A green and facile approach to a graphene-based peroxidase-like nanozyme and its application in sensitive colorimetric detection of L-cysteine.

A facile and green approach to the preparation of peroxidase-like nanozymes by reducing and functionalizing graphene oxide (rGO) with Ganoderma polysaccharide (GP) has been achieved in this work. Our results showed that the as-fabricated nanozyme, namely rGO-GP, possessed the excellent property of simulating peroxidase with higher catalytic activity compared with GO or rGO obtained by using chitosan, which may be due to the better dispersion of rGO-GP in the solution. Steady-state kinetics studies further showed that the catalytic process conformed to Michaelis-Menten equation and ping-pong mechanism. Benefiting from the excellent peroxidase property of rGO-GP, we have also successfully established a highly sensitive and selective colorimetric detection approach to trace detection of L-cysteine (L-Cys). The limit of detection (LOD) of L-cysteine is 0.1 µM and the linear detection range is 2-30 µM. Furthermore, the nanozyme was successfully applied for detecting L-cysteine in serum. This work therefore demonstrates the advantages of rGO-GP as an effective nanozyme in both its green synthesis and detecting application.

Highly Stretchable and Strain-Insensitive Fiber-Based Wearable Electrochemical Biosensor to Monitor Glucose in the Sweat.

Development of high-performance fiber-shaped wearable sensors is of great significance for next-generation smart textiles for real-time and out-of-clinic health monitoring. The previous focus has been mainly on monitoring physical parameters such as pressure and strains associated with human activities. Development of an enzyme-based non-invasive wearable electrochemical sensor to monitor biochemical vital signs of health such as the glucose level in sweat has attracted increasing attention recently, due to the unmet clinical needs for the diabetic patients. To achieve this, the key challenge lies in the design of a highly stretchable fiber with high conductivity, facile enzyme immobilization, and strain-insensitive properties. Herein, we demonstrate an elastic gold fiber-based three-electrode electrochemical platform that can meet the aforementioned criteria toward wearable textile glucose biosensing. The gold fiber could be functionalized with Prussian blue and glucose oxidase to obtain the working electrode and modified by Ag/AgCl to serve as the reference electrode; and the nonmodified gold fiber could serve as the counter electrode. The as-fabricated textile glucose biosensors achieved a linear range of 0-500 µM and a sensitivity of 11.7 µA mM-1 cm-2. Importantly, such sensing performance could be maintained even under a large strain of 200%, indicating the potential applications in real-world wearable biochemical diagnostics from human sweat.

Real-Time and In-Situ Monitoring of H2O2 Release from Living Cells by a Stretchable Electrochemical Biosensor Based on Vertically Aligned Gold Nanowires.

Traditional electrochemical biosensing electrodes (e.g., gold disk, glassy carbon electrode, etc.) can undergo sophisticated design to detect chemicals/biologicals from cells. However, such electrodes are typically rigid and nonstretchable, rendering it challenging to detect cellular activities in real-time and in situ when cells are in mechanically deformed states. Here, we report a new stretchable electrochemical cell-sensing platform based on vertically aligned gold nanowires embedded in PDMS (v-AuNWs/PDMS). Using H2O2 as a model analyte, we show that the v-AuNWs/PDMS electrode can display an excellent sensing performance with a wide linear range, from 40 µM to 15 mM, and a high sensitivity of 250 mA/cm2/M at a potential of -0.3 V. Moreover, living cells can grow directly on our stretchable high-surface area electrodes with strong adhesion, demonstrating their excellent biocompatibility. Further cell stimulation by adding chemicals induced H2O2 generation, which can be detected in real-time and in situ using our v-AuNWs/PDMS platform for both natural and stretched states of cells. Our results indicate the v-AuNWs/PDMS electrochemical biosensor may serve as a general cell-sensing platform for living organisms under deformed states.

Embedding Pinhole Vertical Gold Nanowire Electronic Skins for Braille Recognition.

Electronic skins (e-skins) have the potential to be conformally integrated with human body to revolutionize wearable electronics for a myriad of technical applications including healthcare, soft robotics, and the internet of things, to name a few. One of the challenges preventing the current proof of concept translating to real-world applications is the device durability, in which the strong adhesion between active materials and elastomeric substrate or human skin is required. Here, a new strategy is reported to embed vertically aligned standing gold nanowires (v-AuNWs) into polydimethylsiloxane, leading to a robust e-skin sensor. It is found that v-AuNWs with pinholes can have an adhesion energy 18-fold greater than that for pinhole-free v-AuNWs. Finite element modeling results show that this is due to friction force from interfacial embedment. Furthermore, it is demonstrated that the robust e-skin sensor can be used for braille recognition.

Fractal Gold Nanoframework for Highly Stretchable Transparent Strain-Insensitive Conductors.

Percolation networks of one-dimensional (1D) building blocks (e.g., metallic nanowires or carbon nanotubes) represent the mainstream strategy to fabricate stretchable conductors. One of the inherent limitations is the control over junction resistance between 1D building blocks in natural and strained states of conductors. Herein, we report highly stretchable transparent strain-insensitive conductors using fractal gold (F-Au) nanoframework based on a one-pot templateless wet chemistry synthesis method. The monolayered F-Au nanoframework (∼20 nm in thickness) can be obtained from the one-pot synthesis without any purification steps involved and can be transferred directly to arbitrary substrates like polyethylene terephthalate, food-wrap, polydimethylsiloxane (PDMS), and ecoflex. The F-Au thin film with no capping agents leads to a highly conductive thin film without any post-treatment and can be stretched up to 110% strain without significantly losing conductivity yet with the optical transparency of 70% at 550 nm. Remarkably, the F-Au thin film shows the strain-insensitive behavior up to 20% stretching strain. This originates from the unique fractal nanomesh-like structure which can absorb external mechanical forces, thus maintaining electron pathways throughout the nanoframework. In addition, a semitransparent bilayered F-Au film on 100% prestrained PDMS could achieve to a high stretchability of 420% strain with negligible resistance changes under low-level strains.

Effective defluorination of novel hexafluoropropylene oxide oligomer acids under mild conditions by UV/sulfite/iodide: mechanisms and ecotoxicity.

It has recently been discovered that HFPO-TA (a processing aid in the production of fluoropolymers) has high levels of bioaccumulation and biotoxicity. Hydrated electrons (eaq-) have been proposed to be potent nucleophiles that may decompose PFAS. Unlike previous studies in which the generation of eaq- was often restricted to anaerobic or highly alkaline environments, in this study, we applied the UV/SO32-/I- process under mild conditions of neutrality, low source chemical demand, and open-air, which achieved effective degradation (81.92 %, 0.834 h-1) and defluorination (48.99 %, 0.312 h-1) of HFPO-TA. With I- as the primary source of eaq-, SO32- acting as an I- regenerator and oxidizing substances scavenger, UV/SO32-/I- outperformed others under mild circumstances. The eaq- were identified as the main active species by quenching experiments and electron paramagnetic resonance (EPR). During degradation, the first site attacked by eaq- was the ether bond (C6-O7), followed by the generation of HFPO-DA, TFA, acetic and formic acid. Degradation studies of other HFPOs have shown that the defluorination of HFPOs was accompanied by a clear chain-length correlation. At last, toxicological experiments confirmed the safety of the process. This study updated our understanding of the degradation of newly PFASs and the application of eaq- mediated photoreductive approaches under mild conditions.

Dynamic evolution characteristics and hazard assessment of compound drought/waterlogging and low temperature events for maize.

Hazard assessment is fundamental in the field of disaster risk management. With the increase in global warming, compound water and temperature events have become more frequent. Current research lacks risk assessments of low temperatures and their compound events, necessitating relevant hazard assessment work to improve the accuracy and diversity of maize disaster prevention and mitigation strategies. This study comparatively analyzed the dynamic evolution characteristics and hazards of compound drought/waterlogging and low temperature events (CDLEs and CWLEs) for maize in the Songliao Plain during different growth periods from 1981 to 2020. First, composite drought/waterlogging and low temperature magnitude indices (CDLMI and CWLMI) were constructed to quantify the intensity of CDLEs and CWLEs by fitting non-exceedance probabilities. Next, static and dynamic hazard assessment models were developed by fitting probability density and cumulative probability density curves to CDLMI and CWLMI. The results showed that the correlations between SPRI and LTI across different decades were mainly negative during the three growth periods. The hazard ratings for both CDLEs and CWLEs were relatively high in the northern part of the study area, consistent with the higher occurrence, duration, and severity of both CDLEs and CWLEs at higher latitudes. Relative to 2001-2010, the center of gravity of hazard shifted southward for CDLEs and northward for CWLEs in 2011-2020. The mean duration, frequency, and hazard were generally higher for CWLEs, but CDLEs were associated with more severe maize yield reductions. This study provides new insights into compound disaster risk assessment, and the research methodology can be generalized to other agricultural growing areas to promote sustainable development of agricultural systems and food security.

Real-time hazard assessment of maize based on the chilling injury process -- Using a standard curve to establish a daily cumulative assessment method.

Cold damage caused by low temperatures is known as chilling injury (CI), and it has consistently been one of the primary meteorological disasters affecting maize. With ongoing global climate change, the issue of chilling injury is becoming more prominent, exhibiting new characteristics and presenting new challenges. Consequently, understanding the disaster process and conducting a more refined real-time chilling injury identification have become significant challenges. In this study, we divided maize planting areas into seven maturity types based on the accumulated temperature, constructed a standard curve of the daily accumulated temperature from 1991 to 2020, proposed real-time identification indicators based on the CI process, and developed a real-time CI hazard assessment model. The results indicated that the model can capture independent CI events and rapidly determine the location, intensity, duration and scope of CIs, thereby providing a basis for accurately understanding the impact of chilling injury and taking timely countermeasures. The combination of accumulated temperature standard curves for seven maturity types of maize and the CI curve was used to construct the CI daily scale identification indicator, ΔEAT. Judgment thresholds for the CI identification indicators at various maturity levels were obtained by correlating them with historical disaster data. The frequency and intensity of maize CI gradually increased from the extremely late-maturing zone to the extremely early-maturing zone, with the seeding and emergence periods being the peak periods for CI. The spatiotemporal evolution characteristics of the three different degrees of CI events in 1992, 2004, and 2017 were consistent with the historical disaster records. Northeastern Inner Mongolia and most of Heilongjiang were found to be high-hazard areas for maize CIs. The constructed daily CI identification indicators can accurately and rapidly identify maize CIs, providing practical and targeted guidance for combating these injuries.

Residues, potential source and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in surface water of the East Liao River, Jilin Province, China.

The environmental risks posed by polycyclic aromatic hydrocarbons (PAHs) and the diversity of their anthropogenic origins make them a global issue. Therefore, it is of utmost significance for protecting the aquatic environment and the growth of neighboring populations to identify their possible origins and ecological risk. Here, we detail the contamination profiles of 15 PAHs found in the East Liao River's surface waters in Jilin Province and use the receptor model Absolute Principal Component Analysis - Multiple Linear Regression (APCS-MLR) and diagnostic ratios method to identify the primary potential sources of pollution. Based on the natural hazard risk formation theory (NHRFT), an ecological risk assessment (ERA) model for PAHs in the East Liao River was developed. The method assesses the ecological risk status of PAHs by integrating the risk quotient (RQ) approach and the DPSIRM (driving force, pressure, state, impact, response, management) conceptual framework. Total concentrations in the surface water body were between 396.42 and 624.06 ng/L, with an average of 436.99 ng/L. The source research revealed that coal, biomass, and traffic emission sources are the most likely PAH contributors to the East Liao River. The ERA found that the majority of the sites' locations of the study were at low risk for PAHs in surface water bodies (30.7 % and 32.2 %, respectively), while only a tiny percentage of sites were at high or very high risk (1.8 % and 13.6 %). The study results provide theoretical support for the East Liao River's ecological, environmental protection, and policy formulation.

Hydrated electron based photochemical processes for water treatment.

Hydrated electron (eaq-) based photochemical processes have emerged as a promising technology for contaminant removal in water due to the mild operating conditions. This review aims to provide a comprehensive and up-to-date summary on eaq- based photochemical processes for the decomposition of various oxidative contaminants. Specifically, the characteristics of different photo-reductive systems are first elaborated, including the environment required to generate sufficient eaq-, the advantages and disadvantages of each system, and the comparison of the degradation efficiency of contaminants induced by eaq-. In addition, the identification methods of eaq- (e.g., laser flash photolysis, scavenging studies, chemical probes and electron spin resonance techniques) are summarized, and the influences of operating conditions (e.g., solution pH, dissolved oxygen, source chemical concentration and UV type) on the performance of contaminants are also discussed. Considering the complexity of contaminated water, particular attention is paid to the influence of water matrix (e.g., coexisting anions, alkalinity and humic acid). Moreover, the degradation regularities of various contaminants (e.g., perfluorinated compounds, disinfection by-products and nitrate) by eaq- are summarized. We finally put forward several research prospects for the decomposition of contaminants by eaq- based photochemical processes to promote their practical application in water treatment.

Stretchable gold fiber-based wearable electrochemical sensor toward pH monitoring.

Sweat pH is a key health indicator related to metabolism and homeostasis level through hydrogen ion concentration in biological bio-fluid. Therefore, increasing research efforts have been directed to develop wearable pH sensors towards continuous non-invasive monitoring of sweat pH values in the out-of-hospital environments. Herein, we report a stretchable gold fiber-based electrochemical pH sensor based on our recently developed elastomer-bonded gold nanowire coating technology. The densely packed gold film offers superior strain-insensitive conductivity, high stretchability and large electrochemical active surface area (EASA). By electrodepositing polyamine (PANI) and Ag/AgCl onto the gold fibers, we could selectively detect the pH based on open circuit potentials in an ion-selective electrode design. The obtained fiber-based pH sensors feature a great sensitivity (60.6 mV per pH), high selectivity against cationic interference and high stretchability (up to 100% strain). One of the attributes for the fiber-based sensors is that they can be weaved into textiles, holding great potential for integration into everyday clothing for "unfeelable" personal health monitoring.

Hierarchically Structured Vertical Gold Nanowire Array-Based Wearable Pressure Sensors for Wireless Health Monitoring.

We have recently demonstrated that vertically aligned gold nanowires (v-AuNWs) are outstanding material candidates for wearable biomedical sensors toward real-time and noninvasive health monitoring because of their excellent tunable electrical conductivity, biocompatibility, chemical inertness, and wide electrochemical window. Here, we show that v-AuNWs could also be used to design a high-performance wearable pressure sensor when combined with rational structural engineering such as pyramid microarray-based hierarchical structures. The as-fabricated pressure sensor featured a low operation voltage of 0.1 V, high sensitivity in a low-pressure regime, a fast response time of <10 ms, and high durability with stable signals for the 10 000 cycling test. In conjunction with printed electrode arrays, we could generate a multiaxial map for spatial pressure detection. Furthermore, our flexible pressure sensor could be seamlessly connected with a Bluetooth low-energy module to detect high-quality artery pulses in a wireless manner. Our solution-based gold coating strategy offers the benefit of conformal coating of nanowires onto three-dimensional microstructured elastomeric substrates under ambient conditions, indicating promising applications in next-generation wearable biodiagnostics.

Highly Stretchable Fiber-Shaped Supercapacitors Based on Ultrathin Gold Nanowires with Double-Helix Winding Design.

The ability of developing highly durable fiber-shaped electronic devices is crucial for next-generation smart textile electronics. Past several years have witnessed encouraging progress made in stretchable fiber-shaped supercapacitors using carbon materials, transition metal oxides, and conducting polymers. Here, we report a dry-spun strategy to produce scalable ultrathin gold nanowire-based fibers, which can lead to highly stretchable fiber-based supercapacitors using a double-helix winding design. Hildebrand's and Hansen's solubility parameters of gold nanowire-binding oleylamine ligands match those of styrene-ethylene/butylene-styrene and tetrahydrofuran, enabling the formation of high-quality dry-spun fibers. In conjunction with conductivity enhancement by electroless plating and pseudocapacitance by polyaniline, we obtained fiber-shaped supercapacitors stretchable up to 360% with a capacitance of 16.80 mF cm-2. The capacitance retention is about 85% after 2000 cycles of 0-200-0% stretching/releasing. Our fiber capacitors can be woven into an everyday glove, with negligible capacitance changes for normal finger movements.

A location- and sharpness-specific tactile electronic skin based on staircase-like nanowire patches.

Human skin can sense an external object in a location-specific manner, simultaneously recognizing whether it is sharp or blunt. Such tactile capability can be achieved in both natural and stretched states. It is impractical to mimic this tactile function of human skin by designing pixelated sensor arrays across our whole curvilinear human body. Here, we report a new tactile electronic skin sensor based on staircase-like vertically aligned gold nanowires (V-AuNWs). With a back-to-back linear or spiral assembly of two staircase structures into a single sensor, we are able to recognize pressure in a highly location-specific manner for both non-stretched and stretched states (up to 50% strain); with a concentric design on the fingertip, we can identify the sharpness of an external object. We believe that our strategy opens up a new route to highly specific second-skin-like tactile sensors for electronic skin (E-skin) applications.

Self-assembled gold nanorime mesh conductors for invisible stretchable supercapacitors.

Thin, skin-conformal, transparent and stretchable energy devices are ideal for powering future wearable and implantable electronics. However, it is difficult to achieve such "unfeelable" and "invisible" devices with traditional materials and design methodologies because of the challenge of simultaneously achieving high optical transparency, high electrical conductivity and high mechanical stretchability. Here, we report a two-step nanowire growth approach for fabricating gold nanorime mesh conductors, enabling skin-thin, transparent and stretchable supercapacitors. Solution-state oleylamine-capped 2 nm-thin gold nanowires self-assemble into highly transparent nanomeshes, which then serve as templates for growing highly conductive vertically aligned nanowires. This two-step solution-plus-surface nanowire growth strategy leads to elastic gold nanorime mesh conductors with an optical transparency up to 90.3% at 550 nm, a low sheet resistance as low as 1.7 ± 0.8 Ω sq-1, and a stretchability of over 100% strain. Such elastic conductors are successfully used to construct symmetrical supercapacitors that can simultaneously achieve high areal capacitance and high stretchability, demonstrating the potential to power future bio-integratable electronics.