Implementation of π-π interaction in AuNPs@GDY to boost the bioelectrocatalysis in enzymatic biofuel cells.

The main challenges (sluggish electron transfer, low energy density) hinder the future application of enzymatic biofuel cells (EBFCs), which urgent to take effective measures to solve these issues. In this work, a composite of Au nanoparticles decorated graphdiyne (AuNPs@GDY) is fabricated and employed as the carrier of enzyme (G6PDH), and a mechanism based on π-π interaction of electron transfer is proposed to understand bioelectrocatalysis processes. The results show that the AuNPs@GDY composite exhibits the highest current density among the three materials (GDY, AuNPs, and AuNPs@GDY), which is 3.4 times higher than that of GDY and 2.5 times higher than that of AuNPs. Furthermore, the results reveal that the AuNPs could increase the loading of enzymes and provide more active site for reaction, while GDY provides highly π-conjugated structure and unique sp/sp2-hybridized linkages interface. This work provides new insights to explore a theoretical basis for the development of more efficient bioelectrocatalytic systems.

Electromagnetic Field Drives the Bioelectrocatalysis of γ-Fe2O3-Coated Shewanella putrefaciens CN32 to Boost Extracellular Electron Transfer.

The microbial hybrid system modified by magnetic nanomaterials can enhance the interfacial electron transfer and energy conversion under the stimulation of a magnetic field. However, the bioelectrocatalytic performance of a hybrid system still needs to be improved, and the mechanism of magnetic field-induced bioelectrocatalytic enhancements is still unclear. In this work, γ-Fe2O3 magnetic nanoparticles were coated on a Shewanella putrefaciens CN32 cell surface and followed by placing in an electromagnetic field. The results showed that the electromagnetic field can greatly boost the extracellular electron transfer, and the oxidation peak current of CN32@γ-Fe2O3 increased to 2.24 times under an electromagnetic field. The enhancement mechanism is mainly due to the fact that the surface modified microorganism provides an elevated contact area for the high microbial catalytic activity of the outer cell membrane's cytochrome, while the magnetic nanoparticles provide a networked interface between the cytoplasm and the outer membrane for boosting the fast multidimensional electron transport path in the magnetic field. This work sheds fresh scientific light on the rational design of magnetic-field-coupled electroactive microorganisms and the fundamentals of an optimal interfacial structure for a fast electron transfer process toward an efficient bioenergy conversion.

Graphdiyne marries PEDOT:PSS to form high-stable heterostructure from 2-unstable components toward ultra-low detection limit of uric acid detection in sweat.

PEDOT: PSS has been used as a biomimetic uric acid (UA) sensor but suffers from unfortunate low detection limit (LOD), narrow detection range and poor stability. Herein, we get graphdiyne (GDY) marry PEDOT:PSS to create a very stable GDY@PEDOT:PSS heterostructure for a biomimetic UA sensor, which accomplishes the lowest LOD (6 nM), the widest detection range (0.03 µM-7 mM) and the longest stability (98.1% for 35 days) among the related UA sensors. The sensor was successfully used to in situ real-time detection of  UA in sweat. The enhancement mechanisms of the sensor were investigated, and results discover that C≡C of GDY and C = C of PEDOT:PSS can cross-link each other by π-π interactions, making not only the former strongly resistant against oxidation deterioration, but also causes the latter to efficiently prevent water swelling of polymer for poor conductivity, thereby leading to high stability from both components. While the stabilized heterostructure can also offer more active sites by enhanced absorption of UA via π-π interactions for highly sensitive detection of UA. This work holds great promise for a practical sweat UA sensor while providing scientific insight to design a stable and electrocatalytically active structure from two unstable components.

Tuning metal atom doped interface of electrospinning nanowires to toward fast bioelectrocatalysis.

Metal doping plays a key role in overcoming inefficient extracellular electron transfer between electrode interface and electricity-producing microorganisms. However, it is unknown whether different metals play distinctive roles in the doping process. Herein, three different metal ions (Fe, Ni and Cu) are added to the spinning precursor to obtain the corresponding electrospinning metal doped carbon nanofibers. It is found that the maximum output power of iron doped carbon nanofiber anode is 641.96 mW m-2, which is better than that of nickel doped carbon nanofiber (411.26 mW m-2) and copper doped carbon nanofiber (336.01 mW m-2), as well as 7.62 times higher than that of CNF. The results proved that due to the various number and types of active sites formed, as well as the distinction in surface morphology and structure, the electronegativity of each material is different. The different bio-abiotic interface could affect the direct contact between the anode interface and the extracellular protein of electricity producing microorganisms, which leading to a significant gap in the improvement of bioelectrocatalytic performance of different metal anode materials. This work provides a synthetic idea for designing highly efficient anode materials with directional metal modification and interface regulation.

Integrated Sandwich-Paper 3D Cell Sensing Device to In Situ Wirelessly Monitor H2O2 Released from Living Cells.

Point-of-care testing (POCT) has attracted great interest because of its prominent advantages of rapidness, precision, portability, and real-time monitoring, thus becoming a powerful biomedical device in early clinical diagnosis and convenient medical treatments. However, its complicated manufacturing process and high expense severely impede mass production and broad applications. Herein, an innovative but inexpensive integrated sandwich-paper three-dimensional (3D) cell sensing device is fabricated to in situ wirelessly detect H2O2 released from living cells. The paper-based electrochemical sensing device was constructed by a sealed sandwiched bottom plastic film/fiber paper/top hole-centered plastic film that was printed with patterned electrodes. A new (Fe, Mn)3(PO4)2/N-doped carbon nanorod was developed and immobilized on the sensing carbon electrode while cell culture solution filled the exposed fiber paper, allowing living cells to grow on the fiber paper surrounding the electrode. Due to the significantly shortening diffusion distance to access the sensing sites by such a unique device and a rationally tuned ratio of Fe2+/Mn2+, the device exhibits a fast response time (0.2 s), a low detection limit (0.4 µM), and a wide detection range (2-3200 µM). This work offers great promise for a low-cost and highly sensitive POCT device for practical clinic diagnosis and broad POCT biomedical applications.

The Enhancement Mechanism of Different Single-Transition Metal Atomic Catalysts/Sulfur Cathode on High-Performance of Li-S Batteries.

Materials with various single-transition metal atoms dispersed in nitrogenated carbons (M─N─C, M = Fe, Co, and Ni) are synthesized as cathodes to investigate the electrocatalytic behaviors focusing on their enhancement mechanism for performance of Li-S batteries. Results indicate that the order of both electrocatalytic activity and rate capacity for the M─N─C catalysts is Co > Ni > Fe, and the Co─N─C delivers the highest capacity of 1100 mAh g-1 at 1 C and longtime stability at a decay rate of 0.05% per cycle for 1000 cycles, demonstrating excellent battery performance. Theoretical calculations for the first time reveal that M─N─N─C catalysts enable direct conversion of Li2 S6 to Li2 S rather than Li2 S4 to Li2 S by stronger adsorption with Li2 S6 , which also has an order of Co > Ni > Fe. And Co─N─C has the strongest adsorption energy, not only rendering the highest electrocatalytic activity, but also depressing the polysulfides' dissolution into electrolyte for the longest cycle life. This work offers an avenue to design the next generation of highly efficient sulfur cathodes for high-performance Li-S batteries, while shedding light on the fundamental insight of single metal atomic catalytic effects on Li-S batteries.

Graphdiyne chelated AuNPs for ultrasensitive electrochemical detection of tyrosine.

Tyrosine (Tyr) is a kind of amino acid that can regulate emotions and stimulate the nervous system, and it is of great importance to realize its ultrasensitive detection. A unique material of graphdiyne chelated AuNPs (GDY@AuNPs) is designed and developed to realize high-performance electrochemical sensing of Tyr. GDY promotes the absorption of Tyr via π-π interaction, and its CC strongly chelates with AuNPs for greatly improved sensitivity. GDY@AuNPs delivers a sensitivity of up to 181.2 µA mM-1 cm-2 and a wide range of 0.1-600 µM, among the best for carbon or AuNPs-based materials for the detection of Tyr. It demonstrates the accurate detection of Tyr in human sweat for potential practical applications.

Doping molybdenum oxides with different non-metal atoms to promote bioelectrocatalysis in microbial fuel cells.

The sluggish extracellular electron transfer has been known as one of the bottlenecks to limit the power density of microbial fuel cells (MFCs). Herein, molybdenum oxides (MoOx) are doped with various types of non-metal atoms (N, P, and S) by electrostatic adsorption, followed by high-temperature carbonization. The as-prepared material is further used as MFC anode. Results indicate that all different elements-doped anodes can accelerate the electron transfer rate, and the great enhancement mechanism is attributed to synergistic effect of dopped non-metal atoms and the unique MoOx nanostructure, which offers high proximity and a large reaction surface area to promote microbe colonization. This not only enables efficient direct electron transfer but also enriches the flavin-like mediators for fast extracellular electron transfer. This work renders new insights into doping non-metal atoms onto metal oxides toward the enhancement of electrode kinetics at the anode of MFC.

Electrospinning Mo-Doped Carbon Nanofibers as an Anode to Simultaneously Boost Bioelectrocatalysis and Extracellular Electron Transfer in Microbial Fuel Cells.

The sluggish electron transfer at the interface of microorganisms and an electrode is a bottleneck of increasing the output power density of microbial fuel cells (MFCs). Mo-doped carbon nanofibers (Mo-CNFs) prepared with electrostatic spinning and high-temperature carbonization are used as an anode in MFCs here. Results clearly indicate that Mo2C nanoparticles uniformly anchored on carbon nanowire, and Mo-doped anodes could accelerate the electron transfer rate. The Mo-CNF ΙΙ anode delivered a maximal power density of 1287.38 mW m-2, which was twice that of the unmodified CNFs anode. This fantastic improvement mechanism is attributed to the fact that Mo doped on a unique nanofiber surface could enhance microbial colonization, electrocatalytic activity, and large reaction surface areas, which not only enable direct electron transfer, but also promote flavin-like mediated indirect electron transfer. This work provides new insights into the application of electrospinning technology in MFCs and the preparation of anode materials on a large scale.

Interfacial Regulation of ZIF-67 on Bacteria to Generate Bifunctional Sensing Material on Chip for Qualifying Cell-Released Reactive Oxygen Species.

Cell's activities are highly dependent on signal molecules, of which reactive oxygen species of the superoxide anion (O2•-) and hydrogen peroxide (H2O2) are important ones that always work together to regulate biological processes such as apoptosis and oxidative stress. It is of significance to realize simultaneous qualification of O2•- and H2O2 but it still faces challenges particularly in live-cell assay with a complex environment. We report the design of a bifunctional sensing material by interfacially regulating ZIF-67 on bacteria Shewanella putrefaciens to generate cobalt nanoparticles/nitrogen-doped porous carbon nanorods (Co/N-doped CNRs) and its sensing chip for qualifying cell-released O2•- and H2O2. Co/N-doped CNRs exhibit unique properties including porous structure for significantly increased reaction surface area and coordinating Co nanoparticles for rich active sites. The bifunctional Co/N-doped CNRs is used to fabricate the electrochemical sensing chip, which achieves a fast response time (0.5 s for O2•-, 1.9 s for H2O2), a low detection limit (0.69 nM for O2•-, 2.25 µM for H2O2), and a remarkably high sensitivity (792.30 µA·µM-1·cm-2 for O2•-, 153.91 µA·mM-1·cm-2 for H2O2), among the best of reported bifunctional nanozymes.

Synthesis of NiO/Nitrogen-Doped Carbon Nanowire Composite with Multi-Layered Network Structure and Its Enhanced Electrochemical Performance for Supercapacitor Application.

Multi-layered NiO nanowires linked with a nitrogen-doped carbon backbone grown directly on flexible carbon cloth (NiO/NCBN/CC) was successfully fabricated with a facile synthetic strategy. The NiO/NCBN/CC was further used as a binding-free electrode for flexible energy storage devices, showing a boosted performance including a high capacitance of 1039.4 F g-1 at 1 A g-1 and an 83.4% capacitance retention ratio. More importantly, after 1500 cycles, the capacitance retention can achieve 72.5% at a current density of 20 A g-1. The excellent electrochemical properties of the as-prepared NiO/NCBN/CC are not only attributed to the multi-layered structure that can help to tender unimpeded channels and accommodate the electrolyte ions around the electrode interface during the charge-discharge process, but is also due to the link between the NiO and N-doped carbon backbone and the nitrogen doping on the carbon substrate, which results in extra defects on the surface that could boost the interfacial electron transfer rate of the electrode.

Assess heavy metals-induced oxidative stress of microalgae by Electro-Raman combined technique.

Oxidative stress of aquatic microorganisms under heavy metal stress is closely reflected by metabolite changes in cells but it is very difficult to study due to the fast metabolism process and severe in-situ measurements hurdle. Herein, the oxidative stress of cadmium on Euglena gracilis was systematically studied through multi-combined techniques. In particular, for the first time electrochemical approach was associated with Raman spectroscopy imaging to vividly to investigate temporal-spatially varied oxidative stress and its effects on cells metabolism, in which former real-time measured a volcanic relation of extracellular hydrogen peroxide versus the increase of cadmium stress, while the latter shows the corresponding metabolic changes by Raman imaging of single cells. This work builds a bridge to unravel the mechanism of cellular oxidative stress under harsh conditions in a more systematic and holistic approach, while holding a great promise to construct heavy metal biosensors precisely monitoring high heavy metal tolerance strains for environmental modification.

Vanadium pentoxide flat-nanofiber networked thin layer-structure to initiate intercalated polymerization for rapidly producing superior conductive hydrogel and its biomimetic hydrogen peroxide sensing application.

Poly(3,4-ethylenedioxythiophene) (PEDOT)-based hydrogel has been studied extensively due to its low cost, good chemical/mechanical stability, printability and high biocompatibility, but still suffers from its relatively low conductivity and complex synthesis method. In this work, we use vanadium pentoxide (V2O5) flat-nanofiber networked thin layer-structure to boost EDOT-intercalation reaction for rapidly producing fiber-reinforced conductive gel (FCG), achieving superior conductivity of 10 S cm-1 and extremely fast production time (10 s). The superior FCG formation mechanism is ascribed to the V2O5 flat-nanofiber networked thin layer-structure allowing EDOT rapidly penetrating to inter-layers and replacing inside water molecules for polymerization to high-conductive FCG. The FCG can be used to print various patterns and are further used to fabricate a flexible biomimetic hydrogen peroxide (H2O2) sensor, delivering a high sensitivity of 2100 µA mM-1 cm-2, ranking the best among all flexible enzyme-free H2O2 sensors. More importantly, this flexible biomimetic H2O2 sensor is successfully applied to real-time detect living cells-secreted H2O2, demonstrating its application for in situ monitoring of small biomolecules released from living cells. This work offers a universal approach to synthesize high-conductive printable hydrogels by designing precursors meriting from both physics and chemistry, while holding great promise for mass-manufacturing inexpensive hydrogels in applications of sensing or wearable devices.

Highly stable branched cationic polymer-functionalized black phosphorus electrochemical sensor for fast and direct ultratrace detection of copper ion.

Copper ions (Cu2+) is an indispensable trace element in the process of metabolism and intake of excessive Cu2+ may lead to fatal diseases such as Alzheimer's disease. It is highly demanding to develop a sensitive, selective and convenient method for Cu2+ detection. In this work, thin-layer structured polyethyleneimine (PEI) decorated black phosphorus (BP) nanocomposite is one-step synthesized for an electrochemical sensor toward direct detection of Cu2+. This sensor achieves a wide detection range of 0.25-177 µM, a low detection limit of 0.02 µM much below the Environmental Protection Agency (EPA) maximum contaminant levels for drinking water (20 µM for Cu2+), and much faster response (1.5 s response time) and simpler operation than the conventional tedious anodic stripping voltammetry, ranking one of the best among all reported Cu2+ sensor. The great sensing enhancement is mainly due to a synergistic effect of BP and PEI of the composite, of which the former offers the reactivity while the latter splits the thick BP to thin-layer structured PEI-BP composite for larger reaction area. Meanwhile, a flexible sensor has been successfully fabricated and applied in detecting of Cu2+ in real samples of river, confirming the application feasibility of PEI-BP sensor in water environment control.

Screen-printed analytical strip constructed with bacteria-templated porous N-doped carbon nanorods/Au nanoparticles for sensitive electrochemical detection of dopamine molecules.

Dopamine (DA) as an important neurotransmitter plays an important role in physiological activities, and its abnormal level can cause diseases such as Parkinson's disease. However, the clinical analysis of DA mainly relies on time-consuming and expensive liquid chromatography and molecular spectrometer. We present here a design and fabrication of inexpensive strip sensor constructed from screen printed electrodes for sensitive and selective detection of DA. The ink used for printing the strips contains Shewanella putrefaciens-templated porous N-doped carbon nanorods (N-doped CN) and Au nanoparticles (Au NPs), in which the N-doping enhances CN's negative charge to electrostatically attract the positively charged DA with strong adsorption for achieving fast electron transfer. Moreover, results indicate that the Au NPs impregnation in N-doped CN renders much more catalytic reaction sites toward DA oxidation current. The strip sensor exhibits high sensitivity for DA detection with a broad linear range of 0.02-700 µM and a low detection limit of 0.007 µM as well as good selectivity and superior flexibility for great potential in wearable applications. The strip sensor further performs an accurate detection of DA in human serum, providing a powerful analytical tool for diagnosis of DA related diseases in clinical analysis.

Derivation of empirical model to predict the accumulation of Pb in rice grain.

Lead contamination in soil has become a worldwide threat on food security and human health. To assess the Pb bioavailability and evaluate the safe use of low Pb polluted soil for food production, the speciation of Pb in 19 types of paddy soil were investigated by chemical extraction and X-ray absorption near-edge structure (XANES), and the uptake and accumulation characteristics of Pb in different soil-rice systems were investigated. Moreover, an empirical model was established to predict the content of Pb in rice grain, and field validation was conduct to evaluate model performance. Results showed that the proportion of available Pb in different soil satisfied normal distribution N (0.47, 0.23). Pb(CH3COO)2, GSH-Pb, PbO, PbHPO4 and Pb3(PO4)2 performed well in characterizing the speciation of Pb in different rhizosphere soils, and PbHPO4 accounted for more than 70%. The exceedance of Pb in grain in CK, 0.5X and 1X treatment were 10.5%, 36.1% and 42.1%, respectively, and the accumulation of Pb in grain was significantly related with Pb content in root. Carbonate and organic bound Pb in rhizosphere soil were two major Pb species that influenced the accumulation of Pb in rice. Moreover, content of total Pb, clay and SOM performed well in predicting the Pb content in grain, both for pot and field samples. Above all, our predicting model worked well in evaluating Pb accumulation in rice grain among low polluted paddy farmland (Total Pb < 300 mg/kg).

Controlling Factors and Prediction of Lead Uptake and Accumulation in Various Soil-Pepper Systems.

Lead (Pb) is a typical toxic heavy metal element in soils and plants, which has a potential threat to human health through the food chain. Uptake of Pb in the soil-vegetable system has attracted broad attention, whereas reports on the main controlling factors of Pb uptake and accumulation in different soil-vegetable systems are limited. The effect of soil properties on Pb uptake and accumulation in pepper (Capsicum annuum L.) was studied by a pot experiment with 16 typical soils in China. The results showed that the Pb bioavailability was lower in alkaline soils, and that soil cation exchange capacity (CEC), CaCO3 , and total phosphorus contents might influence the uptake and transfer of Pb by peppers. Soil pH and CEC were the most significant factors affecting Pb accumulation in pepper fruits. Soil pH was negatively correlated with Pb uptake and accumulation due to its influence on Pb mobility and bioavailability. The accumulation of Pb decreased as soil CEC increased, which might inhibit the absorption and transfer of Pb in peppers. The multiple linear regression function based on soil Pb content, pH, and CEC could provide enough information for a good prediction of the accumulation of Pb in soil-pepper systems (R2 = 0.733). The results are in favor of developing a Pb threshold for vegetables in agricultural soils in China, thus improving the food safety of crops. Environ Toxicol Chem 2021;40:1443-1451. © 2021 SETAC.

Wheat (Triticum aestivum L.) grains uptake of lead (Pb), transfer factors and prediction models for various types of soils from China.

Lead (Pb) contaminated in farmlands has become a deep threat to global food security and human health. In this study, the bioavailability of Pb in 18 types of soil to wheat (Triticum aestivum L.) grains were investigated, and reliable empirical models of Pb in wheat grains were established based on soil properties. The results showed that the average bioconcentration factor (BCFgrain/total-Pb) in acidic soils was approximately 3.30 times than that in alkaline soils (ANOVA P < 0.05). Significant positive relationships between wheat grain Pb concentration and soil total Pb or EDTA extractable Pb were presented through the results of simple linear regressions (P < 0.001). The stepwise multiple linear regression models indicated that soil pH and soil total Pb were determined to be the two most reliable and reasonable factors in predicting wheat grain Pb concentration, with 83.8% explanation of variation. Soil total Pb compared with EDTA extractable Pb was applied to better improve prediction models in describing Pb transfer from soils to wheat grains. Furthermore, grouped models divided into two parts with pH of 7.5 also generated well prediction in wheat grain Pb concentration. Our prediction models were successfully verified within 95% prediction intervals for published literature data (including other wheat varieties). Moreover, the results indicated that ungrouped models performed better in predicting accuracy within 400 mg kg-1 of soil total Pb, and grouped models showed better extrapolation stability when Pb in soil were overly high. Our results in the study were conduce to evaluate food security of Pb in contaminated agricultural soils.

Electrical tension-triggered conversion of anaerobic to aerobic respiration of Shewanella putrefaciens CN32 cells while promoting biofilm growth in microbial fuel cells.

A global gene expression analysis of Shewanella putrefaciens CN32 cells nearby a nanostructured microbial anode reveals an electrical tension-triggered conversion of anaerobic respiration to aerobic respiration with increased excretion of flavin electron shuttles and cytochrome C proteins, which sheds light on the role of electric tension in cell organisms.

Nitrogen doping to atomically match reaction sites in microbial fuel cells.

Direct electron transfer at microbial anodes offers high energy conversion efficiency but relies on low concentrations of redox centers on bacterium membranes resulting in low power density. Here a heat-treatment is used to delicately tune nitrogen-doping for atomic matching with Flavin (a diffusive mediator) reaction sites resulting in strong adsorption and conversion of diffusive mediators to anchored redox centers. This impregnates highly concentrated fixed redox centers in the microbes-loaded biofilm electrode. This atomic matching enables short electron transfer pathways resulting in fast, direct electrochemistry as shown in Shewanella putrefaciens (S. putrefaciens) based microbial fuel cells (MFCs), showing a maximum power output higher than the conventional non-matched nitrogen-doped anode based MFCs by 21 times. This work sheds a light on diffusion mediation for fast direct electrochemistry, while holding promise for efficient and high power MFCs.