A hybrid photocatalytic system enables direct glucose utilization for methanogenesis.

Integration of methanogenic archaea with photocatalysts presents a sustainable solution for solar-driven methanogenesis. However, maximizing CH4 conversion efficiency remains challenging due to the intrinsic energy conservation and strictly restricted substrates of methanogenic archaea. Here, we report a solar-driven biotic-abiotic hybrid (biohybrid) system by incorporating cadmium sulfide (CdS) nanoparticles with a rationally designed methanogenic archaeon Methanosarcina acetivorans C2A, in which the glucose synergist protein and glucose kinase, an energy-efficient route for glucose transport and phosphorylation from Zymomonas mobilis, were implemented to facilitate nonnative substrate glucose for methanogenesis. We demonstrate that the photo-excited electrons facilitate membrane-bound electron transport chain, thereby augmenting the Na+ and H+ ion gradients across membrane to enhance adenosine triphosphate (ATP) synthesis. Additionally, this biohybrid system promotes the metabolism of pyruvate to acetyl coenzyme A (AcCoA) and inhibits the flow of AcCoA to the tricarboxylic acid (TCA) cycle, resulting in a 1.26-fold augmentation in CH4 production from glucose-derived carbon. Our results provide a unique strategy for enhancing methanogenesis through rational biohybrid design and reprogramming, which gives a promising avenue for sustainably manufacturing value-added chemicals.

Magnetite nanoparticle coating chemistry regulates root uptake pathways and iron chlorosis in plants.

Understanding the fundamental interaction of nanoparticles at plant interfaces is critical for reaching field-scale applications of nanotechnology-enabled plant agriculture, as the processes between nanoparticles and root interfaces such as root compartments and root exudates remain largely unclear. Here, using iron deficiency-induced plant chlorosis as an indicator phenotype, we evaluated the iron transport capacity of Fe3O4 nanoparticles coated with citrate (CA) or polyacrylic acid (PAA) in the plant rhizosphere. Both nanoparticles can be used as a regulator of plant hormones to promote root elongation, but they regulate iron deficiency in plant in distinctive ways. In acidic root exudates secreted by iron-deficient Arabidopsis thaliana, CA-coated particles released fivefold more soluble iron by binding to acidic exudates mainly through hydrogen bonds and van der Waals forces and thus, prevented iron chlorosis more effectively than PAA-coated particles. We demonstrate through roots of mutants and visualization of pH changes that acidification of root exudates primarily originates from root tips and the synergistic mode of nanoparticle uptake and transformation in different root compartments. The nanoparticles entered the roots mainly through the epidermis but were not affected by lateral roots or root hairs. Our results show that magnetic nanoparticles can be a sustainable source of iron for preventing leaf chlorosis and that nanoparticle surface coating regulates this process in distinctive ways. This information also serves as an urgently needed theoretical basis for guiding the application of nanomaterials in agriculture.

Probing the Surface Layer Modulation on Archaeal Mechanics and Adhesion at the Single-Cell Level.

Addressing the challenge of understanding how cellular interfaces dictate the mechanical resilience and adhesion of archaeal cells, this study demonstrates the role of the surface layer (S-layer) in methanogenic archaea. Using a combination of atomic force microscopy and single-cell force spectroscopy, we quantified the impact of S-layer disruption on cell morphology, mechanical properties, and adhesion capabilities. We demonstrate that the S-layer is crucial for maintaining cell morphology, where its removal induces significant cellular enlargement and deformation. Mechanical stability of the cell surface is substantially compromised upon S-layer disruption, as evidenced by decreased Young's modulus values. Adhesion experiments revealed that the S-layer primarily facilitates hydrophobic interactions, which are significantly reduced after its removal, affecting both cell-cell and cell-bubble interactions. Our findings illuminate the S-layer's fundamental role in methanogen architecture and provide a chemical understanding of archaeal cell surfaces, with implications for enhancing methane production in biotechnological applications.

In Situ Probing of the Intrinsic Adhesion Strength of Single Anaerobic Microbial Cells.

Probing the single-cell mechanobiology in situ is imperative for microbial processes in the medical, industrial, and agricultural realms, but it remains a challenge. Herein, we present a single-cell force microscopy method that can be used to measure microbial adhesion strength under anaerobic conditions in situ. This method integrates atomic force microscopy with an anaerobic liquid cell and inverted fluorescence microscopy. We obtained the nanomechanical measurements of the single anaerobic bacterium Ethanoligenens harbinense YUAN-3 and the methanogenic archaeon Methanosarcina acetivorans C2A and their nanoscale adhesion forces in the presence of sulfoxaflor, a successor of neonicotinoid pesticides. This study presents a new tool for in situ single-cell force measurements of various anoxic and anaerobic species and provides new perspectives for evaluating the potential environmental risk of neonicotinoid applications in ecosystems.

Bubbles Expand the Dissemination of Antibiotic Resistance in the Aquatic Environment.

Antibiotic resistance is a global health challenge, and the COVID-19 pandemic has amplified the urgency to understand its airborne transmission. The bursting of bubbles is a fundamental phenomenon in natural and industrial processes, with the potential to encapsulate or adsorb antibiotic-resistant bacteria (ARB). However, there is no evidence to date for bubble-mediated antibiotic resistance dissemination. Here, we show that bubbles can eject abundant bacteria to the air, form stable biofilms over the air-water interface, and provide opportunities for cell-cell contact that facilitates horizontal gene transfer at and over the air-liquid interface. The extracellular matrix (ECM) on bacteria can increase bubble attachment on biofilms, increase bubble lifetime, and, thus, produce abundant small droplets. We show through single-bubble probe atomic force microscopy and molecular dynamics simulations that hydrophobic interactions with polysaccharides control how the bubble interacts with the ECM. These results highlight the importance of bubbles and its physicochemical interaction with ECM in facilitating antibiotic resistance dissemination and fulfill the framework on antibiotic resistance dissemination.

Model-based mid-infrared spectroscopy for on-line monitoring of volatile fatty acids in the anaerobic digester.

The performance of anaerobic digestion is significantly governed by the concentration of volatile fatty acids (VFAs). Though the titration and near-infrared spectroscopy have been used to measure the VFAs in the digester, there is still lack of the establishment of on-line monitoring of VFAs in practical application. An effective quantification method based on mid-infrared (MIR) spectroscopy was developed, and used to measure the concentrations of VFAs in the anaerobic bioreactor nondestructively in parallel. The wavelet denoising (WD) spectra were used as the spectral preprocessing option. Compared with other pretreatment methods, the established calibration model built by WD spectra showed satisfactory results. Further, the model was verified using high performance liquid chromatography (HPLC), and predictions were made using real reactor effluent samples. Based on this theoretical work, a set of equipment for the in-situ online monitoring of VFAs was designed, which has high feasibility and effectively solves the problems with the current VFAs online monitoring process. These results provide a new solution for on-line monitoring of the anaerobic digestion, and have great potential for practical application.

Evaluation of nine active components of Lu-Jiao Fang in normal and hypertrophic rat myocardia via LC-MS/MS.

Lu-Jiao Fang (LJF), a traditional Chinese medicine prescription, can improve the cardiac function of chronic heart failure (CHF) patients; however, knowledge about the cardiac distribution of LJF, especially in CHF animal models, is rather limited. This work aimed to explore the cardiac distribution of LJF in pressure overload-induced CHF rats at the last gavage administration of LJF after 30 weeks of treatment. LC-MS/MS methods for analyzing nine active components (i.e. loganin, hesperidin, epimedin C, icariin, psoralen, isopsoralen, baohuoside I, morroniside and specnuezhenide) of LJF in cardiac tissue samples were established, and the components were then analyzed in left ventricular wall (LVW) and right ventricular wall (RVW) in parallel at same time point postdose for three dose groups. The results showed that most analytical component levels in LVW (hypertrophic myocardium) were only 39-74% of those in RVW (normal myocardium); however, psoralen and isopsoralen levels in LVW were equal to or even greater than the levels in RVW, suggesting that the hypertrophic myocardium tissue affinity of psoralen and isopsoralen might overcome the negative effect of decreased blood flow on distribution. This study indicated that the pathological state may influence drug distribution, and the efficacy of psoralen and isopsoralen for improving CHF deserves further investigation.

Chemical Dynamics of Selenium Nanoparticles in Archaeal Systems.

Methanogenic archaea, characterized by their cell membrane lipid molecules consisting of isoprenoid chains linked to glycerol-1-phosphate via ether bonds, exhibit exceptional adaptability to extreme environments. However, this distinct lipid architecture also complicates the interactions between methanogenic archaea and nanoparticles. This study addresses this challenge by exploring the interaction and transformation of selenium nanoparticles (SeNPs) within archaeal Methanosarcina acetivorans C2A. We demonstrated that the effects of SeNPs are highly concentration-dependent, with chemical stimulation of cellular processes at lower SeNPs concentrations as well as oxidative stress and metabolic disruption at higher concentrations. Notably, we observed the formation of a protein corona on SeNPs, characterized by the selective adsorption of enzymes critical for methylotrophic methanogenesis and those involved in selenium methylation, suggesting potential alterations in protein function and metabolic pathways. Furthermore, the intracellular transformation of SeNPs into both inorganic and organic selenium species highlighted their bioavailability and dynamic transformation within archaea. These findings provide vital insights into the nano-bio interface in archaeal systems, contributing to our understanding of archaeal catalysis and its broader applications.

Nitrogen Forms Regulate the Response of Microcystis aeruginosa to Nanoplastics at Environmentally Relevant Nitrogen Concentrations.

As essential primary producers, cyanobacteria play a major role in global carbon and nitrogen cycles. Though the influence of nanoplastics on the carbon metabolism of cyanobacteria is well-studied, little is known about how nanoplastics affect their nitrogen metabolism, especially under environmentally relevant nitrogen concentrations. Here, we show that nitrogen forms regulated growth inhibition, nitrogen consumption, and the synthesis and release of microcystin (MC) in Microcystis aeruginosa exposed to 10 µg/mL amino-modified polystyrene nanoplastics (PS-NH2) with a particle size of 50 nm under environmentally relevant nitrogen concentrations of nitrate, ammonium, and urea. We demonstrate that PS-NH2 inhibit M. aeruginosa differently in nitrate, urea, and ammonium, with inhibition rates of 51.87, 39.70, and 36.69%, respectively. It is caused through the differences in impairing cell membrane integrity, disrupting redox homeostasis, and varying nitrogen transport pathways under different nitrogen forms. M. aeruginosa respond to exposure of PS-NH2 by utilizing additional nitrogen to boost the production of amino acids, thereby enhancing the synthesis of MC, extracellular polymeric substances, and membrane phospholipids. Our results found that the threat of nanoplastics on primary producers can be regulated by the nitrogen forms in freshwater ecosystems, contributing to a better understanding of nanoplastic risks under environmentally relevant conditions.

Using colloidal AFM probe technique and XDLVO theory to predict the transport of nanoplastics in porous media.

The plastic concentration in terrestrial systems is orders of magnitude higher than that found in marine ecosystems, which has raised global concerns about their potential risk to agricultural sustainability. Previous research on the transport of nanoplastics in soil relied heavily on the qualitative prediction of the mean-field extended Derjaguin-Landau-Verwey-Overbeek theory (XDLVO), but direct and quantitative measurements of the interfacial forces between single nanoplastics and porous media are lacking. In this study, we conducted multiscale investigations ranging from column transport experiments to single particle measurements. The maximum effluent concentration (C/C0) of amino-modified nanoplastics (PS-NH2) was 0.94, whereas that of the carboxyl-modified nanoplastics (PS-COOH) was only 0.33, indicating PS-NH2 were more mobile than PS-COOH at different ionic strengths (1-50 mM) and pH values (5-9). This phenomenon was mainly attributed to the homogeneous aggregation of PS-COOH. In addition, the transport of PS-NH2 in the quartz sand column was inhibited with the increase of ionic strength and pH, and pH was the major factor governing their mobility. The transport of PS-COOH was inhibited with increasing ionic strength and decreasing pH. Hydrophilicity/hydrophobicity-mediated interactions and particle heterogeneity strongly interfered with interfacial forces, leading to the qualitative prediction of XDLVO, contrary to experimental observations. Through the combination of XDLVO and colloidal atomic force microscopy, accurate and quantitative interfacial forces can provide compelling insight into the fate of nanoparticles in the soil environment.

Single bubble probe atomic force microscope and impinging-jet technique unravel the interfacial interactions controlled by long chain fatty acid in anaerobic digestion.

Anaerobic digestion of lipid-rich wastewater generally suffers from foaming induced by long chain fatty acid (LCFA). However, a systematic understanding of LCFA inhibition, especially the physical inhibition on interfacial interaction still remains unclear. Here, we combined bubble probe atomic force microscope and impinging-jet technique to unravel the interfacial interactions controlled by long chain fatty acids in anaerobic digestion. We showed that LCFA had a significant inhibition on methane production in anaerobic reactors for the inhibition of the conversion of VFAs to methane. By measuring the LCFA influence on methanogenic archaea Methanosarcina acetivorans C2A, the results demonstrated that methanogenesis was limited for substrates utilization but not metabolic pathways. The impinging-jet technique results indicated that LCFA enhanced bubble separation from anaerobic granules and reduced the bubble-bubble coalescence probability. In addition, the bubble probe atomic force microscope (AFM) revealed that LCFA enhanced the adhesion force between bubbles by enhancing electrical double layer (EDL) repulsion and decreasing hydrophobic interactions. Overall, these results complement framework of LCFA inhibition in anerobic digestion and provide a nanomechanical insight into the fundamental interfacial interactions related to bubbles in anaerobic reactors.

The surface groups of polystyrene nanoparticles control their interaction with the methanogenic archaeon Methanosarcina acetivorans.

A better understanding of the interaction between nanoplastics and archaea is crucial to fill the knowledge gaps regarding the ecological safety of nanoplastics. As a vital source for global methane emissions, methanogenic archaea have unique cell membranes that are distinctly different from those in all other forms of life, little is known about their interaction with nanoplastics. Here, we show that polystyrene nanoparticles functionalized with sulfonic acid (PS-SO3H) and amino (PS-NH2) interact with this methanogenic archaeon in distinct ways. Although both of them have no significant phenotype effects on Methanosarcina acetivorans C2A, these nanoparticles could affect DNA-mediated transposition of this methanogenic archaeon, and PS-SO3H also downregulated nitrogen fixation, nitrogen cycle metabolic process, oxidoreductase activity, etc. In addition, both nanoplastics decreased the protein contents in the extracellular polymer substances (EPS), with distinct binding sequences to the functional groups of the EPS. The single particle atomic force microscopy revealed that the force between the amino group and the M. acetivorans C2A was greater than that of sulfonic acid group. Our results exhibit that the surface groups of polystyrene nanoparticles control their risk on the methanogenic archaea, and these effects might influence their contribution on global methane emission.

(Z)-(1,2-Dichloro-vin-yl)diphenyl-phosphine oxide.

The title compound, C(14)H(11)Cl(2)OP, was synthesized by the reaction of diphenyl-phosphine oxide with 1,2-dichloro-ethyne under CuI catalysis. The reaction provided the Z isomer regioselectively. Two O-P-C bond angles [114.3 (1) and 112.5 (1)°] are significantly larger than the C-P-C [107.7 (1), 105.6 (1) and 106.6 (1)°] and another O-P-C angle [109.5 (1)°], indicating significant distortion of the tetra-hedral configuration of the P atom. In the crystal, mol-ecules are linked by weak inter-molecular C-H⋯O hydrogen bonds into centrosymmetric dimers, which are connected by further C-H⋯O inter-actions into chains along [101].

Insights on the inhibition of anaerobic digestion performances under short-term exposure of metal-doped nanoplastics via Methanosarcina acetivorans.

Anaerobic digestion is an attractive waste treatment technology, achieving both pollution control and energy recovery. Though the inhibition of polystyrene nanoplastics in anaerobic granular sludge is well studied, no direct evidence has been found on the interaction of methanogens and nanoplastics. In this study, to characterize the location of nanoplastics, Pd-doped polystyrene nanoplastics (Pd-PS) were used to explore the inhibition mechanism of anaerobic sludge through short-term exposure to Methanosarcina acetivorans C2A. The results showed that Pd-PS inhibited the methanogenesis of the anaerobic sludge, and the methane production decreased as the Pd-PS increased, with a 14.29% reduction at the Pd-PS concentration of 2.36 × 1010 particles/mL. Also, Pd-PS interacted with the protein in the extracellular polymeric substances (EPS). Furthermore, Pd-PS inhibited the methanogenesis of M. acetivorans C2A without exhibiting an evident reduction in the growth. The inhibition of Pd-PS on methane was due to the inhibition of methane production related genes, MtaA and mcrA. These results provide potential explication for the inhibition of nanoplastics on the methanogens, which will fulfill the knowledge on the stability of methanogens under the short-term exposure of nanoplastics.

Attachment and adhesion force between biogas bubbles and anaerobic granular sludge in the up-flow anaerobic sludge blanket.

The performance of the up-flow anaerobic sludge blanket (UASB) is significantly governed by the hydrodynamics of the reactor. Though the influence of hydrodynamics on mass transfer, granular size distribution, and biogas production was well studied, the interaction between biogas bubbles and anaerobic granular sludge (AGS) is poorly understood. This study used the impinging-jet technique and bubble probe atomic force microscope (AFM) to investigate the attachment and adhesion force between biogas bubbles (CH4 and CO2) and AGS. The fluxes of normalized CH4 or CO2 bubble-attachment on two kinds of AGS were directly affected by gas velocity and decreased with an increase in the Reynolds number ranged from 40 to 140. The bubble-attachment had a positive linear relationship with the contact angles, ratio of exopolymeric protein and polysaccharide, and hydrophilic functional groups of AGS. A bubble probe AFM was used to explore the adhesion force between a single bubble and AGS. The results indicated that the adhesion force between the bubbles and the two kinds of AGS also decreased with increasing approach velocity. Overall, these results contribute to a new insight into the understanding of interaction between biogas bubbles and AGS in UASB reactors.