Monolithic silicon for high spatiotemporal translational photostimulation.

Electrode-based electrical stimulation underpins several clinical bioelectronic devices, including deep-brain stimulators1,2 and cardiac pacemakers3. However, leadless multisite stimulation is constrained by the technical difficulties and spatial-access limitations of electrode arrays. Optogenetics offers optically controlled random access with high spatiotemporal capabilities, but clinical translation poses challenges4-6. Here we show tunable spatiotemporal photostimulation of cardiac systems using a non-genetic platform based on semiconductor-enabled biomodulation interfaces. Through spatiotemporal profiling of photoelectrochemical currents, we assess the magnitude, precision, accuracy and resolution of photostimulation in four leadless silicon-based monolithic photoelectrochemical devices. We demonstrate the optoelectronic capabilities of the devices through optical overdrive pacing of cultured cardiomyocytes (CMs) targeting several regions and spatial extents, isolated rat hearts in a Langendorff apparatus, in vivo rat hearts in an ischaemia model and an in vivo mouse heart model with transthoracic optical pacing. We also perform the first, to our knowledge, optical override pacing and multisite pacing of a pig heart in vivo. Our systems are readily adaptable for minimally invasive clinical procedures using our custom endoscopic delivery device, with which we demonstrate closed-thoracic operations and endoscopic optical stimulation. Our results indicate the clinical potential of the leadless, lightweight and multisite photostimulation platform as a pacemaker in cardiac resynchronization therapy (CRT), in which lead-placement complications are common.

Multimodal probing of T-cell recognition with hexapod heterostructures.

Studies using antigen-presenting systems at the single-cell and ensemble levels can provide complementary insights into T-cell signaling and activation. Although crucial for advancing basic immunology and immunotherapy, there is a notable absence of synthetic material toolkits that examine T cells at both levels, and especially those capable of single-molecule-level manipulation. Here we devise a biomimetic antigen-presenting system (bAPS) for single-cell stimulation and ensemble modulation of T-cell recognition. Our bAPS uses hexapod heterostructures composed of a submicrometer cubic hematite core (α-Fe2O3) and nanostructured silica branches with diverse surface modifications. At single-molecule resolution, we show T-cell activation by a single agonist peptide-loaded major histocompatibility complex; distinct T-cell receptor (TCR) responses to structurally similar peptides that differ by only one amino acid; and the superior antigen recognition sensitivity of TCRs compared with that of chimeric antigen receptors (CARs). We also demonstrate how the magnetic field-induced rotation of hexapods amplifies the immune responses in suspended T and CAR-T cells. In addition, we establish our bAPS as a precise and scalable method for identifying stimulatory antigen-specific TCRs at the single-cell level. Thus, our multimodal bAPS represents a unique biointerface tool for investigating T-cell recognition, signaling and function.

Exploring Present and Future Directions in Nano-Enhanced Optoelectronic Neuromodulation.

Electrical neuromodulation has achieved significant translational advancements, including the development of deep brain stimulators for managing neural disorders and vagus nerve stimulators for seizure treatment. Optoelectronics, in contrast to wired electrical systems, offers the leadless feature that guides multisite and high spatiotemporal neural system targeting, ensuring high specificity and precision in translational therapies known as "photoelectroceuticals". This Account provides a concise overview of developments in novel optoelectronic nanomaterials that are engineered through innovative molecular, chemical, and nanostructure designs to facilitate neural interfacing with high efficiency and minimally invasive implantation.This Account outlines the progress made both within our laboratory and across the broader scientific community, with particular attention to implications in materials innovation strategies, studying bioelectrical activation with spatiotemporal methods, and applications in regenerative medicine. In materials innovation, we highlight a nongenetic, biocompatible, and minimally invasive approach for neuromodulation that spans various length scales, from single neurons to nerve tissues using nanosized particles and monolithic membranes. Furthermore, our discussion exposes the critical unresolved questions in the field, including mechanisms of interaction at the nanobio interface, the precision of cellular or tissue targeting, and integration into existing neural networks with high spatiotemporal modulation. In addition, we present the challenges and pressing needs for long-term stability and biocompatibility, scalability for clinical applications, and the development of noninvasive monitoring and control systems.In addressing the existing challenges in the field of nanobio interfaces, particularly for neural applications, we envisage promising strategic directions that could significantly advance this burgeoning domain. This involves a deeper theoretical understanding of nanobiointerfaces, where simulations and experimental validations on how nanomaterials interact spatiotemporally with biological systems are crucial. The development of more durable materials is vital for prolonged applications in dynamic neural interfaces, and the ability to manipulate neural activity with high specificity and spatial resolution, paves the way for targeting individual neurons or specific neural circuits. Additionally, integrating these interfaces with advanced control systems, possibly leveraging artificial intelligence and machine learning algorithms and programming dynamically responsive materials designs, could significantly ease the implementation of stimulation and recording. These innovations hold the potential to introduce novel treatment modalities for a wide range of neurological and systemic disorders.

Multiple roles of released c-type cytochromes in tuning electron transport and physiological status of Geobacter sulfurreducens.

Dissimilatory metal-reducing bacteria (DMRB) can transfer electrons to extracellular insoluble electron acceptors and play important roles in geochemical cycling, biocorrosion, environmental remediation, and bioenergy generation. c-type cytochromes (c-Cyts) are synthesized by DMRB and usually transported to the cell surface to form modularized electron transport conduits through protein assembly, while some of them are released as extracellularly free-moving electron carriers in growth to promote electron transport. However, the type of these released c-Cyts, the timing of their release, and the functions they perform have not been unrevealed yet. In this work, after characterizing the types of c-Cyts released by Geobacter sulfurreducens under a variety of cultivation conditions, we found that these c-Cyts accumulated up to micromolar concentrations in the surrounding medium and conserved their chemical activities. Further studies demonstrated that the presence of c-Cyts accelerated the process of microbial extracellular electron transfer and mediated long-distance electron transfer. In particular, the presence of c-Cyts promoted the microbial respiration and affected the physiological state of the microbial community. In addition, c-Cyts were observed to be adsorbed on the surface of insoluble electron acceptors and modify electron acceptors. These results reveal the overlooked multiple roles of the released c-Cyts in acting as public goods, delivering electrons, modifying electron acceptors, and even regulating bacterial community structure in natural and artificial environments.

Nano- and Microscale Optical and Electrical Biointerfaces and Their Relevance to Energy Research.

Different research fields in energy sciences, such as photovoltaics for solar energy conversion, supercapacitors for energy storage, electrocatalysis for clean energy conversion technologies, and materials-bacterial hybrid for CO2 fixation have been under intense investigations over the past decade. In recent years, new platforms for biointerface designs have emerged from the energy conversion and storage principles. This paper reviews recent advances in nano- and microscale materials/devices for optical and electrical biointerfaces. First, a connection is drawn between biointerfaces and energy science, and how these two distinct research fields can be connected is summarized. Then, a brief overview of current available tools for biointerface studies is presented. Third, three representative biointerfaces are reviewed, including neural, cardiac, and bacterial biointerfaces, to show how to apply these tools and principles to biointerface design and research. Finally, two possible future research directions for nano- and microscale biointerfaces are proposed.

Unrecognized Contributions of Dissolved Organic Matter Inducing Photodamages to the Decay of Extracellular DNA in Waters.

Extracellular DNA (eDNA), which is derived from lysis or secretion of cells, is ubiquitous in various environments and crucial for gene dissemination, bacterial metabolism, biofilm integrity, and aquatic monitoring. However, these processes are largely influenced by damage to eDNA. Photodamage to eDNA, one of the most important types of DNA damage in natural waters, thus far remains unclear. In particular, the roles of the ubiquitous dissolved organic matter (DOM) in this process have yet to be determined. In this study, eDNA photodamage, including both deoxynucleoside damage and strand breaks, proved to be significantly influenced by DOM. DOM competed with eDNA for photons to inhibit the direct photodamage of eDNA. Nevertheless, DOM was photosensitized to produce reactive oxygen species (ROS) (i.e., hydroxyl radicals (·OH) and singlet oxygen (1O2)) to enhance the indirect photodamage of eDNA. The ·OH induced damage to four deoxynucleosides and strand breaks, and the 1O2 substantially enhanced deoxyguanosine damage. The presence of DOM changed the main photodamage products of deoxynucleosides, additional oxidation products induced by ROS formed besides pyrimidine dimers caused by UV. Results indicate that DOM-mediated indirect photodamage contributed significantly to eDNA photodamage in most water bodies. This study revealed the previously unrecognized crucial role of DOM in the decay of eDNA in waters.

Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with Mn1.8Fe1.2O4 Nanospheres: Synergism between Mn and Fe.

A high-efficient, low-cost, and eco-friendly catalyst is highly desired to activate peroxides for environmental remediation. Due to the potential synergistic effect between bimetallic oxides' two different metal cations, these oxides exhibit superior performance in the catalytic activation of peroxymonosulfate (PMS). In this work, novel Mn1.8Fe1.2O4 nanospheres were synthesized and used to activate PMS for the degradation of bisphenol A (BPA), a typical refractory pollutant. The catalytic performance of the Mn1.8Fe1.2O4 nanospheres was substantially greater than that of the Mn/Fe monometallic oxides and remained efficient in a wide pH range from 4 to 10. More importantly, a synergistic effect between solid-state Mn and Fe was identified in control experiments with Mn3O4 and Fe3O4. Mn was inferred to be the primary active site in the surface of the Mn1.8Fe1.2O4 nanospheres, while Fe(III) was found to play a key role in the synergism with Mn by acting as the main adsorption site for the reaction substrates. Both sulfate and hydroxyl radicals were generated in the PMS activation process. The intermediates of BPA degradation were identified and the degradation pathways were proposed. This work is expected to help to elucidate the rational design and efficient synthesis of bimetallic materials for PMS activation.

Harnessing Multiscale Physiochemical Interactions on Nanobiointerface for Enhanced Stress Resilience in Rice.

Nanoagrochemicals present promising solutions for augmenting conventional agriculture, while insufficient utilization of nanobiointerfacial interactions hinders their field application. This work investigates the multiscale physiochemical interactions between nanoagrochemicals and rice (Oryza sativa L.) leaves and devises a strategy for elevating targeting efficiency of nanoagrochemicals and stress resilience of rice. We identified multiple deposition behaviors of nanoagrochemicals on hierarchically structured leaves and demonstrated the crucial role of leaf microarchitectures. A transition from the Cassie-Baxter to the Wenzel state significantly changed the deposition behavior from superlattice assembly, ring-shaped aggregation to uniform monolayer deposition. By fine-tuning the formulation properties, we achieved a 415.9-fold surge in retention efficiency, and enhanced the sustainability of nanoagrochemicals by minimizing loss during long-term application. This biointerface design significantly relieved the growth inhibition of Cd(II) pollutant on rice plants with a 95.2% increase in biomass after foliar application of SiO2 nanoagrochemicals. Our research elucidates the intricate interplay between leaf structural attributes, nanobiointerface design, and biological responses of plants, fostering field application of nanoagrochemicals.

Active biointegrated living electronics for managing inflammation.

Seamless interfaces between electronic devices and biological tissues stand to revolutionize disease diagnosis and treatment. However, biological and biomechanical disparities between synthetic materials and living tissues present challenges at bioelectrical signal transduction interfaces. We introduce the active biointegrated living electronics (ABLE) platform, encompassing capabilities across the biogenic, biomechanical, and bioelectrical properties simultaneously. The living biointerface, comprising a bioelectronics layout and a Staphylococcus epidermidis-laden hydrogel composite, enables multimodal signal transduction at the microbial-mammalian nexus. The extracellular components of the living hydrogels, prepared through thermal release of naturally occurring amylose polymer chains, are viscoelastic, capable of sustaining the bacteria with high viability. Through electrophysiological recordings and wireless probing of skin electrical impedance, body temperature, and humidity, ABLE monitors microbial-driven intervention in psoriasis.

Deciphering the microheterogeneous repartition effect of environmental matrix on surface-enhanced Raman spectroscopy (SERS) analysis for pollutants in natural waters.

Although surface-enhanced Raman spectroscopy (SERS) offers a promising technology for sensitive detection of environmental pollutants in natural waters, its performance can be greatly affected by the environmental matrix. The lack of identification of the origin and the underlying mechanism of matrix effect hinders the application of SERS in practical environmental analysis. Herein, with silver nanoparticles (AgNPs) as a solution-based SERS substrate, the matrix effect from environmental waters on SERS analysis and the underlying mechanisms were investigated. It was found that natural water matrix could deteriorate SERS performance and cause artefacts in SERS spectra. Among various aqueous components, natural organic matter (NOM), including humic substances and proteins, mainly contributed to the matrix effect on SERS detection, while polysaccharides or inorganic ions had minor influence. The matrix effect from NOM was found to be prevalent for different analytes and SERS substrates. The mechanism of the matrix effect from NOM in the ternary system of analyte, NOM, and nanoparticles was investigated through three mutual interactions. The microheterogeneous repartition of analytes by NOM, other than the formation of NOM-corona or competitive adsorption between NOM and analytes on nanoparticles, was found to play the dominating role in interfering with SERS detection. This work illuminates the origin and underlying mechanisms of the matrix effect, which will promote the practical application of SERS technology in environmental analysis.

Anaerobic electrochemical membrane bioreactor effectively mitigates antibiotic resistance genes proliferation under high antibiotic selection pressure.

The spread of antibiotics and antibiotic resistance genes (ARGs) in environments has posed potential threats to public health. Unfortunately, conventional biological wastewater treatment technologies generally show insufficient removal of antibiotics and ARGs. Bioelectrochemical systems, which can effectively degrade refractory organic pollutants via enhancing microbial metabolisms through electrochemical redox reaction, may provide an alternative for the control of antibiotics and ARGs. Herein, an anaerobic electrochemical membrane bioreactor (AnEMBR) was conducted by combining bioelectrochemical system and anaerobic membrane bioreactor to treat antibiotic-containing wastewater. The AnEMBR at open circuit showed stable CH4 production and high removal of COD and chlortetracycline (CTC) in treating 2.5-15 mg/L CTC. However, increasing CTC to 45 mg/L completely inhibited the methanogenesis of AnEMBR at open circuit. After applying external voltage in AnEMBR, the performances of AnEMBR were significantly improved (e.g., increased CH4 production and CTC removal). Moreover, CTC exposure significantly increased the relative abundances of ARGs in sludge, supernatant, and effluent in AnEMBR at open circuit. Applying voltage greatly attenuated the total relative abundances of ARGs in the supernatant and effluent of AnEMBR compared to those at open circuit. This could be attributed to the enrichment of tetracycline degradation gene tetX, which greatly enhanced the removal of CTC by the AnEMBR and thus reduced the selective pressure of CTC on the microorganisms in supernatant and effluent for ARGs proliferation. These results would provide an effective wastewater treatment technology for treating high-level antibiotic-containing wastewater to mitigate the potential risk of ARGs and antibiotics spread in receiving water body.

Adsorption of ciprofloxacin to functionalized nano-sized polystyrene plastic: Kinetics, thermochemistry and toxicity.

Plastic debris is ubiquitous in aquatic systems and has been proven vehicles for the transport of various pollutants including trace organic compounds. Nanoplastics have large specific surface area and hydrophobic characteristics and therefore are capable of adsorbing other organic or inorganic chemicals from the environment. Antibiotics, as another class of emerging contaminants, have raised significant research concern in recent years as they pose threats to the ecosytems and human health. Nevertheless, little information is available on the adsorption behaviors of antibiotics onto nano-sized plastics. The toxicity of combined nanoplastics and antibiotics is also largely unknown. In this study, the physicochemical and thermodynamic interactions between representative nanoplastics, which containing a carboxyl functional group of polystyrene nanoplastics (PS-COOH), and typical antibiotic, i.e., ciprofloxacin (CIP) were investigated in a batch adsorption experiment. The specific thermodynamic correlation function of PS-COOH combined with CIP was obtained through isothermal titration microcalorimetry (ITC) analysis. The adsorption kinetics and isotherm of CIP on PS-COOH closely fit the pseudo-second-order kinetic model (r2 = 0.99) and Freundlich isotherm (r2 = 0.99). The ITC results showed that the adsorption reaction of PS-COOH with CIP was a spontaneous exothermic reaction. The adsorption of antibiotics on nanoplastics may aggravate the negative impacts of these two pollutants on aqueous ecosystems, and we hypothesized that would be reflected in the survival rate of model organism of Caenorhabditis elegans when exposed to this combination. This work used a mechanistic approach to unravel the adsorption behavior of antibiotics on nanoplastics and shed light on their potential impact on aquatic ecosystems.

Selectively Tracking Nanoparticles in Aquatic Plant Using Core-Shell Nanoparticle-Enhanced Raman Spectroscopy Imaging.

Nanoparticles contribute to enormous environmental processes, but, due to analytical challenges, the understanding of nanoparticle fate remains elusive in complex environmental matrices. To address the challenge, a core-shell nanoparticle-enhanced Raman spectroscopy (CSNERS) imaging method was developed to selectively track prevalent SiO2 nanoparticles in an aquatic plant, Lemna minor. By encapsulating gold nanoparticles and Raman reporters inside, the resonance Raman signature was enhanced, thus enabling the sensitive and selective detection of SiO2 nanoparticles at an environmentally relevant concentration. The panoramic visualization of the translocation pathway of nanoparticles shows an unexpected, fast (in hours) and a preferential accumulation of nanoparticles on the node, leaf edge, root cap, etc., implying the ability of CSNERS to spectroscopically determine nanotoxicity. The core-shell design in CSNERS was capable of multiplex labeling two differently charged nanoparticles and distinguishing their biobehavior simultaneously. Meanwhile, the CSNERS method can be further applied for a variety of nanoparticles, implying its promising applications for nanotoxicity research and biogeochemical study.

Highly efficient removal and detoxification of phenolic compounds using persulfate activated by MnOx@OMC: Synergistic mechanism and kinetic analysis.

Persulfate-based advanced oxidation technology exhibits great potential for hazardous organic pollutant removal from wastewater. Acceleration of pollutant degradation needs to be elucidated, particularly for heterogeneous catalytic systems. In this study, manganese oxide ordered mesoporous carbon composites (MnOx@OMC) were prepared by nano-casting method and used for persulfate activation to degrade phenol. Kinetics analysis indicate that the rate of phenol degradation using MnOx@OMC composites was improved by 34.9 folds relative to that using a mixture of MnOx and OMC. The phenol toxicity towards Caenorhabditis elegans could be totally reduced within 8 min. The different roles of MnOx and OMC in persulfate activation were confirmed to validate their synergistic effect. MnOx provided major active sites for persulfate activation in accordance with the surface Mn3+/Mn4+ cycle to induce SO4•- radicals. The OMC matrix provided the adsorption sites to enrich phenol molecules on the catalytic surface and promote the interfacial electron transfer process for persulfate activation. Moreover, a novel kinetic model with two distinct kinetic stages was established to verify the effects of phenol and persulfate on phenol removal.

Redox state of microbial extracellular polymeric substances regulates reduction of selenite to elemental selenium accompanying with enhancing microbial detoxification in aquatic environments.

In nature, many microorganisms show resistance to toxic selenite by reducing selenite to non-soluble and low toxic elemental selenium. Extracellular polymeric substances (EPS), a high-molecular-weight biopolymers originated from microbial metabolism, contain many reducing groups and can induce reductive transformation of pollutants. However, the roles of EPS and its redox state in reductive detoxification or reduction removal of selenite, respectively, remain unknown yet. Herein, the reduction of selenite by different sources of EPS was investigated. Selenite was proved to be reduced by EPS and partly transformed to elemental selenium. The formed elemental selenium was mainly selenium nanoparticles confirmed by transmission electron microscopy coupled with energy dispersive spectroscopy. The redox state of EPS governed selenite reduction and elemental selenium formation, and the reduced state of EPS was in favor of selenite reduction. Dissolved oxygen concentration in water regulated EPS redox state and influenced selenite reduction. The thiols, aldehyde and phenolic groups in EPS were responsible for selenite reduction. Under selenite stress, EPS was capable of increasing cell survivability by enhancing microorganisms-mediated selenite reduction. This work revealed the previously undiscovered roles of EPS in selenite reduction and elemental selenium formation in aquatic environments and also suggested a possible crucial role of EPS in selenium biogeochemical cycle.

Spectroscopic insights into photochemical transformation of effluent organic matter from biological wastewater treatment plants.

The photodegradation of discharged effluent organic matter (EfOM) changes its composition and shifts its impacts on pollutant migration and transformation in receiving waters. However, to date, EfOM photodegradation processes are not well understood due to the complexity and heterogeneity of EfOM. Herein, the spectroscopic analysis including ultra violet-visible (UV-Vis), fluorescence and FTIR spectroscopies coupled with two-dimensional correlation analysis (2D-COS) were used to draw a comprehensive view of EfOM photodegradation and involving mechanisms. Results revealed that the photolability of each component in EfOM followed the order: tannin-like > humic-like > protein-like > carbohydrate-like and aliphatic compounds. The photolability of different components of EfOM were found to be related to the photolability of their functional groups. Specifically, the aromatic, carboxylic, phenolic and quinonoid groups associated with humic or tannin-like compounds were more prone to be photodegraded than amides in proteins or C-OH and C-O-C in carbohydrates. Furthermore, the humic-like components, dominating the light absorption of EfOM, were found to be degraded by direct photolysis. Nevertheless, the photodegradation of tannin-like and protein-like components were mainly due to the indirect photodegradation by ROS and 3OM⁎. Furthermore, results indicated that UV light, rather than visible light, was responsible for the photodegradation of EfOM. The spectroscopic techniques integrated with 2D-COS analysis could serve as a powerful tool with which to clarify complex EfOM photodegradation process as well as to improve our understanding of the fate of discharged EfOM and related environmental processes.

Light-induced reduction of silver ions to silver nanoparticles in aquatic environments by microbial extracellular polymeric substances (EPS).

Microbial extracellular polymeric substances (EPS) widely exist in natural environments and affect the migration and transformation of pollutants in aquatic environments. Previous works report that EPS have some reducing functional groups and can reduce heavy metals. However, because of the weak reducing capability of EPS, the reduction of heavy metals by EPS without cells is extremely slow, and its effect on heavy metals species is insignificant. In this work, the accelerated reduction of silver ions (Ag+) by EPS from Shewanella oneidensis MR-1 under illumination was investigated. UV-visible spectroscopy, transmission electron microscopy (TEM) coupled with an energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS) were used to confirm the formation of silver nanoparticles (AgNPs) via the reduction of Ag+ by EPS under light illumination. The Ag+ reduction by EPS follows pseudo-first-order kinetics under both visible and UV light, and the light irradiation can significantly accelerate AgNPs formation. On the one hand, visible light can excite AgNPs for their surface plasma resonance (SPR) and accelerate the electrons from the EPS to adjacent Ag+. On the other hand, EPS molecules may be excited by UV light to produce strong reducing species, which enhance Ag+ reduction. Moreover, pH, dissolved oxygen were found to affect the formation of AgNPs by EPS. This work proves the reducing capability of EPS on the reduction of Ag+, and this process can be accelerated under light illumination, which may affect the speciation and transformation of heavy metals in natural waters.