Insights into the early-life chemical exposome of Nigerian infants and potential correlations with the developing gut microbiome.

Early-life exposure to natural and synthetic chemicals can impact acute and chronic health conditions. Here, a suspect screening workflow anchored on high-resolution mass spectrometry was applied to elucidate xenobiotics in breast milk and matching stool samples collected from Nigerian mother-infant pairs (n = 11) at three time points. Potential correlations between xenobiotic exposure and the developing gut microbiome, as determined by 16S rRNA gene amplicon sequencing, were subsequently explored. Overall, 12,192 and 16,461 features were acquired in the breast milk and stool samples, respectively. Following quality control and suspect screening, 562 and 864 features remained, respectively, with 149 of these features present in both matrices. Taking advantage of 242 authentic reference standards measured for confirmatory purposes of food bio-actives and toxicants, 34 features in breast milk and 68 features in stool were identified and semi-quantified. Moreover, 51 and 78 features were annotated with spectral library matching, as well as 416 and 652 by in silico fragmentation tools in breast milk and stool, respectively. The analytical workflow proved its versatility to simultaneously determine a diverse panel of chemical classes including mycotoxins, endocrine-disrupting chemicals (EDCs), antibiotics, plasticizers, perfluorinated alkylated substances (PFAS), and pesticides, although it was originally optimized for polyphenols. Spearman rank correlation of the identified features revealed significant correlations between chemicals of the same classification such as polyphenols. One-way ANOVA and differential abundance analysis of the data obtained from stool samples revealed that molecules of plant-based origin elevated as complementary foods were introduced to the infants' diets. Annotated compounds in the stool, such as tricetin, positively correlated with the genus Blautia. Moreover, vulgaxanthin negatively correlated with Escherichia-Shigella. Despite the limited sample size, this exploratory study provides high-quality exposure data of matched biospecimens obtained from mother-infant pairs in sub-Saharan Africa and shows potential correlations between the chemical exposome and the gut microbiome.

Mushroom Tyrosinase: Six Isoenzymes Catalyzing Distinct Reactions.

"Mushroom tyrosinase" from the common button mushroom is the most frequently used source of tyrosinase activity, both for basic and applied research. Here, the complete tyrosinase family from Agaricus bisporus var. bisporus (abPPO1-6) was cloned from mRNA and expressed heterologously using a single protocol. All six isoenzymes accept a wide range of phenolic and catecholic substrates, but display pronounced differences in their specificity and enzymatic reaction rate. AbPPO3 ignores γ-l-glutaminyl-4-hydroxybenzene (GHB), a natural phenol present in mM concentrations in A. bisporus, while AbPPO4 processes 100 µM GHB at 4-times the rate of the catechol l-DOPA. All six AbPPOs are biochemically distinct enzymes fit for different roles in the fungal life cycle, which challenges the traditional concept of isoenzymes as catalyzing the same chemical reaction and varying only in secondary properties. Transferring this approach to other enzymes and organisms will greatly stimulate both the study of the in vivo function(s) of enzymes and the application of these highly efficient catalysts.

Polyphenol exposure of mothers and infants assessed by LC-MS/MS based biomonitoring in breast milk.

Exposure to polyphenols is relevant throughout critical windows of infant development, including the breastfeeding phase. However, the quantitative assessment of polyphenols in human breast milk has received limited attention so far, though polyphenols may positively influence infant health. Therefore, a targeted LC-MS/MS assay was developed to investigate 86 analytes representing different polyphenol classes in human breast milk. The sample preparation consisted of liquid extraction, salting out, freeze-out, and a dilution step. Overall, nearly 70% of the chemically diverse polyphenols fulfilled all strict validation criteria for full quantitative assessment. The remaining analytes did not fulfill all criteria at every concentration level, but can still provide useful semi-quantitative insights into nutritional and biomedical research questions. The limits of detection for all analyzed polyphenols were in the range of 0.0041-87 ng*mL-1, with a median of 0.17 ng*mL-1. Moreover, the mean recovery was determined to be 82% and the mean signal suppression and enhancement effect was 117%. The developed assay was applied in a proof-of-principle study to investigate polyphenols in breast milk samples provided by twelve Nigerian mothers at three distinct time points post-delivery. In total, 50 polyphenol analytes were detected with almost half being phenolic acids. Phase II metabolites, including genistein-7-ß-D-glucuronide, genistein-7-sulfate, and daidzein-7-ß-D-glucuronide, were also detected in several samples. In conclusion, the developed method was demonstrated to be fit-for-purpose to simultaneously (semi-) quantify a wide variety of polyphenols in breast milk. It also demonstrated that various polyphenols including their biotransformation products were present in breast milk and therefore likely transferred to infants where they might impact microbiome development and infant health.

Extraction, Purification, and Characterization of Olive (Olea europaea L., cv. Chemlal) Polyphenol Oxidase.

Among fruits susceptible to enzymatic browning, olive polyphenol oxidase (OePPO) stood out as being unisolated from a natural source until this study, wherein we successfully purified and characterized the enzyme. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) of heated and nonheated OePPO revealed distinct molecular weights of 35 and 54 kDa, respectively, indicative of its oligomeric nature comprising active and C-terminal subunits. OePPO displayed latency, fully activating with 5 mM SDS under optimal conditions of pH 7.5 and 15 °C. The enzyme demonstrated monophenolase activity and showcased the highest efficiency toward hydroxytyrosol. Despite its low optimal temperature, OePPO exhibited high thermal resistance, maintaining stability up to 90 °C. However, beyond this threshold, the oligomeric enzyme disassociated, yielding a denatured main subunit and C-terminal fragments. Six OePPO genes were found in the fruits. Tryptic digestion identified the enzyme as mature OePPO1 (INSDC OY733096), while mass spectrometry detected the active form mass alongside several C-terminal fragments, revealing potential cleavage sites (Gly407, Tyr408).

All-Inorganic Polyoxometalates Act as Superchaotropic Membrane Carriers.

Polyoxometalates (POMs) are known antitumoral, antibacterial, antiviral, and anticancer agents and considered as next-generation metallodrugs. Herein, a new biological functionality in neutral physiological media, where selected mixed-metal POMs are sufficiently stable and able to affect membrane transport of impermeable, hydrophilic, and cationic peptides (heptaarginine, heptalysine, protamine, and polyarginine) is reported. The uptake is observed in both, model membranes as well as cells, and attributed to the superchaotropic properties of the polyoxoanions. In view of the structural diversity of POMs these findings pave the way toward their biomedical application in drug delivery or for cell-biological uptake studies with biological effector molecules or staining agents.

Biochemical Investigations of Five Recombinantly Expressed Tyrosinases Reveal Two Novel Mechanisms Impacting Carbon Storage in Wetland Ecosystems.

Wetlands are globally distributed ecosystems characterized by predominantly anoxic soils, resulting from water-logging. Over the past millennia, low decomposition rates of organic matter led to the accumulation of 20-30% of the world's soil carbon pool in wetlands. Phenolic compounds are critically involved in stabilizing wetland carbon stores as they act as broad-scale inhibitors of hydrolytic enzymes. Tyrosinases are oxidoreductases capable of removing phenolic compounds in the presence of O2 by oxidizing them to the corresponding o-quinones. Herein, kinetic investigations (kcat and Km values) reveal that low-molecular-weight phenolic compounds naturally present within wetland ecosystems (including monophenols, diphenols, triphenols, and flavonoids) are accepted by five recombinantly expressed wetland tyrosinases (TYRs) as substrates. Investigations of the interactions between TYRs and wetland phenolics reveal two novel mechanisms that describe the global impact of TYRs on the wetland carbon cycle. First, it is shown that o-quinones (produced by TYRs from low-molecular-weight phenolic substrates) are capable of directly inactivating hydrolytic enzymes. Second, it is reported that o-quinones can interact with high-molecular-weight phenolic polymers (which inhibit hydrolytic enzymes) and remove them through precipitation. The balance between these two mechanisms will profoundly affect the fate of wetland carbon stocks, particularly in the wake of climate change.

Heterotrophy among Cyanobacteria.

Cyanobacteria have been studied in recent decades to investigate the principle mechanisms of plant-type oxygenic photosynthesis, as they are the inventors of this process, and their cultivation and research is much easier compared to land plants. Nevertheless, many cyanobacterial strains possess the capacity for at least some forms of heterotrophic growth. This review demonstrates that cyanobacteria are much more than simple photoautotrophs, and their flexibility toward different environmental conditions has been underestimated in the past. It summarizes the strains capable of heterotrophy known by date structured by their phylogeny and lists the possible substrates for heterotrophy for each of them in a table in the Supporting Information. The conditions are discussed in detail that cause heterotrophic growth for each strain in order to allow for reproduction of the results. The review explains the importance of this knowledge for the use of new methods of cyanobacterial cultivation, which may be advantageous under certain conditions. It seeks to stimulate other researchers to identify new strains capable of heterotrophy that have not been known so far.

Exposomic Biomonitoring of Polyphenols by Non-Targeted Analysis and Suspect Screening.

Polyphenols, prevalent in plants and fungi, are investigated intensively in nutritional and clinical settings because of their beneficial bioactive properties. Due to their complexity, analysis with untargeted approaches is favorable, which typically use high-resolution mass spectrometry (HRMS) rather than low-resolution mass spectrometry (LRMS). Here, the advantages of HRMS were evaluated by thoroughly testing untargeted techniques and available online resources. By applying data-dependent acquisition on real-life urine samples, 27 features were annotated with spectral libraries, 88 with in silico fragmentation, and 113 by MS1 matching with PhytoHub, an online database containing >2000 polyphenols. Moreover, other exogenous and endogenous molecules were screened to measure chemical exposure and potential metabolic effects using the Exposome-Explorer database, further annotating 144 features. Additional polyphenol-related features were explored using various non-targeted analysis techniques including MassQL for glucuronide and sulfate neutral losses, and MetaboAnalyst for statistical analysis. As HRMS typically suffers a sensitivity loss compared to state-of-the-art LRMS used in targeted workflows, the gap between the two instrumental approaches was quantified in three spiked human matrices (urine, serum, plasma) as well as real-life urine samples. Both instruments showed feasible sensitivity, with median limits of detection in the spiked samples being 10-18 ng/mL for HRMS and 4.8-5.8 ng/mL for LRMS. The results demonstrate that, despite its intrinsic limitations, HRMS can readily be used for comprehensively investigating human polyphenol exposure. In the future, this work is expected to allow for linking human health effects with exposure patterns and toxicological mixture effects with other xenobiotics.

Speciation atlas of polyoxometalates in aqueous solutions.

Speciation is the key parameter in solution chemistry that describes the composition, concentration, and oxidation state of each chemical form of an element present in a sample. The speciation study of complex polyatomic ions has remained challenging because of the large number of factors affecting stability and the limited number of direct methods. To address these challenges, we developed the speciation atlas of 10 polyoxometalates commonly used in catalytic and biological applications in aqueous solutions, where the speciation atlas provides both a species distribution database and a predictive model for other polyoxometalates to be used. Compiled for six different polyoxometalate archetypes with three types of addenda ions based on 1309 nuclear magnetic resonance spectra under 54 different conditions, the atlas has revealed a previously unknown behavior of polyoxometalates that may account for their potency as biological agents and catalysts. The atlas is intended to promote the interdisciplinary use of metal oxides in various scientific fields.

Synthesis, Characterization, and Antibacterial Activity of Ni-Substituted Krebs-type Sandwich-Tungstobismuthates Functionalized with Amino Acids.

Four new Ni-substituted Krebs-type sandwich-tungstobismuthates, K4Ni2[{Ni(ß-ala)(H2O)2}2{Ni(H2O)}2{Ni(H2O)(η2-ß-ala)}2(B-ß-BiW9O33)2]·49H2O {(ß-ala)4(Ni3)2(BiW9)2}, K3.5Na6.5[{Ni(η3-L-asp)}2(WO2)2(B-ß-BiW9O33)2]·36H2O·L-asp {(L-asp)2(NiW)2(BiW9)2}, K4Na6[{Ni(gly)(H2O)2}2(WO2)2(B-ß-BiW9O33)2]·86H2O {(gly)2(NiW)2(BiW9)2}, and K2Na8[{Ni(η2-serinol) (H2O)}2{Ni(H2O)2}2(B-ß-BiW9O33)2]·42H2O {(serinol)2Ni4(BiW9)2} have been synthesized by one-pot solution methods. All compounds have been characterized in the solid state by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), elemental and thermogravimetric analyses, and infrared spectroscopy (IR), as well as by UV-vis spectroscopy in solution. The antibacterial activity of all compounds was studied against four bacterial strains by the determination of the minimum inhibitory concentration (MIC). The results showed that only {(ß-ala)4(Ni3)2(BiW9)2} demonstrates antibacterial activity (MIC is in the range from 8 to 256 µg/mL) compared to three other Ni-Krebs sandwiches.

Immobilization of Agaricus bisporus Polyphenol Oxidase 4 on mesoporous silica: Towards mimicking key enzymatic processes in peat soils.

HYPOTHESIS: The use of immobilized enzyme-type biocatalysts to mimic specific processes in soil can be considered one of the most promising alternatives to overcome the difficulties behind the structural elucidation of riverine humic-derived iron-complexes. Herein, we propose that the immobilization of the functional mushroom tyrosinase, Agaricus bisporus Polyphenol Oxidase 4 (AbPPO4) on mesoporous SBA-15-type silica could contribute to the study of small aquatic humic ligands such as phenols. EXPERIMENTS: The silica support was functionalized with amino-groups in order to investigate the impact of surface charge on the tyrosinase loading efficiency as well as on the catalytic performance of adsorbed AbPPO4. The oxidation of various phenols was catalyzed by the AbPPO4-loaded bioconjugates, yielding high levels of conversion and confirming the retention of enzyme activity after immobilization. The structures of the oxidized products were elucidated by integrating chromatographic and spectroscopic techniques. We also evaluated the stability of the immobilized enzyme over a wide range of pH values, temperatures, storage-times and sequential catalytic cycles. FINDINGS: This is the first report where the latent AbPPO4 is confined within silica mesopores. The improved catalytic performance of the adsorbed AbPPO4 shows the potential use of these silica-based mesoporous biocatalysts for the preparation of a column-type bioreactor for in situ identification of soil samples.

Oxo-Replaced Polyoxometalates: There Is More than Oxygen.

The presence of oxo-ligands is one of the main required characteristics for polyoxometalates (POMs), although some oxygen ions in a metallic environment can be replaced by other nonmetals, while maintaining the POM structure. The replacement of oxo-ligands offers a valuable approach to tune the charge distribution and connected properties like reducibility and hydrolytic stability of POMs for the development of tailored compounds. By assessing the reported catalytic and biological applications and connecting them to POM structures, the present review provides a guideline for synthetic approaches and aims to stimulate further applications where the oxo-replaced compounds are superior to their oxo-analogues. Oxo-replacement in POMs deserves more attention as a valuable tool to form chemically activated precursors for the synthesis of novel structures or to upgrade established structures with extraordinary properties for challenging applications.

Ni12 tetracubane cores with slow relaxation of magnetization and efficient charge utilization for photocatalytic hydrogen evolution.

We report two Ni12 multicubane topologies enclosed in the polyanions [Ni12(OH)9(WO4)3(PO4)(B-α-PW9O34)3]21-{Ni12W30} and [Ni12(OH)9(HPO4)3(PO4)(B-α-PW9O34)(A-α-PW9O34)2]21-{Ni12W27} that magnetically behave as Ni12 units clearly distinguishing them from typical Ni4 cubanes as shown by magnetic studies together with high field and frequency electron paramagnetic resonance (HFEPR). Beyond the unprecedented static properties, {Ni12W30} shows the unusual coexistence of slow relaxation of the magnetization and a diamagnetic ground state (S = 0), providing the unique opportunity of studying the essentially elusive magnetic relaxation behavior in excited states. The cubane-topology dependent activity of {Ni12W30} and {Ni12W27} as homogeneous HER photocatalysts unveils the structural key features significant for the design of photocatalysts with efficient charge utilization exemplified by high quantum yields (QY) of 10.42% and 8.36% for {Ni12W30} and {Ni12W27}, respectively.

Biochemical characterization of Dimocarpus longan polyphenol oxidase provides insights into its catalytic efficiency.

The "dragon-eye" fruits produced by the tropical longan tree are rich in nutrients and antioxidants. They suffer from post-harvest enzymatic browning, a process for which mainly the polyphenol oxidase (PPO) family of enzymes is responsible. In this study, two cDNAs encoding the PPO have been cloned from leaves of Dimocarpus longan (Dl), heterologously expressed in Escherichia coli and purified by affinity chromatography. The prepro-DlPPO1 contains two signal peptides at its N-terminal end that facilitate transportation of the protein into the chloroplast stroma and to the thylakoid lumen. Removal of the two signal peptides from prepro-DlPPO1 yields pro-DlPPO1. The prepro-DlPPO1 exhibited higher thermal tolerance than pro-DlPPO1 (unfolding at 65 °C vs. 40 °C), suggesting that the signal peptide may stabilize the fold of DlPPO1. DlPPO1 can be classified as a tyrosinase because it accepts both monophenolic and diphenolic substrates. The pro-DlPPO1 exhibited the highest specificity towards the natural diphenol (-)-epicatechin (kcat/KM of 800 ± 120 s-1 mM-1), which is higher than for 4-methylcatechol (590 ± 99 s-1 mM-1), pyrogallol (70 ± 9.7 s-1 mM-1) and caffeic acid (4.3 ± 0.72 s-1 mM-1). The kinetic efficiencies of prepro-DlPPO1 are 23, 36, 1.7 and 4.7-fold lower, respectively, than those observed with pro-DlPPO1 for the four aforementioned diphenolic substrates. Additionally, docking studies showed that (-)-epicatechin has a lower binding energy than any other investigated substrate. Both kinetic and in-silico studies strongly suggest that (-)-epicatechin is a good substrate of DlPPO1 and ascertain the affinity of PPOs towards specific flavonoid compounds.

The Preyssler-Type Polyoxotungstate Exhibits Anti-Quorum Sensing, Antibiofilm, and Antiviral Activities.

The increase in bacterial resistance to antibiotics has led researchers to find new compounds or find combinations between different compounds with potential antibacterial action and with the ability to prevent the development of antibiotic resistance. Polyoxotungstates (POTs) are inorganic clusters that may fulfill that need, either individually or in combination with antibiotics. Herein, we report the ability of the polyoxotungstates (POTs) with Wells-Dawson P2W18, P2W17, P2W15, and Preyssler P5W30 type structures to differently affect Gram-negative and Gram-positive microorganisms, either susceptible or resistant to antibiotics. The compound P5W30 showed the highest activity against the majority of the tested bacterial strains in comparison with the other tested POTs (P2W15, P2W17 and P2W18) that did not show inhibition zones for the Gram-negative bacteria, A. baumanii I73775, E. coli DSM 1077, E. coli I73194, K. pneumoniae I7092374, and P. aeruginosa C46281). Generally, the results evidenced that Gram-positive bacteria are more susceptible to the POTs tested. The compound P5W30 was the one most active against S. aureus ATCC 6538 and MRSA16, reaching <0.83 mg·mL−1 (100 µM) and 4.96 mg·mL−1 (600 µM), respectively. Moreover, it was verified by NMR spectroscopy that the most promising POT, P5W30, remains intact under all the experimental conditions, after 24 h at 37 °C. This prompted us to further evaluate the anti-quorum sensing activity of P5W30 using the biosensor Chromobacterium violaceum CV026, as well as its antibiofilm activity both individually and in combination with the antibiotic cefoxitin against the methicillin-resistant Staphylococcus aureus 16 (MRSA16). P5W30 showed a synergistic antibacterial effect with the antibiotic cefoxitin and chloramphenicol against MRSA16. Moreover, the antibiofilm activity of P5W30 was more pronounced when used individually, in comparison with the combination with the antibiotic cefoxitin. Finally, the antiviral activity of P5W30 was tested using the coliphage Qß, showing a dose-dependent response. The maximum inactivation was observed at 750 µM (6.23 mg·mL−1). In sum, P5W30 shows anti-quorum sensing and antibiofilm activities besides being a potent antibacterial agent against S. aureus and to exhibit antiviral activities against enteric viruses.

Inhibition of SERCA and PMCA Ca2+-ATPase activities by polyoxotungstates.

Plasma membrane calcium ATPases (PMCA) and sarco(endo) reticulum calcium ATPases (SERCA) are key proteins in the maintenance of calcium homeostasis. Herein, we compare for the first time the inhibition of SERCA and PMCA calcium pumps by several polyoxotungstates (POTs), namely by Wells-Dawson phosphotungstate anions [P2W18O62]6- (intact, {P2W18}), [P2W17O61]10- (monolacunary, {P2W17}), [P2W15O56]12- (trilacunary, {P2W15}), [H2P2W12O48]12- (hexalacunary, {P2W12}), [H3P2W15V3O62]6- (trivanadium-substituted, {P2W15V3}) and by Preyssler-type anion [NaP5W30O110]14- ({P5W30}). The speciation in the solutions of tested POTs was investigated by 31P and 51V NMR spectroscopy. The tested POTs inhibited SERCA Ca2+-ATPase activity, whereby the Preyssler POT showed the strongest effect, with an IC50 value of 0.37 µM. For {P2W17} and {P2W15V3} higher IC50 values were determined: 0.72 and 0.95 µM, respectively. The studied POTs showed to be more potent inhibitors of PMCA Ca2+-ATPase activity, with lower IC50 values for {P2W17}, {P5W30} and {P2W15V3}.

The Novel Role of Tyrosinase Enzymes in the Storage of Globally Significant Amounts of Carbon in Wetland Ecosystems.

Over the last millennia, wetlands have been sequestering carbon from the atmosphere via photosynthesis at a higher rate than releasing it and, therefore, have globally accumulated 550 × 1015 g of carbon, which is equivalent to 73% of the atmospheric carbon pool. The accumulation of organic carbon in wetlands is effectuated by phenolic compounds, which suppress the degradation of soil organic matter by inhibiting the activity of organic-matter-degrading enzymes. The enzymatic removal of phenolic compounds by bacterial tyrosinases has historically been blocked by anoxic conditions in wetland soils, resulting from waterlogging. Bacterial tyrosinases are a subgroup of oxidoreductases that oxidatively remove phenolic compounds, coupled to the reduction of molecular oxygen to water. The biochemical properties of bacterial tyrosinases have been investigated thoroughly in vitro within recent decades, while investigations focused on carbon fluxes in wetlands on a macroscopic level have remained a thriving yet separated research area so far. In the wake of climate change, however, anoxic conditions in wetland soils are threatened by reduced rainfall and prolonged summer drought. This potentially allows tyrosinase enzymes to reduce the concentration of phenolic compounds, which in turn will increase the release of stored carbon back into the atmosphere. To offer compelling evidence for the novel concept that bacterial tyrosinases are among the key enzymes influencing carbon cycling in wetland ecosystems first, bacterial organisms indigenous to wetland ecosystems that harbor a TYR gene within their respective genome (tyr+) have been identified, which revealed a phylogenetically diverse community of tyr+ bacteria indigenous to wetlands based on genomic sequencing data. Bacterial TYR host organisms covering seven phyla (Acidobacteria, Actinobacteria, Bacteroidetes, Firmicutes, Nitrospirae, Planctomycetes, and Proteobacteria) have been identified within various wetland ecosystems (peatlands, marshes, mangrove forests, bogs, and alkaline soda lakes) which cover a climatic continuum ranging from high arctic to tropic ecosystems. Second, it is demonstrated that (in vitro) bacterial TYR activity is commonly observed at pH values characteristic for wetland ecosystems (ranging from pH 3.5 in peatlands and freshwater swamps to pH 9.0 in soda lakes and freshwater marshes) and toward phenolic compounds naturally present within wetland environments (p-coumaric acid, gallic acid, protocatechuic acid, p-hydroxybenzoic acid, caffeic acid, catechin, and epicatechin). Third, analyzing the available data confirmed that bacterial host organisms tend to exhibit in vitro growth optima at pH values similar to their respective wetland habitats. Based on these findings, it is concluded that, following increased aeration of previously anoxic wetland soils due to climate change, TYRs are among the enzymes capable of reducing the concentration of phenolic compounds present within wetland ecosystems, which will potentially destabilize vast amounts of carbon stored in these ecosystems. Finally, promising approaches to mitigate the detrimental effects of increased TYR activity in wetland ecosystems and the requirement of future investigations of the abundance and activity of TYRs in an environmental setting are presented.

Immobilization of a [CoIIICoII(H2O)W11O39]7- Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction.

The ongoing transition to renewable energy sources and the implementation of artificial photosynthetic setups call for an efficient and stable water oxidation catalyst (WOC). Here, we heterogenize a molecular all-inorganic [CoIIICoII(H2O)W11O39]7- ({CoIIICoIIW11}) Keggin-type polyoxometalate (POM) onto a model TiO2 surface, employing a 3-aminopropyltriethoxysilane (APTES) linker to form a novel heterogeneous photosystem for light-driven water oxidation. The {CoIIICoIIW11}-APTES-TiO2 hybrid is characterized using a set of spectroscopic and microscopic techniques to reveal the POM integrity and dispersion to elucidate the POM/APTES and APTES/TiO2 binding modes as well as to visualize the attachment of individual clusters. We conduct photocatalytic studies under heterogeneous and homogeneous conditions and show that {CoIIICoIIW11}-APTES-TiO2 performs as an active light-driven WOC, wherein {CoIIICoIIW11} acts as a stable co-catalyst for water oxidation. In contrast to the homogeneous WOC performance of this POM, the heterogenized photosystem yields a constant WOC rate for at least 10 h without any apparent deactivation, demonstrating that TiO2 not only stabilizes the POM but also acts as a photosensitizer. Complementary studies using photoluminescence (PL) emission spectroscopy elucidate the charge transfer mechanism and enhanced WOC activity. The {CoIIICoIIW11}-APTES-TiO2 photocatalyst serves as a prime example of a hybrid homogeneous-heterogeneous photosystem that combines the advantages of solid-state absorbers and well-defined molecular co-catalysts, which will be of interest to both scientific communities and applications in photoelectrocatalysis and CO2 reduction.

Quantifying up to 90 polyphenols simultaneously in human bio-fluids by LC-MS/MS.

Establishing a method for human biomonitoring (HBM) of polyphenols enables the assessment of internal concentrations of these food bio-actives and the correlation with potential health effects such as antioxidant or anti-inflammatory properties. Thus, a targeted LC-MS/MS method for quantifying up to 90 analytes, representing the main polyphenol classes including flavanones, isoflavones, stilbenes, and phenolic acids, was developed for human urine, serum, and plasma. The method was established for low sample volumes and with a cost and time efficient sample preparation protocol for high-throughput, which is critical for its application in large cohort and exposome-wide association studies. On average, the sample preparation yielded extraction efficiencies of 98% for urine, 98% for serum, and 87% for plasma. Limits of detection were between 0.11 ng mL-1 and 300 ng mL-1 for urine, 0.12 ng mL-1 and 190 ng mL-1 for serum, and 0.12 ng mL-1 and 340 ng mL-1 for plasma, excluding one analyte. In-house validation revealed that 66, 49, and 64 analytes for urine, serum, and plasma, respectively, fulfilled all stringent requirements, that are usually utilized for tailored single analyte methods, at all evaluated concentration levels. After validation, this method was applied in a proof-of-principle study that detected 39 polyphenols in urine. Changes in the concentrations of the analytes after the ingestion of a high polyphenol smoothie was examined over 24 h. The study further confirmed that the majority of polyphenols detected were phenolic acids, and phase II conjugated metabolites were more abundant than their respective non-conjugated forms.

Trisubstituted 4f- and 4d tungstoantimonates as artificial phosphoesterases for nerve agent degradation.

Three new trisubstituted 4f- and 4d tungstoantimonates (TA) K3Na21[(M(CH3COO))3(HPO3)(WO4)(SbW9O33)3]·nH2O {M3(HPO3)Sb3W28} (M = GdIII, YIII, YbIII, n = 35-36) were synthesized using a double-template synthetic approach. Following their characterization in the solid state employing single- and powder X-ray diffraction (XRD), IR-spectroscopy, and elemental - and thermogravimetric analyses (TGA), {M3(HPO3)Sb3W28} were subjected to a comprehensive set of solution characterization methods including UV/vis- and multinuclear 31P and 13C NMR spectroscopy. All representatives were shown to be highly active, recyclable, and stable Lewis-acid catalysts towards the nerve agent simulant O,O-dimethyl O-(4-nitrophenyl) phosphate (DMNP) at neutral pH (in Tris-HCl [125 mM] at pD 7.0 25 °C). Control experiments showing catalytic activity of the unsubstituted trilacunary TA [SbW9O33]9- suggest the non-innocence of Tris in the DMNP hydrolysis for the first time.