Virus Disease 2019 and influenza, resulting in unanticipated environmental pollution. Herein, to investigate the environmental risks of the unanticipated arbidol contamination, a novel in vivo sampling probe was developed based on a bromo-substituted porous organic polymer (Br-POP) and then adopted for tracking the bio-accumulation and bio-transformation of arbidol in living plants by coupling with a nano-electrospray ionization fourier-transform ion cyclotron resonance mass spectrometry (Nano-ESI-FT-ICR-MS) method. The established method showed good extraction performance towards arbidol with limit of detection (LOD) of 0.48 ng g−1, and relative standard deviation (RSD) of single-and multiple- probe of 2.2 and 14 %. Owing to the interactions between the Br-POP and the target analytes, as well as the fast analysis process of Nano-ESI-FT-ICR-MS, <6 min was cost for total sampling and analysis duration, achieving hourly tracking of arbidol and its metabolites in this work. During 21-d in vivo tracking, the concentration of arbidol in living plant stems increased rapidly within 6 h and peaked at 413.93 ± 47.09 ng g−1. Meanwhile, it was found that dissolved organic matters (DOM) had significant effect on arbidol behaviors in living plants, resulting in a decrease of the maximum concentration of arbidol in plant stems (152.70 ± 42.44 ng g−1) and the change of dominant metabolite of arbidol that the S-oxidation rather than N-demethylation product of arbidol was dominant with DOM participation. Additionally, the plant root secretion was found to be significantly altered by arbidol exposure. To summarized, the combination of in vivo SPME and the FT-ICR-MS analysis provide new and important information regarding arbidol contamination and related alternation of plant root metabolism.

Enhanced hydrothermal liquefaction of tires using zinc and MoS2

This study introduces a novel approach for tire liquefaction employing zinc and unsupported catalyst MoS2 to mitigate oxygen, nitrogen, and sulfur content, while inhibiting poly-aromatic formation. Autoclave experiments were conducted under subcritical water conditions at 360 and 410 °C. Comprehensive characterization of char and oil was performed, encompassing elemental analysis, functional-group assessment, and composition analysis using gas chromatography-mass spectrometry (GC-MS) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). During the liquefaction, zinc metal pellets react with water to form ZnO and hydrogen, aiding hydrogenation, and MoS2 preserves its catalytic stability. ZnO shows a catalytic effect on deoxygenation, desulfurization, and denitrification reactions. However, the reaction between ZnO and H2S is not favorable under hydrothermal conditions. Zinc and MoS2 synergistically promote cracking of heavier compounds into lighter ones, particularly evident at higher temperatures, without diminishing the overall oil yield. Incorporating zinc pellets and MoS2 slightly facilitates sulfur and oxygen migration from liquid to solid and gas phases. FT-ICR MS analysis reveals oxygen, sulfur, and nitrogen-containing compounds in heavy fraction of oils. The oxygen-containing compounds, predominantly comprised of stearic acid and its derivatives, are identified. Concurrently, the nitrogen-containing compounds manifest primarily as basic nitrogen compounds. MoS2 possesses the capability of forming more N-containing compounds, leading to the generation of a broader spectrum of N-containing compounds. This work elucidates the synergistic role of zinc-assisted catalysis and MoS2, offering insights into tire liquefaction mechanisms and product composition, vital for sustainable waste management and resource recovery.

Thermal Denaturation of Fresh Frozen Tissue Enhances Mass Spectrometry Detection of Peptides.

Thermal denaturation (TD), known as antigen retrieval, heats tissue samples in a buffered solution to expose protein epitopes. Thermal denaturation of formalin-fixed paraffin-embedded samples enhances on-tissue tryptic digestion, increasing peptide detection using matrix-assisted laser desorption ionization imaging mass spectrometry (MALDI IMS). We investigated the tissue-dependent effects of TD on peptide MALDI IMS and liquid chromatography-tandem mass spectrometry signal in unfixed, frozen human colon, ovary, and pancreas tissue. In a triplicate experiment using time-of-flight, orbitrap, and Fourier-transform ion cyclotron resonance mass spectrometry platforms, we found that TD had a tissue-dependent effect on peptide signal, resulting in a (22.5%) improvement in peptide detection from the colon, a (73.3%) improvement in ovary tissue, and a (96.6%) improvement in pancreas tissue. Biochemical analysis of identified peptides shows that TD facilitates identification of hydrophobic peptides.

Differential interaction modes of As(III)/As(V) with microbial cell membrane induces opposite effects on organic contaminant biodegradation in groundwater

Arsenic, a widespread toxic metalloid in groundwater, derives both from natural geological environment and industrial discharge, is extensively detected to be coexisting with organic contaminants, such as 2,4,6-trichlorophenol (TCP), a prior concerned pollutant. During biological remediation of groundwater, arsenic potentially intervenes microbial behaviors. This study found an opposite interference of arsenic in its two different valences (III and V) on the degradation of TCP by the functional bacteria, Sphingomonas fennica K101. As(III) inhibited TCP degradation in a concentration-dependent manner (from 0.1-10 mg/L), with a maximum inhibition rate of 35.5 %, whereas As(V) exhibited promoting effects by 13.8 % and 33.2 % at 1 mg/L and 10 mg/L, respectively. Employing field emission transmission electron microscopy, quantum chemical calculation, fourier-transform ion cyclotron resonance mass spectrometry and metabolomic analysis, we unveil distinct interactions between cell membranes and arsenic in two valence states. Exposure to As(III) led to significant accumulation of As(III) in the cytoplasm, followed by interaction with intracellular ferritin (ferritin heavy chain 1), releasing iron ions and generating ROS. Subsequently, it induced ferroptosis and disrupted bacterial basal metabolism, thereby inhibiting TCP biodegradation. Oppositely, As(V) bound to a critical component sphingosine and triggered sphingosine polymerization, increasing membrane permeability, which was evidenced by measuring lactate dehydrogenase release. This process facilitated TCP transmembrane permeation by reducing membrane or extracellular secretion resistance. As(V) concurrently upregulated energy metabolism and accelerated TCP degradation. Our study elucidates the influence of prevalent arsenic on biodegradation efficacy, particularly amidst changing redox conditions associated with varying arsenic valences.

Molecular insights into pilot-scale selective removal of emerging contaminants in hospital wastewater

Advanced oxidation processes (AOPs) are a promising technology for removing emerging organic contaminants (EOCs) from wastewater, while the coexisting dissolved organic matter (DOM) significantly hinders effective oxidative removal of EOCs. Understanding the effects of DOM on EOCs removal in real water matrices is crucial for designing more efficient AOPs. Herein, a pilot-scale integrated in-situ ozonation/ultrafiltration process was conducted to remove EOCs from hospital wastewater. Furthermore, the ozonation reactivity of DOM and EOCs was contrastingly analyzed at the molecular level. Our integrated process selectively removed 85 % of EOCs at a relatively low oxidant dosage of 0.44 mg O3 per mg dissolved organic carbon (DOC). Using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we reveal that ozone selectivity for EOCs arose from their overall reductive characteristics of being more aromatic and unsaturated in molecular composition compared to DOM. Additionally, specific DOM compounds potentially facilitate EOCs removal. This work provides pilot-scale experience in EOCs removal from hospital wastewater and in-depth understanding of DOM’s role in the integrated process, guiding the development of effective AOPs for selective removal of emerging contaminants.

Molecular–level insights into the synergistic activation of peracetic acid by ultraviolet and ferrous ions for the degradation of sedimentation sludge water in drinking water treatment plants based on Fourier transform-ion cyclotron resonance mass spectrometry

Sedimentation sludge water (SSW) from sedimentation tanks in drinking water treatment plants contains significant amounts of dissolved organic matter (DOM) and precursors of disinfection byproducts, raising increasing concerns about the safety of finished water following SSW recycling. This study explores the alterations in bulk properties and molecular characteristics of DOM in SSW treated with ultraviolet (UV)/ferrous ions (Fe2+) and peracetic acid (PAA) using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS). The primary reactive species, hydroxyl radicals (·OH) and acylperoxy radicals (CH3C(O)OO·) achieved degradation rates of up to 82.0%, eliminating 84.5% of total fluorescent components and reducing molecular intensity and apparent molecular count by 90.9% and 69.8%, respectively. This treatment significantly reduced the aromaticity of DOM, leading to the formation of more oxidized and stable compounds. Reaction mechanisms indicate that ·OH and CH3C(O)OO· primarily facilitate oxygen addition and dehydrogenation, while CH3C(O)OO· promotes decarboxylation through weak electron transfer processes. The treatment preferentially removes complex DOM containing nitrogen and sulfur heteroatoms, which are key precursors of disinfection byproducts. These findings enhance our understanding of DOM transformations during UV/Fe2+/PAA treatment and provide valuable insights into the safe recycling of SSW.

Targeted and non-targeted identification of dye and chemical contaminants in Loji River, Indonesia using FT-ICR-MS

This study utilized liquid chromatography (LC) alongside Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the dyes and chemical contaminants in Loji River, Indonesia. We tentatively identified a total of 655 contaminants at various confidence level, subsequently classifying them into 22 distinct categories. Of the 54 dyes we detected, 12 corresponded with entries in our specialized in-house database. These 12 dyes were further confirmed by reference standards, matching both retention time (RT) and MS/MS spectra. LC-FT-ICR MS data showed that dyes from printing batik and textile industries are key contributors to river pollution. Particularly noteworthy were two sample locations that displayed substantial contamination, predominantly from azoic and reactive dyes. Additionally, pharmaceuticals were identified as one of the most frequently occurring contaminants, underscoring the inadequacies in the area's sewage management. To corroborate these findings, we conducted physicochemical, phytotoxicity, and acute toxicity tests, all of which verified the harmful effects of the Loji River's water on both the local flora and human populations. Notably, water samples that tested positive for dye contamination exhibited elevated toxicity levels. To the best of our knowledge, this study is pioneering in its molecular-level investigation of dye contamination in Southeast Asian rivers. Our results accentuate the pressing need for both targeted and non-targeted screening methods to identify contaminants in the surface waters of developing nations.

Analysis of dissolved organic matter characteristics in pharmaceutical wastewater via spectroscopy combined with Fourier-transform ion cyclotron resonance mass spectrometry

Studying the changes in organic matter and characteristic pollutants during the treatment of penicillin-containing pharmaceutical wastewater, which can be reflected by changes in dissolved organic matter (DOM), is crucial for improving the effectiveness of wastewater treatment units and systems. Herein, water quality indicators, spectroscopic methods, and Fourier-transform ion cyclotron resonance mass spectrometry were utilized to characterize the general molecular compositions and specific molecular changes in DOM during the treatment of typical penicillin-containing pharmaceutical wastewater, including in each of the influent, physicochemical treatment, biological treatment, oxidation treatment, and effluent stages. The influent exhibited a high organic matter content (concentration of dissolved organic carbon >10,000 mg·L−1), its DOM mainly contained protein- and lignin-like substances composed of CHON and CHONS molecules, and the relative intensity (RI) of penicillin was extremely high (RI = 0.220). Compared with the influent, the abundance of CHON and CHONS molecules detected after physicochemical treatment decreased by 70.3 % and 62.5 %, respectively, and the RI of penicillin decreased by 85.5 %. Biological treatment caused substantial changes in DOM components through oxidation, dealkylation, and denitrification reactions, accounting for 36.8 %, 28.9 %, and 14.8 % of the total identified reactions, respectively. Additionally, lignin-like substances were generated in large quantities, the overall humification level significantly increased, and the RI value increased for the penicillin intermediate, 6-aminopenicillanic acid (6-APA). Oxidation treatment effectively removed phosphorus-containing substances and some lignin-like substances produced by biological treatment; however, it was not effective in removing characteristic pollutants such as 6-APA. Such characteristic substances continued to be present in the effluent, and the DOM mainly contained protein- and humus-like substances, accounting for 30.8 % and 47.3 %, respectively. The study findings reveal the changes in organic matter and characteristic pollutants during the treatment of penicillin-containing wastewater from the perspective of the general molecular composition and specific molecular changes in DOM, providing support for further exploration of wastewater treatment mechanisms and improvements in treatment unit efficiency.

Recovering Valuable Chemicals from Polypropylene Waste via a Mild Catalyst-Free Hydrothermal Process.

Waste polypropylene (PP) presents a significant environmental challenge, owing to its refractory nature and inert C-C backbone. In this study, we introduce a practical chemical recovery strategy from PP waste using a mild catalyst-free hydrothermal treatment (HT). The treatment converts 64.1% of the processed PP into dissolved organic products within 2 h in an air atmosphere at 160 °C. Higher temperatures increase the PP conversion efficiency. Distinct electron absorption and emission characteristics of the products are identified by spectral analysis. Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) reveals the oxidative cracking of PP into shorter-chain homologues (10-50 carbon atoms) containing carboxylic and carbonyl groups. Density functional theory (DFT) calculations support a reaction pathway involving thermal C-H oxidation at the tertiary carbon sites in the polymer chain. The addition of 1% H2O2 further enhances the oxidation reaction to produce valuable short-chain acetic acids, enabling gram-scale recycling of both pure PP and disposable surgical masks from the real world. Techno-economic analysis (TEA) and environmental life cycle costing (E-LCC) analysis suggest that this hydrothermal oxidation recovery technology is financially viable, which shows significant potential in tackling the ongoing plastic pollution crisis and advancing plastic treatment methodologies toward a circular economy paradigm.

Characterization of the Bioavailability of Per- and Polyfluoroalkyl Substances in Farmland Soils and the Factors Impacting Their Translocation to Edible Plant Tissues.

In this study, various crops and farmland soils were collected from the Fen-Wei Plain, China, to investigate the bioavailability of perfluoroalkyl substances (PFAS), their accumulation in edible plant tissues, and the factors impacting their accumulation. PFAS were frequently detected in all of the crops, with total concentrations ranging from 0.61 to 35.8 ng/g. The results of sequential extractions with water, basic methanol, and acidic methanol indicate that water extraction enables to characterize the bioavailability of PFAS in soil to edible plant tissues more accurately, especially for the shorter-chain homologues. The bioavailability of PFAS was remarkably enhanced in the rhizosphere (RS) soil, with the strongest effect observed for leafy vegetables. The water-extracted Σ16PFAS in RS soil was strongly correlated with the content of dissolved organic carbon in the soil. Tannins and lignin, identified as the main components of plant root exudates by Fourier transform-ion cyclotron resonance mass spectrometry, were found to enhance the bioavailability of PFAS significantly. Redundancy analysis provided strong evidence that the lipid and protein contents in edible plant tissues play important roles in the accumulation of short- and long-chain PFAS, respectively. Additionally, the high water demand of these tissues during the growth stage greatly facilitated the translocation of PFAS, particularly for the short-chain homologues and perfluorooctanoic acid.

Stability of sedimentary organic matter: Insights from molecular and redox analyses

Sedimentary organic matter (SOM) affects the stability of the aquatic carbon pool. The degradation process of SOM is complex for its multifaceted composition. The concentration and properties of SOM affect its steady state, yet the transformation processes of SOM in lakes remain unclear. Here we show the molecular and redox perspectives of SOM stability in polluted sediments with high organic matter content and diverse vegetation. We find significant differences in carbon fractions across various sites. The origin of the organic matter, determined using excitation-emission matrix spectra, influences the consistency of organic matter composition and biochemical degradation in lacustrine sediment. We also observe that sulfur-containing substances decrease carbon chain length and reduce organic matter stability. Fourier-transform ion cyclotron resonance mass spectrometry shows that sulfur-containing substances decrease the degree of saturation and cause reduction. In contrast, nitrogen-containing compounds increase the modified aromaticity index and humin content, enhancing organic carbon complexity and stability (p < 0.05). These results complement the characteristics and transformations of SOM. In a broader perspective, this study contributes to laying the foundation for understanding SOM stability in the carbon cycle and its future effects.

The mechanism on liquefaction of waste tire by ethanolysis

Thermo-chemical treatment methods are pivotal for effectively managing waste tire rubber (WTR) while promoting energy efficiency and emission reduction. This study investigates the liquefaction of WTR within a thermal ethanol environment, exploring temperature ranges (200–300 °C) and residence times (0–80 min) to discern the role of ethanol in tire degradation. Additionally, the study includes liquefaction experiments with cyclohexane as a solvent to contrast the effect of ethanol, and comparison between ethanol and water to elucidate solvent impact. Results indicate that at 300 °C for 40 min, oil yields peak at 53.05 % for a WTR/ethanol mass ratio of 1:8 and at 51.64 % for a ratio of 1:6, notably surpassing hydrolysis outcomes. By contracting with the results from the liquefaction with cyclohexane as solvent, the involvement of ethanol can facilitate liquid phase products, primarily alkenes and oxygen-containing compounds, attributed to aromatization inhibition. Heavy oils and heteroatomic compounds are characterized through Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), detecting hydrocarbons and heteroatom compounds like NxOy, Ox, Sx, NxOySz, NxSy, and Nx. Notably, sulfur, a significant pollutant, predominantly manifests as sulfide in chars. These findings offer valuable insights into advancing waste tire recycling technologies.

Rock-to-Pharma: Characterization of Shale Oil-Based Nonbiological Complex Drugs along the Production Process by High-Resolution Mass Spectrometry.

Antibiotic resistance has become a primary concern in medicine because of the overuse and misuse of classical pharmaceuticals. Recently, nonbiological complex drugs (NBCDs) have gained interest for their complex pharmacological profiles. Bituminosulfonates, which have lately been tentatively allocated toward NBCDs, are pharmacologically well-studied and show low potential in resistance development. However, molecular composition knowledge is limited. With this work, we present a comprehensive approach to investigate the manufacturing process of complex pharmaceuticals like bituminosulfonates on a molecular level via Fourier-transform ion cyclotron resonance mass spectrometry. The application of various hyphenations and ionization techniques comprehensively covers the entire mass and polarity range of the matrix, and the high sensitivity enables the identification of significant and minor chemical alterations caused by the multistep manufacturing process. The distillation of the shale crude oil eliminates highly aromatic PAH and PASH constituents. ESI(-) revealed strong PAH- and PASH-sulfonate formation after reacting the shale oil distillate with sulfuric acid. Increasing alkylation reduced the sulfonation yield, instead causing oligomerization side reactions, as observed by APPI analysis. Furthermore, multidimensional gas chromatography coupled with high-resolution mass spectrometry verified core structural motifs. With this work, we demonstrate the high potential of FT-ICR MS in NBCD process analysis. The results also give valuable information for future pharmacological investigations focusing on specific compound classes or properties.

Comparison of dissolved organic matter composition from various sorbents using ultra-high resolution mass spectrometry

Solid phase extraction (SPE) of a variety of diverse dissolved organic matter (DOM) endmembers through eight commercially available sorbents was examined (ENV, PLEXA, PPL, HLB, Isolute 101, C18/ENV+, C18, EnvirElut) representing styrene divinylbenzene polymer (SDVB) and silica-based sorbents. We assessed dissolved organic carbon (DOC) recovery and DOM composition via 21T Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). DOC recoveries and SPE-DOM composition differed more by endmember type than by sorbent. Silica-based sorbents retained DOM with many N-containing formulae, while SDVB-based sorbents retained DOM with more S-containing formulae. Extraction pH exerted a greater influence on DOM composition, notably through the presence of strong groupings composed of saturated and lowly oxygenated formulae at basic pH, and of aromatic and highly oxygenated formulae at pH 2, irrespective of endmember or sorbent. There was above 25% DOC recovery, regardless of sorbent or endmember; >90% of the relative abundance (RA) of molecular formulae were shared with PPL, which is currently the most commonly utilized sorbent for DOM. This clearly highlights the ability of the selected sorbents to retain representative DOM across diverse endmembers. Such findings may be useful for future targeted DOM studies (e.g., bioincubations, wastewater and drinking water applications) interested in focusing on specific compositional changes and will provide a better understanding of how organic carbon cycling is impacted by anthropogenic processes.

Exploring transformation of dissolved organic matters and dissolved organic nitrogen in full-scale anammox wastewater treatment: Temperature and microbial roles

Variation of dissolved organic matters (DOM) in mainstream anammox process has received limited attention. This study systematically characterized DOM and dissolved organic nitrogen (DON) in a full-scale mainstream anammox wastewater treatment plant (WWTP) using spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry. Roles of bacterial community structures related with temperatures on DOM and DON transformations were analyzed. Results indicated that the WWTP removed highly bioavailable, S-containing DOM while producing more unsaturated, aromatic, and N-containing DOM. Higher relative abundances of Proteobacteria and Chloroflexi at low temperature resulted in greater removal rates of proteins, SMP-like and humic acid-like substances. At high temperature, higher relative abundance of Actinobacteriota increased lignin production. Principal component analysis revealed that temperature significantly impacted DOM characteristics compared to DON. These findings are crucial for understanding DOM and DON transformation during mainstream anammox WWTP.

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

Lentisk (Pistacia lentiscus) Oil Nanoemulsions Loaded with Levofloxacin: Phytochemical Profiles and Antibiofilm Activity against Staphylococcus spp.

Most clinical isolates of both Staphylococcus aureus and Staphylococcus epidermidis show the capacity to adhere to abiotic surfaces and to develop biofilms resulting in a contribution to chronic human skin infections. Antibiotic resistance and poor biofilm penetration are the main causes of ineffective therapeutic treatment in killing bacteria within biofilms. A possible strategy could be represented by drug delivery systems, such as nanoemulsions (composed of bioactive oil, surfactant and water phase), which are useful for enhancing the drug permeation of a loaded drug inside the biofilm and its activity. Phytochemical characterization of Pistacia lentiscus oil (LO) by direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) allowed the identification of bioactive compounds with antimicrobial properties, including fatty acids and phenolic compounds. Several monoterpenes and sesquiterpenes have been also detected and confirmed by gas chromatography-mass spectrometric (GC-MS) analysis, together providing a complete metabolomic profiling of LO. In the present study, a nanoemulsion composed of LO has been employed for improving Levofloxacin water solubility. A deep physical-chemical characterization of the nanoemulsion including hydrodynamic diameter, ζ-potential, morphology, entrapment efficiency, stability release and permeation studies was performed. Additionally, the antimicrobial/antibiofilm activity of these preparations was evaluated against reference and clinical Staphylococcus spp. strains. In comparison to the free-form antibiotic, the loaded NE nanocarriers exhibited enhanced antimicrobial activity against the sessile forms of Staphylococcus spp. strains.

Dissolved organic matter released from beach wrack is source-specific and molecularly highly diverse

Beach wrack is an important supplier of nutrients and organic matter to sandy beach ecosystems and underlying subterranean estuaries (STEs), producing metabolic hotspots in these otherwise organic carbon- and nutrient-poor environments. To assess the impact of beach wrack type (e.g., marine, terrestrial, plant, animal) and environmental settings (e.g., tidal inundation, precipitation, and solar irradiation) on nutrient and dissolved organic matter (DOM) release, a series of leaching experiments was conducted. Quantities of leached nutrients and dissolved organic carbon (DOC) were determined, and DOM molecular composition was investigated using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Millimolar—to molar amounts of DOC and dissolved nitrogen were released from the beach cast per kg dry weight, with type of wrack and leaching medium (fresh- vs. saltwater) exerting the biggest influences. Exemplary for animal cast, jellyfish leached up to two 100-fold more, mostly organic, nitrogen compared to all other beach wrack types. FT-ICR-MS data of solid-phase extracted DOM indicated that beach wrack releases compounds with putative mono- and oligosaccharide-, amino acid- and vitamin-type molecular formulae, which likely serve as valuable substrate for heterotrophic microorganisms. DOM from the brown seaweed Fucus sp. was more aromatic than seawater DOM and even beach wrack of terrestrial origin, probably from structural components and secondary metabolites such as phlorotannins. We conclude that DOM and nutrient release from beach wrack strongly depends on wrack type and leaching medium, may obscure molecular provenance proxies (e.g., terrestrial indices), and adds a nutritional boost to infiltrating sea- and rainwater which likely impact microbial respiration rates in the STE.

Revealing Molecular Structures of Nitrogen-Containing Compounds in Dissolved Black Carbon Using Ultrahigh-Resolution Mass Spectrometry Combined with Thermodynamic Calculations.

Landscape wildfires generate a substantial amount of dissolved black carbon (DBC) annually, yet the molecular nitrogen (N) structures in DBC are poorly understood. Here, we systematically compared the chemodiversity of N-containing molecules among three different DBC samples from rice straw biochar pyrolyzed at 300, 400, and 500 °C, one leached dissolved organic carbon (LDOC) sample from composted rice straw, and one fire-affected soil dissolved organic matter (SDOMFire) sample using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). N-Containing molecules contributed 20.0%, 36.1%, and 43.7% of total compounds in Combined DBC (pooling together the three DBC), LDOC, and SDOMFire, respectively, and molecules with fewer N atoms had higher proportions (i.e., N1 > N2 > N3). The N-containing molecules in Combined DBC were dominated by polycyclic aromatic (62.2%) and aromatic (14.4%) components, while those in LDOC were dominated by lignin-like (50.4%) and aromatic (30.1%) components. The composition and structures of N-containing molecules in SDOMFire were more similar to those in DBC than in LDOC. As the temperature rose, the proportion of the nitrogenous polycyclic aromatic component in DBC significantly increased with concurrent enhanced oxidation and unsaturation of N. As indicated by density functional theory (DFT)-based thermodynamic calculations, the proportion of aliphatic amide N decreased from 23.2% to 7.9%, whereas that of nitroaromatic N increased from 10.0% to 39.5% as the temperature increased from 300 to 500 °C; alternatively, the proportion of aromatic N in the 5/6 membered ring remained relatively stable (∼31%) and that of aromatic amide N peaked at 400 °C (32.7%). Our work first provides a comprehensive and thorough description of molecular N structures of DBC, which helps to better understand and predict their fate and biogeochemical behavior.