Recent advances in discovery and biosynthesis of natural products from myxobacteria: an overview from 2017 to 2023.

Covering: 2017.01 to 2023.11Natural products biosynthesized by myxobacteria are appealing due to their sophisticated chemical skeletons, remarkable biological activities, and intriguing biosynthetic enzymology. This review aims to systematically summarize the advances in the discovery methods, new structures, and bioactivities of myxobacterial NPs reported in the period of 2017-2023. In addition, the peculiar biosynthetic pathways of several structural families are also highlighted.

Highly Selective CO2 Electroreduction to C2H4 Using a Dual-Sites Cu(II) Porphyrin Framework Coupled with Cu2O Nanoparticles via a Synergetic-Tandem Strategy.

Low *CO coverage on the active sites is a major hurdle in the tandem electrocatalysis, resulting in unsatisfied C2H4 production efficiencies. In this work, we developed a synergetic-tandem strategy to construct a copper-based composite catalyst for the electroreduction of CO2 to C2H4, which was constructed via the template-directed polymerization of ultrathin Cu(II) porphyrin organic framework incorporating atomically isolated Cu(II) porphyrin and Cu(II) bipyridine sites on a carbon nanotube (CNT) scaffold, and then Cu2O nanoparticles were uniformly dispersed on the CNT scaffold. The presence of dual active sites within the Cu(II) porphyrin organic framework create a synergetic effect, leading to an increase in local *CO availability to enhance the C-C coupling step implemented on the adjacent Cu2O nanoparticles for further C2H4 production. Accordingly, the resultant catalyst affords an exceptional CO2-to-C2H4 Faradaic efficiency (FEC2H4) of 71.0 % at -1.1 V vs reversible hydrogen electrode (RHE), making it one of the most effective copper-based tandem catalysts reported to date. The superior performance of the catalyst is further confirmed through operando infrared spectroscopy and theoretic calculations.

Constructing a Myxobacterial Natural Product Database to Facilitate NMR-Based Metabolomics Bioprospecting of Myxobacteria.

Myxobacteria are fascinating prokaryotes featuring a potent capacity for producing a wealth of bioactive molecules with intricate chemical topology as well as intriguing enzymology, and thus it is critical to developing an efficient pipeline for bioprospecting. Herein, we construct the database MyxoDB, the first public compendium solely dedicated to myxobacteria, which enabled us to provide an overview of the structural diversity and taxonomic distribution of known myxobacterial natural products. Moreover, we demonstrated that the cutting-edge NMR-based metabolomics was effective to differentiate the biosynthetic priority of myxobacteria, whereby MyxoDB could greatly streamline the dereplication of multifarious known compounds and accordingly speed up the discovery of new compounds. This led to the rapid identification of a class of linear di-lipopeptides (archangimins) and a rare rearranged sterol (corasterol) that were endowed with unique chemical architectures and/or biosynthetic enzymology. We also showcased that NMR-based metabolomics, MyxoDB, and genomics can also work concertedly to accelerate the targeted discovery of a polyketidic compound pyxipyrrolone C. All in all, this study sets the stage for the discovery of many more novel natural products from underexplored myxobacterial resources.

A stable dye-sensitized photoelectrosynthesis cell mediated by a NiO overlayer for water oxidation.

In the development of photoelectrochemical cells for water splitting or CO2 reduction, a major challenge is O2 evolution at photoelectrodes that, in behavior, mimic photosystem II. At an appropriate semiconductor electrode, a water oxidation catalyst must be integrated with a visible light absorber in a stable half-cell configuration. Here, we describe an electrode consisting of a light absorber, an intermediate electron donor layer, and a water oxidation catalyst for sustained light driven water oxidation catalysis. In assembling the electrode on nanoparticle SnO2/TiO2 electrodes, a Ru(II) polypyridyl complex was used as the light absorber, NiO was deposited as an overlayer, and a Ru(II) 2,2'-bipyridine-6,6'-dicarboxylate complex as the water oxidation catalyst. In the final electrode, addition of the NiO overlayer enhanced performance toward water oxidation with the final electrode operating with a 1.1 mA/cm2 photocurrent density for 2 h without decomposition under one sun illumination in a pH 4.65 solution. We attribute the enhanced performance to the role of NiO as an electron transfer mediator between the light absorber and the catalyst.

A molecular tandem cell for efficient solar water splitting.

Artificial photosynthesis provides a way to store solar energy in chemical bonds. Achieving water splitting without an applied external potential bias provides the key to artificial photosynthetic devices. We describe here a tandem photoelectrochemical cell design that combines a dye-sensitized photoelectrosynthesis cell (DSPEC) and an organic solar cell (OSC) in a photoanode for water oxidation. When combined with a Pt electrode for H2 evolution, the electrode becomes part of a combined electrochemical cell for water splitting, 2H2O → O2 + 2H2, by increasing the voltage of the photoanode sufficiently to drive bias-free reduction of H+ to H2 The combined electrode gave a 1.5% solar conversion efficiency for water splitting with no external applied bias, providing a mimic for the tandem cell configuration of PSII in natural photosynthesis. The electrode provided sustained water splitting in the molecular photoelectrode with sustained photocurrent densities of 1.24 mA/cm2 for 1 h under 1-sun illumination with no applied bias.

Dissolved Organic Matter and Lignin Modulate Aquatic Toxicity and Oxidative Stress Response Activated by Layered Double Hydroxides Nanomaterials.

Advanced nanomaterials can be released into the environment and can coexist with natural organic matter (NOM). However, evidence on the impacts of NOM on the environmental behavior and toxicity of advanced nanomaterials is still scarce. Here, we investigated the behavior and toxic effects of two layered double hydroxides (LDHs) nanomaterials with different metallic constituents (Mg-Al-LDH and Zn-Al-LDH) at relatively low exposure concentrations on a freshwater green alga (Chlorella pyrenoidosa) in the absence and presence of two types of NOM, namely dissolved organic matter (DOM) and dealkaline lignin (DL). The DOM or DL interaction with the LDHs at different mixture levels was shown to be an antagonistic effect on the growth inhibition toxicity to C. pyrenoidosa mainly. The estimation of the index of Integrated Biological Responses version 2 indicated that the joint interaction of the LDHs with DOM or DL occurred in the following order of frequency synergism > antagonism > additivity. Furthermore, the physicochemical characteristics of LDHs were crucial for illuminating the mechanism by which the DOM or DL modified the LDH-induced oxidative stress response. These findings highlighted the important role of NOM in the behavior and effect of LDHs as a representative of a new class of multifunctional nanomaterials in the freshwater environment.

A Semiconductor-Mediator-Catalyst Artificial Photosynthetic System for Photoelectrochemical Water Oxidation.

In fabricating an artificial photosynthesis (AP) electrode for water oxidation, we have devised a semiconductor-mediator-catalyst structure that mimics photosystem II (PSII). It is based on a surface layer of vertically grown nanorods of Fe2 O3 on fluorine doped tin oxide (FTO) electrodes with a carbazole mediator base and a Ru(II) carbene complex on a nanolayer of TiO2 as a water oxidation co-catalyst. The resulting hybrid assembly, FTO|Fe2 O3 |-carbazole|TiO2 |-Ru(carbene), demonstrates an enhanced photoelectrochemical (PEC) water oxidation performance compared to an electrode without the added carbaozle base with an increase in photocurrent density of 2.2-fold at 0.95 V vs. NHE and a negatively shifted onset potential of 500 mV. The enhanced PEC performance is attributable to carbazole mediator accelerated interfacial hole transfer from Fe2 O3 to the Ru(II) carbene co-catalyst, with an improved effective surface area for the water oxidation reaction and reduced charge transfer resistance.

Encapsulation of Polymetallic Oxygen Clusters in a Mesoporous/Microporous Thorium-Based Porphyrin Metal-Organic Framework for Enhanced Photocatalytic CO2 Reduction.

Solar-initiated CO2 reduction is significant for green energy development. Herein, we have prepared a new mesoporous/microporous porphyrin metal-organic framework (MOF), IHEP-20, loaded with polymetallic oxygen clusters (POMs) to form a composite material POMs@IHEP-20 for visible-light-driven photocatalytic CO2 reduction. The as-made composite material exhibits good stability in water from pH 0 to 11. After POMs were introduced to IHEP-20, they showed superior activity toward photocatalytic CO2 reduction with a CO production rate of 970 µmol·g-1·h-1, which is 3.27 times higher than that of pristine IHEP-20. This study opens a new door for the design and synthesis of high-performance catalysts for the photocatalytic reduction of CO2.

Predicting joint toxicity of chemicals by incorporating a weighted descriptor into a mixture model: Cases for binary antibiotics and binary nanoparticles.

A prediction method that integrated a mixture descriptor with an established mixture toxicology method was proposed for the joint toxicity of chemical pollutants. A weighted descriptor derived from the single descriptor of each component was employed to calculate a mixture descriptor, which was successfully embedded into the generalized concentration addition (GCA) model named the extended GCA (XGCA) model. To develop and validate the proposed approach, binary antibiotic mixtures (ciprofloxacin and oxytetracycline) and metal-oxide (copper oxide and zinc oxide) nanoparticle mixtures were selected to study their toxicity to freshwater green algae. The results showed that concentration-response curve (CRC) derived from the XGCA model was closer to the observed CRC than those from the GCA, Concentration Addition (CA), and Independent Action (IA) models. The difference between effect concentrations predicted by the XGCA model and observed did not exceed a factor of 1.6. The XGCA model was relatively more accurate at predicting joint toxicity (in terms of effect concentrations and effect errors) than the reference models, independent of component types and mixture ratios. The XGCA model predicts the joint toxicity through molecular structural or nanostructural characters, thus modes of toxic action are not preconditions for predicting the toxicity of the mixtures. This result demonstrates the practicability of using the XGCA method in toxicity assessments of mixture pollutants with unknown modes of action.

Dissolved organic matter heightens the toxicity of tetrabromobisphenol A to aquatic organisms.

Tetrabromobisphenol A (TBBPA) is a new type of persistent organic pollutant, which causes environmental pollution and health problems, and has attracted the attention of the international research community. Once released into the environment, TBBPA can interact with dissolved organic matter (DOM), which affects its behavior. However, the effect of DOM on the biological toxicity of TBBPA remains unclear. The toxic effects of TBBPA on three model aquatic organisms (Chlorella pyrenoidosa, Daphnia magna, and Danio rerio), in the absence and presence of DOM were investigated. The order of acute toxicity of TBBPA to the three aquatic organisms was D. magna > D. rerio > C. pyrenoidosa. In the presence of DOM the median effect/lethal concentrations values of TBBPA to the three aquatic organisms decreased by at least 32 (C. pyrenoidosa), 52 (D. magna), and 6.6% (D. rerio), implying that DOM enhanced the acute toxicity of TBBPA to all the organisms. Moreover, the higher the concentration of DOM, the higher the acute toxicity of TBBPA. Furthermore, the presence of DOM increased total reactive oxygen species (ROS) induced by TBBPA in a concentration-dependent manner. A tracking analysis of total ROS in the three aquatic organisms also showed that the presence of DOM aggravated the accumulation of total ROS induced by TBBPA, indicating that oxidative stress is a characteristic mechanism of toxicity of TBBPA to aquatic organisms when DOM is present. In addition, the evaluated risk quotient indicated that the ecological risk of TBBPA to aquatic organisms can increase in environments rich in DOM.

The Discovery and Biosynthesis of Nicotinic Myxochelins from an Archangium sp. SDU34.

Myxobacteria are a prolific source of structurally diverse natural products, and one of the best-studied myxobacterial products is the siderophore myxochelin. Herein, we report two new compounds, myxochelins N (1) and O (2), that are nicotinic paralogs of myxochelin A, from the terrestrial myxobacterium Archangium sp. SDU34; 2 is functionalized with a rare 2-oxazolidinone. A precursor-feeding experiment implied that the biosynthesis of 1 or 2 was due to altered substrate specificity of the loading module of MxcE, which likely accepts nicotinic acid and benzoic acid instead of more conventional 2,3-dihydroxybenzoic acid. We also employed a phylogenomic approach to map the evolutionary relationships of the myxochelin biosynthetic gene clusters (BGCs) in all the available myxobacterial genomes, to pave the way for the future discovery of potentially hidden myxochelin derivatives. Although the biological function of 1 and 2 is unclear yet, this work underpins that even extensively studied BGCs in myxobacteria can still produce new chemistry.

CO2 reduction to acetate in mixtures of ultrasmall (Cu) n ,(Ag) m bimetallic nanoparticles.

Monodispersed mixtures of 6-nm Cu and Ag nanoparticles were prepared by electrochemical reduction on electrochemically polymerized poly-Fe(vbpy)3(PF6)2 film electrodes on glassy carbon. Conversion of the complex to poly-Fe(vbpy)2(CN)2 followed by surface binding of salts of the cations and electrochemical reduction gave a mixture of chemically distinct clusters on the surface, (Cu) m ,(Ag) n |polymer|glassy carbon electrode (GCE), as shown by X-ray photoelectron spectroscopy (XPS) measurements. A (Cu)2,(Ag)3|(80-monolayer-poly-Fe(vbpy)32+|GCE electrode at -1.33 V vs. reversible hydrogen electrode (RHE) in 0.5 M KHCO3, with 8 ppm added benzotriazole (BTA) at 0 °C, gave acetate with a faradaic efficiency of 21.2%.

Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators.

Stabilized photoanodes for light-driven water oxidation have been prepared on nanoparticle core/shell electrodes with surface-stabilized donor-acceptor chromophores, a water oxidation catalyst, and an electron-transfer mediator. For the electrode, fluorine-doped tin oxide FTO|SnO2/TiO2|-Org1-|1.1 nm Al2O3|-RuP2+-WOC (water oxidation catalyst) with Org1 (1-cyano-2-(4-(diphenylamino)phenyl)vinyl)phosphonic acid), the mediator RuP2+ ([Ru(4,4-(PO3H2)2-2,2-bipyridine)(2,2-bipyridine)2]2+), and the WOC, Ru(bda)(py(CH2)(3or10)P(O3H)2)2 (bda is 2,2-bipyridine-6,6-dicarboxylate with x = 3 or 10), solar excitation resulted in photocurrents of ∼500 µA/cm2 and quantitative O2 evolution at pH 4.65. Related results were obtained for other Ru(II) polypyridyl mediators. For the organic dye PP (5-(4-(dihydroxyphosphoryl)phenyl)-10,15,20-Tris(mesityl)porphyrin), solar water oxidation occurred with a driving force near 0 V.

Spatial analysis of metformin use compared with nicotine and caffeine consumption through wastewater-based epidemiology in China.

Monitoring the consumption of pharmaceuticals and licit drugs is important for assessing the needs of public health owing to the impact on individuals as well as society. The present work applied wastewater-based epidemiology to profile the spatial patterns of metformin, nicotine, and caffeine use and their correlations. Influent wastewater samples were collected from 27 wastewater treatment plants in 22 typical Chinese cities that covered all geographic regions of the country. The consumption of metformin ranged from 0.02 g/d/1000 inh to 8.92 g/d/1000 inh, whereas caffeine and nicotine consumption ranged from 4.33 g/d/1000 inh to 394 g/d/1000 inh and 0.17 g/d/1000 inh to 1.88 g/d/1000 inh, respectively. There were significant regional differences in the consumption of caffeine, with the highest consumption in East China and the lowest consumption in Northeast China. The consumption and concentration of caffeine were related to the gross domestic product and per capita disposable income of urban residents, respectively. There was a correlation between the concentrations of caffeine and cotinine (a nicotine metabolite), thereby indicating that individuals that use one of these substances are likely to use the other substance. A significant relationship was found between the concentration of metformin and cotinine, thereby implying that the use of tobacco may be correlated with type 2 diabetes. Co-analysis of these substances in wastewater may provide a more accurate picture of substance use situations within different communities and provide more information on human health, human behavior, and the economy. This report describes the newest study related to the consumption of metformin among the general population in China.

Estimating dynamic population served by wastewater treatment plants using location-based services data.

Wastewater-based epidemiology is a useful approach to estimate population-level exposure to a wide range of substances (e.g., drugs, chemicals, biological agents) by wastewater analysis. An important uncertainty in population normalized loads generated is related to the size and variability of the actual population served by wastewater treatment plants (WWTPs). Here, we built a population model using location-based services (LBS) data to estimate dynamic consumption of illicit drugs. First, the LBS data from Tencent Location Big Data and resident population were used to train a linear population model for estimating population (r2 = 0.92). Then, the spatiotemporal accuracy of the population model was validated. In terms of temporal accuracy, we compared the model-based population with the time-aligned ammonia nitrogen (NH4-N) population within the WWTP of SEG, showing a mean squared error of < 10%. In terms of spatial accuracy, we estimated the model-based population of 42 WWTPs in Dalian and compared it with the NH4-N and design population, indicating good consistency overall (5% less than NH4-N and 4% less than design). Furthermore, methamphetamine consumption and prevalence based on the model were calculated with an average of 111 mg/day/1000 inhabitants and 0.24%, respectively, and dynamically displayed on a visualization system for real-time monitoring. Our study provided a dynamic and accurate population for estimating the population-level use of illicit drugs, much improving the temporal and spatial trend analysis of drug use. Furthermore, accurate information on drug use could be used to assess population health risks in a community.

Pristine Hollow Metal-Organic Frameworks: Design, Synthesis and Application.

Metal-organic frameworks (MOFs), featuring porous crystalline structures with coordinated metal nodes and organic linkers, have recently found increasing interest in diverse applications. By virtue of their versatile and highly tunable compositions and structures, constructing hollow architectures will further endow MOFs with enhanced properties and designability, exceeding the molecular scale. MOFs could be considered as promising building units to fabricate complex hollow nanocomposites with faster mass transport, multiple active components, more exposed active sites, and better compatibility than bulk MOFs. To construct a promising blueprint for hollow pristine MOFs, this review provides a comprehensive overview for structural design strategies and applications of hollow pristine MOFs. We will highlight the merits, challenges and future potential by structuring and applying MOFs in sensing, separation, storage, catalysis, environmental remediation, photochemical and electrochemical energy conversion. This review might pave a new avenue for future development of novel pristine hollow MOFs.

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O2 production prepared by layer-by-layer self-assembly.

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor-chromophore-catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a RuII(bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L)2] (bda = 2,2'-bipyridine-6,6'-dicarboxylate)2, were linked by ALD by addition of the bridge precursors TiO2, ZrO2, and Al2O3 as the bridging groups giving the assemblies, FTO|nanoITO|-MV2+-ALD MO2-RuP2 2+-ALD M'O2-WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

Oxidation of alkyl benzenes by a flavin photooxidation catalyst on nanostructured metal-oxide films.

We describe here a surface-bound, oxide-based procedure for the photooxidation of a family of aromatic hydrocarbons by a phosphate-bearing flavin mononucleotide (FMN) photocatalyst on high surface area metal-oxide films.

Plasmon-enhanced light-driven water oxidation by a dye-sensitized photoanode.

Dye-sensitized photoelectrosynthesis cells (DSPECs) provide a flexible approach for solar water splitting based on the integration of molecular light absorption and catalysis on oxide electrodes. Recent advances in this area, including the use of core/shell oxide interfacial structures and surface stabilization by atomic layer deposition, have led to improved charge-separation lifetimes and the ability to obtain substantially improved photocurrent densities. Here, we investigate the introduction of Ag nanoparticles into the core/shell structure and report that they greatly enhance light-driven water oxidation at a DSPEC photoanode. Under 1-sun illumination, Ag nanoparticle electrodes achieved high photocurrent densities, surpassing 2 mA cm-2 with an incident photon-to-current efficiency of 31.8% under 450-nm illumination.

Comparative Acute Toxicity and Oxidative Stress Responses in Three Aquatic Species Exposed to Stannic Oxide Nanoparticles and Stannic Chloride.

We experimentally investigated the toxicity of stannic oxide nanoparticles (SnO2 NPs) to three freshwater species including Scenedesmus obliquus, Daphnia magna, and Danio rerio. To evaluate effect, toxicological impacts were compared to that of stannic chloride (SnCl4). Based on the actual concentration of Sn, SnO2 NPs suspensions inhibited growth of S. obliquus in a dose-dependent manner, demonstrating a median effect concentration of 2.28 ± 0.53 mg/L. However, SnO2 NP suspensions were found to exhibit limited acute toxicity in D. magna and D. rerio. Moreover, the toxicity of the SnO2 NP suspension was lower than SnCl4 for all three trophic aquatic organisms. Comparison of component-specific contribution to overall toxicity indicated that, in SnO2 NP suspensions, particulate Sn more significantly contributed to toxicity than dissolved Sn-ions. Furthermore, we found that the toxic mechanism of the SnO2 NP suspension involved the induction of oxidative stress by increasing intracellular ROS accumulation.