ABSTRACT
The development of a sustainable and environmentally friendly energy economy encompasses efficient hydrogen production from renewable energy via electrolysis. In this context, great efforts have recently been dedicated to the development of more efficient and cost-effective electrocatalysts. Understanding the mechanism of the oxygen evolution reaction (OER) on transition metal oxide catalysts is of great interest, but the reaction and system complexity render the characterization of active sites and the understanding of reaction mechanisms challenging. Time resolved Quick X-ray Absorption Spectroscopy (XAS) can provide dynamic snapshots of the electronic and local structure of nanocatalysts, revealing the 'real active phase' of the catalyst, which can substantially differ from the as-prepared catalyst powder or the catalyst in form of an electrode under non-operating conditions. In this contribution, several examples will be presented showing how operando XAS can reveal catalyst-support interactions, changes in the reaction mechanism, and dynamic reversible/irreversible changes in the electronic and local structure of OER catalysts.
ABSTRACT
In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due to the high tridentate-ligand-centered character of the excited states, the P-related radiative rate is rather low while showing a significant boost upon replacement of the P donor by heavier As- and Sb-based units. The syntheses of the three complexes containing PPh3, AsPh3, and SbPh3 were completed by unambiguous characterization of the clean products using exact mass spectrometry, X-ray diffractometry, bidimensional NMR, and 121Sb-Mössbauer spectroscopy (for [PtL(SbPh3)]) as well as steady state and time-resolved photoluminescence spectroscopies. Hence, it was shown that the hybridization defects of the Vth main-group atoms can be overcome by complexation with the Pt center. Notably, the enhancement of the radiative rate constants mediated by heavier coligands was achieved without significantly influencing the character of the excited states. A rationalization of the results was achieved by TD-DFT. Even though the Bi-based homologue was not accessible due to phenylation side reactions, the experimental data allowed a reasonable extrapolation of the structural features whereas the hybridization defects and the excited state properties related to the Bi-species and its phosphorescence rate can be predicted by theory. The three complexes showed an interesting antiprotozoal activity, which was unexpectedly notorious for the P-containing complex. This work could pave the road toward new efficient materials for optoelectronics and novel antiparasitic drugs.
ABSTRACT
Over the past decades, the electrochemical CO2-reduction reaction (CO2RR) has emerged as a promising option for facilitating intermittent energy storage while generating industrial raw materials of economic relevance such as CO. Recent studies have reported that Au-Cu bimetallic nanocatalysts feature a superior CO2-to-CO conversion as compared with the monometallic components, thus improving the noble metal utilization. Under this premise and with the added advantage of a suppressed H2-evolution reaction due to absence of a carbon support, herein, we employ bimetallic Au3Cu and AuCu aerogels (with a web thickness ≈7 nm) as CO2-reduction electrocatalysts in 0.5 M KHCO3 and compare their performance with that of a monometallic Au aerogel. We supplement this by investigating how the CO2RR-performance of these materials is affected by their surface composition, which we modified by systematically dissolving a part of their Cu-content using cyclic voltammetry (CV). To this end, the effect of this CV-driven composition change on the electrochemical surface area is quantified via Pb underpotential deposition, and the local structural and compositional changes are visually assessed by employing identical-location transmission electron microscopy and energy-dispersive X-ray analyses. When compared to the pristine aerogels, the CV-treated samples displayed superior CO Faradaic efficiencies (≈68 vs ≈92% for Au3Cu and ≈34 vs ≈87% for AuCu) and CO partial currents, with the AuCu aerogel outperforming the Au3Cu and Au counterparts in terms of Au-mass normalized CO currents among the CV-treated samples.
ABSTRACT
In the search for new bioactive agents against the infectious pathogen responsible for the neglected tropical disease (NTD) mycetoma, we tested a collection of 27 essential oils (EOs) in vitro against Madurella mycetomatis, the primary pathogen responsible for the fungal form of mycetoma, termed eumycetoma. Among this series, the EO of Santalum album (Santalaceae), i.e., East Indian sandalwood oil, stood out prominently with the most potent inhibition in vitro. We, therefore, directed our research toward 15 EOs of Santalum species of different geographical origins, along with two samples of EOs from other plant species often commercialized as "sandalwood oils". Most of these EOs displayed similar strong activity against M. mycetomatis in vitro. All tested oils were thoroughly analyzed by GC-QTOF MS and most of their constituents were identified. Separation of the sandalwood oil into the fractions of sesquiterpene hydrocarbons and alcohols showed that its activity is associated with the sesquiterpene alcohols. The major constituents, the sesquiterpene alcohols (Z)-α- and (Z)-ß-santalol were isolated from the S. album oil by column chromatography on AgNO3-coated silica. They were tested as isolated compounds against the fungus, and (Z)-α-santalol was about two times more active than the ß-isomer.
Subject(s)
Madurella , Mycetoma , Oils, Volatile , Plant Oils , Santalum , Sesquiterpenes , Madurella/drug effects , Plant Oils/pharmacology , Plant Oils/chemistry , Oils, Volatile/pharmacology , Oils, Volatile/chemistry , Mycetoma/microbiology , Mycetoma/drug therapy , Santalum/chemistry , Sesquiterpenes/pharmacology , Sesquiterpenes/chemistry , Antifungal Agents/pharmacology , Antifungal Agents/chemistry , Microbial Sensitivity TestsABSTRACT
Co-based catalysts are promising candidates to replace Ir/Ru-based oxides for oxygen evolution reaction (OER) catalysis in an acidic environment. However, both the reaction mechanism and the active species under acidic conditions remain unclear. In this study, by combining surface-sensitive soft X-ray absorption spectroscopy characterization with electrochemical analysis, we discover that the acidic OER activity of Co-based catalysts are determined by their surface oxidation/spin state. Surfaces composed of only high-spin CoII are found to be not active due to their unfavorable water dissociation to form CoIII-OH species. By contrast, the presence of low-spin CoIII is essential, as it promotes surface reconstruction of Co oxides and, hence, OER catalysis. The correlation between OER activity and Co oxidation/spin state signifies a breakthrough in defining the structure-activity relationship of Co-based catalysts for acidic OER, though, interestingly, such a relationship does not hold in alkaline and neutral environments. These findings not only help to design efficient acidic OER catalysts, but also deepen the understanding of the reaction mechanism.
ABSTRACT
Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite family RBaCuFeO5+δ (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with ab initio DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe3+ is the transition metal cation the most prone to donate electrons. We also show that similar R3+/Ba2+ ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples (δ > 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO5.49), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting.
ABSTRACT
Alstonia boonei De Wild is a common plant in West Africa used in traditional medicine for various indications. While the stem bark has frequently been investigated, not much is known about the phytochemistry and bioactivity of the leaves. Within the current study, the major alkaloids of a hydroethanolic leaf extract were therefore isolated and characterized by MS, NMR, and ECD. This led to the identification of alstoboonine 1, a new ulean-type alkaloid, along with eight previously reported indole alkaloids, 15-hydroxyangustilobine A (2), 6,7-seco-angustilobine B (3), 6,7-seco-19,20-α-epoxyangustilobine B (4), alstrostine E (5), alstrostine C (6), alstrostine D (7), 12-methoxyechitamidine (8), and 19-oxo-12-methoxyechitamidine (9). 1 was moderately active in vitro against Plasmodium falciparum NF54 (IC50 6.9 µM), but inactive against other protozoan parasites (Trypanosoma brucei, Trypanosoma cruzi, Leishmania donovani). No significant cytotoxic effects were observed in L6 rat skeletal myoblast cells and MCF-7 breast cancer cells. Similarly, compounds 3 to 9 did not show cytotoxicity in MCF-7 cells. Due to the reported traditional use of the plant as an anthelmintic, the major alkaloids 2, 5, 6, and 8 were tested against the nematode Caenorhabditis elegans. Nematicidal effects were observed for 6 (LC50 400 µM), whereas 2, 5, and 8 were inactive.
Subject(s)
Alkaloids , Alstonia , Humans , Rats , Animals , Plant Extracts/pharmacology , Plant Extracts/chemistry , Alstonia/chemistry , Alkaloids/pharmacology , Indole Alkaloids/pharmacology , Indole Alkaloids/chemistry , MCF-7 Cells , Plasmodium falciparum , Plant LeavesABSTRACT
The parasites Trypanosoma brucei (Tb) and Leishmania major (Lm) cause the tropical diseases sleeping sickness, nagana, and cutaneous leishmaniasis. Every year, millions of humans, as well as animals, living in tropical to subtropical climates fall victim to these illnesses' health threats. The parasites' frequent drug resistance and widely spread natural reservoirs heavily impede disease prevention and treatment. Due to pteridine auxotrophy, trypanosomatid parasites have developed a peculiar enzyme system consisting of dihydrofolate reductase-thymidylate synthase (DHFR-TS) and pteridine reductase 1 (PTR1) to support cell survival. Extending our previous studies, we conducted a comparative study of the T. brucei (TbDHFR, TbPTR1) and L. major (LmDHFR, LmPTR1) enzymes to identify lead structures with a dual inhibitory effect. A pharmacophore-based in silico screening of three natural product databases (approximately 4880 compounds) was performed to preselect possible inhibitors. Building on the in silico results, the inhibitory potential of promising compounds was verified in vitro against the recombinant DHFR and PTR1 of both parasites using spectrophotometric enzyme assays. Twelve compounds were identified as dual inhibitors against the Tb enzymes (0.2 µM < IC50 < 85.1 µM) and ten against the respective Lm enzymes (0.6 µM < IC50 < 84.5 µM). These highly promising results may represent the starting point for the future development of new leads and drugs utilizing the trypanosomatid pteridine metabolism as a target.
Subject(s)
Leishmania major , Trypanosoma brucei brucei , Trypanosomiasis, African , Humans , Animals , Tetrahydrofolate Dehydrogenase/metabolism , Pteridines/chemistry , Trypanosomiasis, African/drug therapyABSTRACT
GluN2B subunit-containing N-methyl-d-aspartate (NMDA) receptors have been implicated in various neurological disorders. Nonetheless, a validated fluorine-18 labeled positron emission tomography (PET) ligand for GluN2B imaging in the living human brain is currently lacking. The aim of this study was to develop a novel synthetic approach that allows an enantiomerically pure radiosynthesis of the previously reported PET radioligands (R)-[18F]OF-NB1 and (S)-[18F]OF-NB1 as well as to assess their in vitro and in vivo performance characteristics for imaging the GluN2B subunit-containing NMDA receptor in rodents. A novel synthetic approach was successfully developed, which allows for the enantiomerically pure radiosynthesis of (R)-[18F]OF-NB1 and (S)-[18F]OF-NB1 and the translation of the probe to the clinic. While both enantiomers were selective over sigma2 receptors in vitro and in vivo, (R)-[18F]OF-NB1 showed superior GluN2B subunit specificity by in vitro autoradiography and higher volumes of distribution in the rodent brain by small animal PET studies.
Subject(s)
Positron-Emission Tomography , Receptors, N-Methyl-D-Aspartate , Animals , Humans , Receptors, N-Methyl-D-Aspartate/metabolism , Positron-Emission Tomography/methods , Brain/diagnostic imaging , Brain/metabolism , Fluorine RadioisotopesABSTRACT
Product water transport via the microporous layer (MPL) and gas diffusion layer (GDL) substrate during polymer electrolyte fuel cell (PEFC) operation was directly and quantitatively observed by X-ray tomographic microscopy (XTM). The liquid water distribution in two types of MPLs with different pore size distributions (PSDs) was characterized as a function of the inlet gas relative humidity (RH) and current density under humid operating conditions at 45 °C. During the first minute of PEFC operation, liquid water mainly accumulated at the catalyst layer (CL)/MPL interface and in the GDL substrate close to the flow fields. Furthermore, under all tested conditions, saturation in the MPL was low (<25%), whereas under the rib, the saturation in the GDL was up to ca. 70%. Based on these XTM results, it is confirmed that in the high porosity MPLs, vapor transport was non-negligible even at high humidity conditions. Therefore, on top of the widely discussed MPL pore size and its distribution, it is proposed that the lower thermal conductivity from the high porosity of MPLs can also be a main cause of promoted vapor transport, reducing water saturation near the CL.
ABSTRACT
Dear readers, authors, reviewers, editors, coworkers and staff of Molecules, [...].
ABSTRACT
Arnica montana L. (Asteraceae) has a long and successful tradition in Europe as herbal medicine. Arnica flowers (i.e., the flowerheads of Arnica montana) are monographed in the European Pharmacopoeia (Ph. Eur.), and a European Union herbal monograph exists, in which its use as traditional herbal medicine is recommended. According to this monograph, Arnica flowers (Arnicae flos Ph. Eur.) and preparations thereof may be used topically to treat blunt injuries and traumas, inflammations and rheumatic muscle and joint complaints. The main bioactive constituents are sesquiterpene lactones (STLs) of the helenanolide type. Among these, a variety of esters of helenalin and 11α,13-dihydrohelenalin with low-molecular-weight carboxylic acids, namely, acetic, isobutyric, methacrylic, methylbutyric as well as tiglic acid, represent the main constituents, in addition to small amounts of the unesterified parent STLs. A plethora of reports exist on the pharmacological activities of these STLs, and it appears unquestioned that they represent the main active principles responsible for the herbal drug's efficacy. It has been known for a long time, however, that considerable differences in the STL pattern occur between A. montana flowers from plants growing in middle or Eastern Europe with some originating from the Iberic peninsula. In the former, Helenalin esters usually predominate, whereas the latter contains almost exclusively 11α,13-Dihydrohelenalin derivatives. Differences in pharmacological potency, on the other hand, have been reported for the two subtypes of Arnica-STLs in various instances. At the same time, it has been previously proposed that one should distinguish between two subspecies of A. montana, subsp. montana occurring mainly in Central and Eastern Europe and subsp. atlantica in the southwestern range of the species distribution, i.e., on the Iberian Peninsula. The question hence arises whether or not the geographic origin of Arnica montana flowers is of any relevance for the medicinal use of the herbal drug and the pharmaceutical quality, efficacy and safety of its products and whether the chemical/pharmacological differences should not be recognized in pharmacopoeia monographs. The present review attempts to answer these questions based on a summary of the current state of botanical, phytochemical and pharmacological evidence.
ABSTRACT
The phytochemical investigation of the ethylacetate fraction of an ethanolic extract obtained from the stem bark of Ficus sagittifolia (Moraceae) led to the isolation of four flavonoids: (2R)-eriodictyol (1), 2'- hydroxygenistein (2), erycibenin A (3), and genistein (4); a dihydrobenzofuran: moracin P (5); a coumarin: peucedanol (6); and an apocarotenoid terpenoid: dihydrophaseic acid (7). These were identified via 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and ultra-high-resolution liquid chromatography-quadrupole time-of-flight mass spectroscopy (UHPLC-QTOF MS). Moracin P (5) is being reported for the first time in the genus Ficus, while the others are known compounds (1-4 and 6-7) isolated previously from the genus but being reported for the first time from the species F. sagittifolia. Their antimicrobial activity against various pathogens (five bacteria: Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus aureus, and Salmonella typhi; two fungi: Aspergillus niger and Candida albicans) was tested. The mixture of genistein and moracin P (4+5) exhibited strong activity against K. pneumoniae (MIC < 0.0039 mg/mL), whereas dihydrophaseic acid (7) was the most active against P. aeruginosa and A. niger (MIC = 0.0078 and <0.0039 mg/mL, respectively). These compounds might be considered potential antimicrobial agents with the potential to be starting points for the development of antimicrobial drugs.
ABSTRACT
The use of hydrocarbon-based proton conducting membranes in fuel cells is currently hampered by the insufficient durability of the material in the device. Membrane aging is triggered by the presence of reactive intermediates, such as HOâ , which attack the polymer and eventually lead to chain breakdown and membrane failure. An adequate antioxidant strategy tailored towards hydrocarbon-based ionomers is therefore imperative to improve membrane lifetime. In this work, we perform studies on reaction kinetics using pulse radiolysis and γ-radiolysis as well as fuel cell experiments to demonstrate the feasibility of increasing the stability of hydrocarbon-based membranes against oxidative attack by implementing a Nature-inspired antioxidant strategy. We found that metalated-porphyrins are suitable for damage transfer and can be used in the fuel cell membrane to reduce membrane aging with a low impact on fuel cell performance.
ABSTRACT
Natural products (NPs) from plants, fungi, animals, and microorganisms have historically played important roles in drug discovery [...].
Subject(s)
Biological Products , Animals , Biological Products/pharmacology , Biological Products/therapeutic use , Drug Discovery , Fungi , PlantsABSTRACT
Leishmaniasis, a parasitic disease that represents a threat to the life of millions of people around the globe, is currently lacking effective treatments. We have previously reported on the antileishmanial activity of a series of synthetic 2-phenyl-2,3-dihydrobenzofurans and some qualitative structure-activity relationships within this set of neolignan analogues. Therefore, in the present study, various quantitative structure-activity relationship (QSAR) models were created to explain and predict the antileishmanial activity of these compounds. Comparing the performance of QSAR models based on molecular descriptors and multiple linear regression, random forest, and support vector regression with models based on 3D molecular structures and their interaction fields (MIFs) with partial least squares regression, it turned out that the latter (i.e., 3D-QSAR models) were clearly superior to the former. MIF analysis for the best-performing and statistically most robust 3D-QSAR model revealed the most important structural features required for antileishmanial activity. Thus, this model can guide decision-making during further development by predicting the activity of potentially new leishmanicidal dihydrobenzofurans before synthesis.
Subject(s)
Antiprotozoal Agents , Leishmaniasis , Humans , Quantitative Structure-Activity Relationship , Antiprotozoal Agents/pharmacology , Antiprotozoal Agents/chemistry , Molecular ConformationABSTRACT
Non-noble metal catalysts (NNMCs) hold the potential to replace the expensive Pt-based materials currently used to speed up the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes, but they feature poor durability that inhibits their implementation in commercial PEMFCs. This performance decay is commonly ascribed to the operative demetallation of their ORR-active sites, the electro-oxidation of the carbonaceous matrix that hosts these active centers, and/or the chemical degradation of the ionomer, active sites, and/or carbon support by radicals derived from the H2O2 produced as an ORR by-product. However, little is known regarding the relative contributions of these mechanisms to the overall PEMFC performance loss. With this motivation, in this study, we combined four degradation protocols entailing different cathode gas feeds (i.e., air vs N2), potential hold values, and durations to decouple the relative impact of the above deactivation mechanisms to the overall performance decay. Our results indicate that H2O2-related instability does not depend on the operative voltage but only on the ORR charge. Moreover, the electro-oxidation of the carbon matrix at high potentials (which for the catalyst tested herein triggers at 0.7 V) seems to be more detrimental to the NNMCs' activity than the demetallation occurring at low potentials.
ABSTRACT
The unassisted cold-start capability of polymer electrolyte fuel cells (PEFCs) remains challenging for large-scale automotive applications. Various studies have shown that the freezing of produced water at the cathode catalyst layer (CL) and gas diffusion layer (GDL) interface blocks the oxidant gas and leads to a cold-start failure. However, the impact of GDL properties, including substrate, size, and hydrophobicity, on the freezing behavior of supercooled water is yet to be thoroughly investigated. We use differential scanning calorimetry to perform non-isothermal calorimetric measurements on untreated and waterproofed GDLs (Toray TGP-H-060, Freudenberg H23). By conducting a large number of experiments (>100) for each type of GDL, we obtained the corresponding distribution of onset freezing temperature (Tonset) and found noticeable sample-to-sample variations in both untreated and waterproofed GDLs. Furthermore, ice crystallization is affected by GDL wettability, coating load, coating distribution, and GDL size, whereas the impact of the GDL substrate and saturation level is not apparent. The Tonset distribution allows for predicting the capability of PEFC freeze-start and the freezing probability of residual water at a given subzero temperature. Our work paves the way for GDL modifications toward the improved cold-start capability of PEFC by identifying and avoiding the features that systematically trigger the freezing of supercooled water with high probability.
ABSTRACT
In recent years, operando/in situ X-ray absorption spectroscopy (XAS) has become an important tool in the electrocatalysis community. However, the high catalyst loadings often required to acquire XA-spectra with a satisfactory signal-to-noise ratio frequently imply the use of thick catalyst layers (CLs) with large ion- and mass-transport limitations. To shed light on the impact of this variable on the spectro-electrochemical results, in this study we investigate Pd-hydride formation in carbon-supported Pd-nanoparticles (Pd/C) and an unsupported Pd-aerogel with similar Pd surface areas but drastically different morphologies and electrode packing densities. Our in situ XAS and rotating disk electrode (RDE) measurements with different loadings unveil that the CL-thickness largely determines the hydride formation trends inferred from spectro-electrochemical experiments, therewith calling for the minimization of the CL-thickness in such experiments and the use of complementary thin-film control measurements.
ABSTRACT
The oleo-gum resin of Commiphora myrrha (Nees) Engl. has a long history of medicinal use, although many of its constituents are still unknown. In the present investigation, 34 secondary metabolites were isolated from myrrh resin using different chromatographic techniques (silica flash chromatography, CPC, and preparative HPLC) and their structures were elucidated with NMR spectroscopy, HRESIMS, CD spectroscopy, and ECD calculations. Among the isolated substances are seven sesquiterpenes (1-7), one disesquiterpene (8), and two triterpenes (23, 24), which were hitherto unknown, and numerous substances are described here for the first time for C. myrrha or the genus Commiphora. Furthermore, the effects of selected terpenes on cervix cancer cells (HeLa) were studied in an MTT-based in vitro assay. Three triterpenes were observed to be the most toxic with moderate IC50 values of 60.3 (29), 74.5 (33), and 78.9 µM (26). Due to the different activity of the structurally similar triterpenoids, the impact of different structural elements on the cytotoxic effect could be discussed and linked to the presence of a 1,2,3-trihydroxy substructure in the A ring. The influence on TNF-α dependent expression of the intercellular adhesion molecule 1 (ICAM-1) in human microvascular endothelial cells (HMEC-1) was also tested for 4-6, 9-11, 17, 18, 20, and 27 in vitro, but revealed less than 20% ICAM-1 reduction and, therefore, no significant anti-inflammatory activity.