Beyond Photosynthesis: H2O/H2O2/O2 Self-Circulation-Based Biohybrid Photoelectrochemical Cells for Direct and Sustainable Solar-to-Fuel-to-Electric Power Conversion.

Solar-to-fuel conversion followed by secondary utilization in fuel cells provides an appealing approach to alleviating global energy shortages but is largely restricted by the complex design of power systems and the development of functional catalysts. Herein, we presented a biohybrid photoelectrochemical cell (BPEC) to implement sustainable solar-to-fuel-to-electric power conversion in a single compartment, by ingeniously combining reliable photoelectrochemical H2O2 generation with efficient bioelectrochemical H2O2 consumption. Specifically, the BPEC is composed of a Mo-modified BiVO4 (Mo:BiVO4) photoanode and a horseradish peroxidase (HRP)/pyrene-modified 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (bis-Pyr-ABTS)/carbon nanotubes with an encapsulated Co nanoparticle (Co/CNTs) biocathode. Upon photoexcitation, two-electron H2O oxidation can be carried out at the Mo-BiVO4 photoanode to produce H2O2, followed by electroenzymatic reduction of H2O2 to H2O by HRP with the help of a bis-Pyr-ABTS redox mediator at the biocathode. Besides, in response to the insufficient Faradaic efficiency of H2O2 generation at the photoanode, the functional Co/CNTs catalysts, possessing prominent electrocatalytic selectivity toward two-electron O2 reduction (electron transfer number = 2.6), are modified on the biocathode, thus clearly defining effective H2O/H2O2/O2 self-circulation in this device. This developed BPEC obtains an open-circuit potential of 1.03 ± 0.02 V and a maximum power density of 0.18 ± 0.02 mW cm-2. Moreover, inspired by the particular advantage of enzymatic biofuel cells for easy miniaturization, an enclosed "sandwich-like" BPEC of approximately 1 cm3 size is fabricated and delivers a power output of 0.13 ± 0.03 mW cm-2. Our work represents a controllable approach for meaningful solar energy utilization, beyond traditional artificial photosynthesis, and can further provide a significant paradigm shift in building an energy-sustainable society.

Water/Oxygen Circulation-Based Biophotoelectrochemical System for Solar Energy Storage and Release.

Fabricating an artificial photoelectrochemical device to provide electric power on demand is highly desirable but remains a challenge. In response to the intermittent nature of sunlight, we develop a water/oxygen circulation-based biophotoelectrochemical system (BPECS) by integrating a polypyrrole (PPy) capacitor electrode into a photobiofuel cell (PBFC). Unlike traditional PEC devices, the modular and integrated system design of BPECS can not only improve compatibility among PEC cells, BFCs, and capacitor devices, but also offers a feasible way for tackling the intermittent nature of sunlight. In this system, the molecules of water and oxygen can form a self-circulation, thus making this device intrinsically safe and cost-effective. Through the alternate two-step energy conversion (i.e., solar-to-chemical/electric and chemical-to-electric), this conceptual model obtains maximum power output densities of 0.34 ± 0.01 and 0.19 ± 0.02 mW cm-2 in light and dark conditions, respectively, and presents stable long-term cycling performance for solar energy storage and release. Our results demonstrate that such a BPECS achieves high-effective solar energy utilization, which carries great significance to the development of artificial BPECS and provides research opportunities to explore a deployable route for grid-scale photovoltaic energy storage.

Alternative to Noble Metal Substrates: Metallic and Plasmonic Ti3O5 Hierarchical Microspheres for Surface Enhanced Raman Spectroscopy.

Compared with noble metals, improving the sensitivity of semiconducting surface-enhanced Raman scattering (SERS) substrates is of great significance to their fundamental research and practical application of Raman spectroscopy. In this paper, it is found that the SERS sensitivity is increased by 10 000 times by reducing the semiconducting TiO2 microspheres to quasi-metallic Ti3O5 microspheres. Its lowest detectable limit is up to 10-10 M, which may be the best among the non-noble metal substrates and even reaches or exceeds certain Au/Ag nanostructures to the best of our knowledge. This new type of non-noble metal SERS substrate breaks through the bottleneck of poor stability of conventional semiconductor substrate and can withstand high temperature oxidation at 200 °C and strong acid-base corrosion without performance degradation. Benefiting from its excellent ability of visible-light photocatalytic degradation of organic molecules, the substrate can be reused. Moreover, the new material also exhibits excellent photothermal conversion properties.

Characterization and analysis of non-ionic surfactants by supercritical fluid chromatography combined with ion mobility spectrometry-mass spectrometry.

Comprehensive separation and analysis of non-ionic surfactants have been conducted by coupling supercritical fluid chromatography (SFC) with ion mobility spectrometry-mass spectrometry (IMS-MS). Representative non-ionic surfactants were investigated, including alkylphenol ethoxylates (APEOs), e.g., octylphenol ethoxylates (OPEOs) and fatty alcohol ethoxylates (FAEs), e.g., lauryl alcohol ethoxylates (LAEs). A sub-2-µm high-density diol column was used for chromatographic separation by the first-dimensional SFC due to the differences in ethoxy chain prior to electrospray ionization (ESI). Maintaining the fidelity of pre-ionization separation in the first dimension, the introduction of IMS provided additional post-ionization resolution by broadly fractionating the oligometric ethoxymers based on their size and electric charge within 13.78 ms. Distinguishable series of singly and multiply charged non-ionic species could be clearly observed. The millisecond timescale ion mobility separation perfectly fits the elution time of a chromatographic peak, while effectively feeding components into the fast-scanning time-of-flight (TOF) mass analyzer for characterization and analysis. The orthogonality of the developed separation and analysis system was evaluated, revealing a correlation coefficient and peak spreading angle of 0.2729 and 74.16° for the studied OPEOs and 0.1962 and 78.69° for LAEs. Significant enhancement in peak capacity was achieved for the developed SFC-IMS-MS system with the actual peak capacity measured to be approximately 41 and 160 times higher than that of the dimensions of SFC and IMS, respectively, when used alone. Graphical abstract.

S100A4 protects mice from high-fat diet-induced obesity and inflammation.

As a member from S100 calcium-binding protein family, S100A4 is ubiquitous and elevated in tumor progression and metastasis, but its role in regulating obesity has not been well characterized. In this study, we showed that S100A4 was mainly expressed by stromal cells in adipose tissue and the S100A4 level in adipose tissue was decreased after high-fat diet (HFD). S100A4 deficient mice exhibited aggravated symptoms of obesity and suppressed insulin signaling after 12 weeks of HFD. Aggravated obesity in S100A4 deficient mice were found to be positively correlated with higher inflammatory status of the liver. Then, we found that extracellular S100A4 or overexpressed S100A4 inhibited adipogenesis and decreased mRNA levels of inflammation gene in 3T3-L1 adipocytes in vitro; whereas small interfering RNA (siRNA)-mediated suppression of S100A4 displayed the opposite results. Additionally, the protective effect induced by S100A4 during HFD-induced obesity was tightly related with activation of Akt signaling in adipose tissues, as well as livers and muscles. Taken together, we demonstrate that S100A4 is an inhibitory factor for obesity and attenuates the inflammatory reaction, while activating the Akt signaling, which suggest that S100A4 is a potential candidate for the treatment of diet-induced obesity and its complications.

A Nanoscale Multichannel Closed Bipolar Electrode Array for Electrochemiluminescence Sensing Platform.

In this work, we report a nanoscale multichannel closed bipolar electrode (BPE) array based on the poly(ethylene terephthalate) (PET) membrane for the first time. With our design, oxidants, coreactants, quenchers, and even biomarkers can be detected in a Ru(bpy)3(2+)/TPA (tripropylamine) electrochemiluminescence (ECL) system. The multichannel PET membrane was etched according to our desire by NaOH, and then Au nanofibers were decorated in the inner region of the channel as a BPE array. Using ECL as a signal readout, a series of targets including TPA, Ru(bpy)3(2+), dopamine, H2O2, alpha-fetoprotein (AFP), and carcino-embryonic antigen (CEA) can be detected with this device. The practical application of the proposed multichannel closed BPE array was verified in the detection of AFP and CEA in human serum with satisfying results. This kind of nanoscale device holds promising potential for multianalysis. More importantly, as the PET membrane used in this device can be etched with a desirable diameter (nano- to microscale) and different BPE array densities (ion tracks of 10(8)/cm(2), 10(6)/cm(2), 10(4)/cm(2)), our design can be served as a useful platform for future advances in nanoscale bipolar electrochemistry.

An amperometric sensor for detection of tryptophan based on a pristine multi-walled carbon nanotube/graphene oxide hybrid.

We report the fabrication of a novel amperometric sensor for tryptophan (Trp) based on a pristine multi-walled carbon nanotube/graphene oxide (pMWCNT/GO) hybrid obtained through the sonication of pMWCNTs in an aqueous solution of GO. The results of transmission electron microscopy and electrochemical impedance spectroscopy demonstrate the successful formation and the excellent charge transfer ability of the resulting hybrid. Compared with the commonly used acid-treated MWCNTs and GO, the resulting hybrid exhibits better electrocatalytic activity towards the oxidation of Trp, which is attributed to the synergistic effect of MWCNTs and GO. The current-time curve reveals that the catalytic oxidation current is linearly dependent on Trp concentration in the range of 50 nM to 4.25 µM with a detection limit of 8 nM (S/N = 3). In addition, the proposed sensor is successfully employed to detect Trp in the real samples with satisfactory results.

A Novel Thin-Layer Flow Cell Sensor System Based on BDD Electrode for Heavy Metal Ion Detection.

An electrochemical sensor based on a thin-layer flow cell and a boron-doped diamond (BDD) working electrode was fabricated for heavy metal ions determination using anodic stripping voltammetry. Furthermore, a fluidic automatic detection system was developed. With the wide potential window of the BDD electrode, Zn2+ with high negative stripping potential was detected by this system. Due to the thin-layer and fluidic structure of the sensor system, the electrodepositon efficiency for heavy metal ions were improved without using conventional stirring devices. With a short deposition time of 60 s, the system consumed only 0.75 mL reagent per test. A linear relationship for Zn2+ determination was displayed ranging from 10 µg/L to 150 µg/L with a sensitivity of 0.1218 µA·L·µg-1 and a detection limit of 2.1 µg/L. A high repeatability was indicated from the relative standard deviation of 1.60% for 30 repeated current responses of zinc solution. The system was applied to determine Zn2+ in real water samples by using the standard addition method with the recoveries ranging from 92% to 118%. The system was also used for the simultaneous detection of Zn2+, Cd2+, and Pb2+. The detection results indicate its potential application in on-site monitoring for mutiple heavy metal ions.

A novel colorimetric biosensor for monitoring and detecting acute toxicity in water.

This work presents a new colorimetric microorganism biosensor for monitoring and detecting acute toxicity in water, where prussian blue (PB) is used as the colorimetric indicator and E. coli as the model bacterial. In this biosensor, the electron mediator, ferricyanide, accepts electrons from E. coli during respiration to produce ferrocyanide, which subsequently reacts with ferric ions to yield PB, a famous material with a blue color. Since toxicants can inhibit the respiratory activity of E. coli and then reduce the ferrocyanide and consequent PB production, toxicity can be easily detected by measuring the decrease in the production of PB induced by toxicants. Three important toxicants, 3,5-dichlorophenol (DCP), As(3+), Cr(6+) are tested and the detection limits are 3.2, 25, and 3.2 ppm, respectively. Moreover, we could identify the yellow green to dark green color change by naked eye even at concentrations as low as 12.5 ppm for both DCP and Cr(6+). Subsequently, the acute toxicities of groundwater and south lake water are successfully determined by this sensor. This biosensor is rapid, sensitive and cost-effective, and can thus be regarded as a promising biosensor for giving an early warning of acute water toxicity.

A rapid and sensitive p-benzoquinone-mediated bioassay for determination of heavy metal toxicity in water.

Determining and monitoring toxicity of chemicals in water are very important for human health and country security. Electrochemical measurement of respiratory chain activity is a rapid and reliable screening of the toxicity towards microorganisms. Here, we report a rapid and sensitive toxicity bioassay using p-benzoquinone as the artificial electron mediator and Escherichia coli as the test organism. Four heavy metal ions, Cu(2+), Ag(+), Hg(2+) and Co(2+), are tested as the model toxicants, and the corresponding 50% respiration inhibition concentrations (IC50) are determined to be 0.95, 8.14, 11.69 and 42.76 mg L(-1), respectively. Based on the IC50 values, the descending order of toxicity is: Cu(2+) > Ag(+) > Hg(2+) > Co(2+). The presented bioassay not only provides a good foundation for further toxicity tests using E. coli, but also the potential for expanding the technique to utilize other bacteria with complementary toxicity responses, thereby allowing use of the bioassay in a wide range of applications.

Gut microbiota influences feeding behavior via changes in olfactory receptor gene expression in Colorado potato beetles.

The Colorado potato beetle (CPB) is an internationally recognized plant quarantine pest that causes serious losses to potato agricultural production. The gut microbiota plays an important role in its growth and development, and the olfactory system plays an important role in insect feeding behavior. The gut microbiota is known to be capable of inducing changes in the olfactory systems of insects. However, the way these associated gut microbes influence the feeding-related behaviors of CPBs remains unclear. To explore the relationship between them, fresh potato leaves immersed in a mixture of five antibiotics (tetracycline, penicillin, ofloxacin, ciprofloxacin, and ampicillin) at specific concentrations for 1 h were fed to adult CPBs to reduce the abundance of gut microbes. We found that the feeding behavior of CPBs was significantly affected by the gut microbiota and that Pseudomonas was significantly higher in abundance in the control group than in the antibiotic group. We then used transcriptome sequencing to explore the differences in olfactory receptor genes in the heads of non-treatment and antibiotic-fed CPBs. Through Illumina Hiseq™ sequencing and screening of differential genes, we found that the olfactory receptor gene LdecOR9 was significantly upregulated and LdecOR17 was significantly downregulated after antibiotic feeding. A real-time polymerase chain reaction was used to verify the changes in olfactory receptor gene expression in the non-treatment groups and antibiotic-treated groups. The feeding behavior was partially rescued after CPBs were re-fed with intestinal bacteria. These results indicate that a certain amount of gut microbiota can result in the loss of the olfactory discrimination ability of CPBs to host plants. In summary, this study investigated the relationship between gut microbiota and olfactory genes, providing a reference for research on microbial control.

A biodegradable, flexible photonic patch for in vivo phototherapy.

Diagnostic and therapeutic illumination on internal organs and tissues with high controllability and adaptability in terms of spectrum, area, depth, and intensity remains a major challenge. Here, we present a flexible, biodegradable photonic device called iCarP with a micrometer scale air gap between a refractive polyester patch and the embedded removable tapered optical fiber. ICarP combines the advantages of light diffraction by the tapered optical fiber, dual refractions in the air gap, and reflection inside the patch to obtain a bulb-like illumination, guiding light towards target tissue. We show that iCarP achieves large area, high intensity, wide spectrum, continuous or pulsatile, deeply penetrating illumination without puncturing the target tissues and demonstrate that it supports phototherapies with different photosensitizers. We find that the photonic device is compatible with thoracoscopy-based minimally invasive implantation onto beating hearts. These initial results show that iCarP could be a safe, precise and widely applicable device suitable for internal organs and tissue illumination and associated diagnosis and therapy.

Sensitive and selective detection of silver(I) ion in aqueous solution using carbon nanoparticles as a cheap, effective fluorescent sensing platform.

In this Letter, we demonstrate the first use of carbon nanoparticles (CNPs) obtained from carbon soot by lighting a candle as a cheap, effective fluorescent sensing platform for Ag(+) detection with a detection limit as low as 500 pM and high selectivity. We further demonstrate its practical application to detect Ag(+) in a real sample.

Highly sensitive and selective detection of silver(I) ion using nano-C60 as an effective fluorescent sensing platform.

In this Communication, we report water-soluble nano-C(60) in the first use as an effective fluorescent sensing platform for the highly sensitive and selective detection of Ag(+). The general concept used in this approach is based on a fluorescently labeled single-stranded DNA (ssDNA) probe that adsorbs on nano-C(60), leading to substantial dye fluorescence quenching; however, in the presence of Ag(+), C-Ag(+)-C coordination induces the probe to fold into a hairpin structure, which does not adsorb on nano-C(60) and thus retains the dye fluorescence. This sensing system exhibits a detection limit as low as 1 nM and has a high selectivity against other metal ions. Finally and most importantly, we demonstrate its performance in real sample analysis.

Poly(2,3-diaminonaphthalene) microspheres as a novel quencher for fluorescence-enhanced nucleic acid detection.

In this Communication, we report on the first preparation of conjugation polymer poly(2,3-diaminonaphthalene) (PDAN) microspheres via chemical oxidation polymerization of 2,3-diaminonaphthalene (DAN) monomers by ammonium persulfate (APS) at room temperature. We further demonstrate the use of PDAN microspheres as a novel quencher for fluorescence-enhanced nucleic acid detection.

Titanium silicalite-1 zeolite microparticles for enzymeless H2O2 detection.

In this communication, we demonstrate for the first time that titanium silicalite-1 zeolite microparticles (TSZMs) can effectively catalyze the reduction of H(2)O(2), leading to an enzymeless H(2)O(2) sensor with a linear detection range from 100 µM to 40 mM (r = 0.994) and a detection limit of 0.5 µM at a signal-to-noise ratio of 3.

Fluorescence-enhanced potassium ions detection based on inherent quenching ability of deoxyguanosines and K(+)-induced conformational transition of G-rich ssDNA from duplex to G-quadruplex structures.

Herein, we develop a novel single fluorophore-labeled double-stranded oligonucleotide (OND) probe for rapid fluorescence-enhanced K(+) detection, based on an inherent quenching ability of guanine bases and G-rich OND conformation transition from duplex to G-quadruplex. This probe presents high sensitivity and good selectivity for the detection of K(+), and the assay process is simple and fast.

Coordination polymer nanobelts as an effective sensing platform for fluorescence-enhanced nucleic acid detection.

In this communication, the application of coordination polymer nanobelts (CPNs) assembled from H(2)PtCl(6) and 3,3',5,5'-tetramethylbenzidine (TMB) are explored as an effective fluorescent sensing platform for nucleic acid detection for the first time. The suggested method has a high selectivity down to single-base mismatch. DNA detection is accomplished by the following two steps: (1) CPN binds fluorecent dye-labeled single-stranded DNA (ssDNA) probe via both electrostatic attraction and π-π stacking interactions between unpaired DNA bases and CPN. As a result, the fluorescent dye is brought into close proximity to CPN and substantial fluorescence quenching occurs due to photoinduced electron transfer from the nitrogen atom in CPN to the excited fluorophore. (2) The hybridization of adsorbed ssDNA probe with its target generates a double stranded DNA (dsDNA). The duplex cannot be adsorbed by CPN due to its rigid conformation and the absence of unpaired DNA bases, leading to an obvious fluorescence enhancement.

A naked-eye readout self-powered electrochemical biosensor toward indoor formaldehyde: On-site detection and exposure risk warning.

The determination of indoor formaldehyde is of great importance to protect individuals against its well-known adverse impact on health. Here, we report on a design of a naked-eye readout self-powered electrochemical biosensor (SPEB) toward gaseous formaldehyde based on the efficient catalytic activity of the formaldehyde dehydrogenase/poly (methylene green)/buckypaper bioanode and the excellent electrochromic property of the Prussian blue (PB) cathode. The SPEB has a planar configuration and is covered with poly(vinyl alcohol) (PVA) as gel electrolyte to provide an inner lateral resistance large enough to enable the progressive discoloration of the patterned PB at cathode, which in turn, making the determination of gaseous formaldehyde feasible by measuring the distance consumed after 10-min exposure. The use of PVA gel electrolyte can also facilitate the observation of the color change due to its excellent transparency. The SPEB shows obvious responses to gaseous formaldehyde in a broad concentration range of 80 and 3000 ppb, covering the important permissible limits of indoor formaldehyde related to human health. The SPEB also exhibits satisfactory results in sensing gaseous formaldehyde released from the real plywood that is one of the dominating sources of the gaseous indoor formaldehyde. The results shown here demonstrate the good potential of the naked-eye readout SPEB as a fast, reliable, and portable tool for on-site determination of gaseous formaldehyde, with the appealing characteristics such as ease of operation, simplicity of configuration, and no requirement of external power sources.

Comparison of Microbial Communities in Colorado Potato Beetles (Leptinotarsa decemlineata Say) Collected From Different Sources in China.

Microbial communities in insects are related to their geographical sources and contribute to adaptation to the local habitat. The Colorado potato beetle (Leptinotarsa decemlineata) (CPB) is a potato pest that causes serious economic losses in Xinjiang Uygur Autonomous Region (XJ) and Heilongjiang Province (HL), China. The influence of microorganisms in the invasion and dispersal of CPB is unclear. We studied microbial communities of CPB collected from nine geographic sources in China using high throughput sequencing technology. Bacteroidetes, Firmicutes, and Proteobacteria were the most dominant phyla, Clostridia, Bacteroidetes, and γ-Proteobacteria were the most dominant classes, Enterobacterales, Lactobacillales, Clostridiales, and Bacteroidales were the most dominant orders, and Enterobacteriaceae, Streptococcidae, Verrucomicrobiaceae, and Rikenellaceae were the most dominant families. There were significant differences, among sources, in the relative abundance of taxa at the genus level. A total of 383 genera were identified, and the dominant bacteria at the genus level were compared between XJ and HL. Pseudomonas was the unique dominant microorganism in the HL area, and the other four microorganisms (Lelliottia, Enterococcus, Enterobacter, and Lactococcus) were common within the 2 regions. Bacterial community diversity in CPB from Urumqi, Jimunai, and Wenquan was higher than diversity in other regions. T-Distributed Stochastic Neighbor Embedding (tSNE) analysis indicated that order and genus were appropriate taxonomic levels to distinguish geographical sources of CPB. These findings provide insight into the diversity of microorganisms of CPB in the differences among geographically isolated populations.