Water-soluble non-conjugated polymer dots with strong green fluorescence for sensitive detection of organophosphate pesticides.

Water-soluble non-conjugated polymer dots (PDs) have been synthesized using hyperbranched polyethyleneimine (PEI) and dihydroxybenzaldehyde (DHB) for the first time via the Schiff base reaction at room temperature. The yielded non-conjugated PDs of PEI-DHB could display the well-defined spheric structure and good water solubility. In contrast to the common PDs otherwise showing blue emission, the PEI-DHB PDs could give out strong green fluorescence in aqueous media. Especially, the fluorescence of the PEI-DHB PDs could be specifically quenched by MnO2 nanosheets through the inner filter effects and further restored by the thiocholine that could reduce MnO2 nanosheets into Mn2+. Herein, thiocholine could be produced in hydrolysis reaction of acetylthiocholine catalyzed by the acetylcholinesterase (AChE), of which the catalytic activity could be irreversibly inhibitted by the introduction of organophosphates. A highly selective fluorimetric method was thereby been developed for the detection of organophosphorus pesticides using dimethyl-dichloro-vinyl phosphate as a model. The linear concentrations ranges from 0.050 to 2.5 µM. Importantly, the non-conjugated PDs probes with strong green fluorescence and high water solubility may promise the extensive applications in the environmental, food, and clinical analysis fields.

Construction of Porous Tubular In2S3@In2O3 with Plasma Treatment-Derived Oxygen Vacancies for Efficient Photocatalytic H2O2 Production in Pure Water Via Two-Electron Reduction.

Tubular In2O3 was fabricated by the annealing of In-MIL-68 and further treated by Ar plasma to yield oxygen vacancies (Ov) followed by the growth of In2S3 nanoflowers. Unexpectedly, the resulting porous In2S3@In2O3 composites were discovered to display a broad visible-light response and especially enhanced capacities for efficient photocatalytic production of H2O2 in pure water, with a rate of 4.59 µmol·g-1·min-1. An apparent quantum yield of 28.9% at 420 nm can also be expected without the use of noble metals or organic scavengers. Herein, the high light utilization might be profited from their porous tubular heterostructure for powerful "light captivity". Moreover, the Ar plasma-derived Ov sites on the composites might tune the H2O2 generation route from the single-electron reduction to the two-electron one toward the significantly enhanced photocatalysis, as validated by the Koutecky-Levich plots. This work demonstrates a new perspective of designing porous heterostructures with the advantages of high light harvest and plasma-derived Ov active sites. Importantly, it may provide a promising defect-induced strategy of two-electron reduction triggered by the plasma treatment for the efficient photocatalytic H2O2 production under visible light.

A highly selective and recyclable sensor for the electroanalysis of phosphothioate pesticides using silver-doped ZnO nanorods arrays.

Silver-doped ZnO nanorods (Ag/ZnO) arrays have in-situ grown onto indium tin oxide (ITO) via the one-pot hydrothermal route towards a highly selective and recyclable electroanalysis of phosphothioate pesticides (PTs) with phoxim (Phox) as a model. It was discovered that the Ag/ZnO arrays-modified electrode could obtain a steady and sharp electrochemical output of solid-state Ag/AgCl at a low potential (i.e., 0.12 V). More importantly, the achieved Ag/AgCl signals could decrease selectively induced by sulfide (S)-containing Phox by the specific Cl-S displacement reaction, which would trigger AgCl into non-electroactive Ag-Phox complex. The Ag/ZnO arrays-modified sensors present a linear range from 0.050 to 700.0 µM for the detection of Phox, with a limit of detection down to 0.010 µM. The practical applicability of the developed electroanalysis strategy was successfully employed to detect Phox in the tap water and cabbage samples. Moreover, the photocatalytic performances of the Ag/ZnO arrays were subsequently verified for the degradation of Phox, displaying the higher photocatalytic efficiency than pure ZnO nanorods. Besides, the as-developed sensor can allow for the recyclable detection of Phox by the Ag/ZnO-photocatalyzed removal of Phox after each of the detection cycles. Therefore, the sensors platform based on Ag/ZnO arrays can be expected to have potential for the electrochemical monitoring and photocatalytic degradation of toxic pesticides in the food and environmental fields.

Turning on the Photoelectrochemical Responses of Cd Probe-Deposited g-C3N4 Nanosheets by Nitrogen Plasma Treatment toward a Selective Sensor for H2S.

A selective photoelectrochemical (PEC) sensor has been designed for the signal-on detection of H2S using g-C3N4 nanosheets that were treated with N2 plasma for depositing Cd probes. It was discovered that the yielded Cd/N@g-C3N4 nanocomposites could present enhanced photocurrents of specific responses to H2S under visible light irradiation, in contrast to the ones without the pretreatment of N2 plasma showing no H2S response. Herein, the Cd probes deposited on g-C3N4 nanosheets might react with H2S to generate CdS on Cd/N@g-C3N4, forming the efficient heterojunctions. Especially, the plasma-derived N contents might act as the "bridge" to promote charge transfer between the generated CdS and g-C3N4, resulting in the "signal-on" PEC responses to H2S. A selective PEC sensor was thereby developed for sensing H2S of concentrations linearly ranging from 40.0 to 10,000 pM, with a detection limit of about 21 pM. Also, the feasibility of sensing H2S in industrial waste gas was demonstrated by recovery tests. More importantly, this N2 plasma treatment route for g-C3N4 nanosheets may open a new door toward the construction of a Cd probe-based heterojunction for the signal-on PEC sensing platform, which is promising for the wide application in the fields of environmental monitoring, food safety, and biomedical analysis.

A fluorimetric testing strip for the visual evaluation of mercury in blood using copper nanoclusters with DMSO-enhanced fluorescence and stability.

A fluorimetric analytical method using test strips has been fabricated for detecting Hg2+ ions in blood by using copper nanoclusters (Cu NCs) prepared via a biomineralization route. Unexpectedly, the as-prepared Cu NCs displayed greatly amplified red fluorescence once dispersed in DMSO, the intensity of which decreased specifically in the presence of Hg2+. Moreover, the resultant Cu NCs were deposited onto test strips to be further fast dried on superhydrophobic substrates in vacuum. The test strip-based fluorimetry can allow for the direct analysis of Hg2+ in blood in the linear concentration range of 0.10-1000 nM. Importantly, this solvent-enhanced fluorescence protocol for different metal probes such as Cu NCs promises extensive analysis applications for designing numerous fluorimetric platforms such as test strips.

Synergetic Ag2S and ZnS quantum dots as the sensitizer and recognition probe: A visible light-driven photoelectrochemical sensor for the "signal-on" analysis of mercury (II).

A visible-light-driven photoelectrochemical (PEC) sensor has been developed for the "signal-on" analysis of Hg2+ by the synergetic combination of low-bandgap Ag2S and wide-bandgap ZnS quantum dots (QDs). Ag2S QDs were synthesized with bead-chain-like structure by the self-assembly route and further covalently bound with ZnS QDs to be coated onto the indium tin oxide (ITO) electrodes. It was discovered that the ZnS@Ag2S-modified electrodes could display the visible-light-driven PEC behavior, of which Ag2S and ZnS QDs could act as the PEC sensitizer and Hg2+-recognition probe, respectively. More importantly, the photocurrent responses of the developed electrodes could be specifically turned on in the presence of Hg2+ under the visible-light irradiation, presumably due to that Hg2+ might conduct a Zn-to-Hg exchange on ZnS QDs to trigger the formation of HgS/ZnS@Ag2S heterojunction towards the enhanced electron-hole separation. The as-prepared PEC sensor could facilitate the detection of Hg2+ with concentrations ranging from 0.010-1000 nM, with a detection limit of about 1.0 pM. Besides, the feasibility of practical applications of the developed PEC analysis strategy was verified by probing Hg2+ in environmental water samples. Such a visible-light-driven PEC detection platform with the unique "turn-on" signal output may promise for the extensive applications for Hg2+ evaluation.

Polyhydric polymer-functionalized fluorescent probe with enhanced aqueous solubility and specific ion recognition: A test strips-based fluorimetric strategy for the rapid and visual detection of Fe3+ ions.

A polyhydric polymer-functionalized probe with enhanced aqueous solubility was designed initially by coupling 1-pyrenecarboxyaldehyde (Pyr) onto poly(vinyl alcohol) (PVA) via the one-step condensation reaction. Polyhydric PVA polymer chains could facilitate the Pyr fluorophore with largely improved aqueous solubility and especially strong cyan fluorescence. Importantly, the fluorescence of the PVA-Pyr probes could thereby be quenched specifically by Fe3+ ions through the strong PVA-Fe3+ interaction triggering the polymeric probe aggregation. Furthermore, a test strips-based fluorimetric method was developed with the stable and uniform probe distribution by taking advantage of the unique film-forming ability and the depression capacity of "coffee-stain" effects of PVA matrix. The as-developed test strips could allow for the rapid and visual detections of Fe3+ ions simply by a dipping way, showing a linear concentration range of 5.00-300µM, with the detection limit of 0.73µM. Moreover, the proposed method was applied to the evaluation of Fe3+ ions in natural water samples, showing the analysis performances better or comparable to those of current detection techniques. This test strips-based fluorimetric strategy promises the extensive applications for the rapid on-site monitoring of Fe3+ ions in environmental water and the outdoor finding of the potential iron mines.

Fluorimetric Mercury Test Strips with Suppressed "Coffee Stains" by a Bio-inspired Fabrication Strategy.

A fluorimetric Hg2+ test strip has been developed using a lotus-inspired fabrication method for suppressing the "coffee stains" toward the uniform distribution of probe materials through creating a hydrophobic drying pattern for fast solvent evaporation. The test strips were first loaded with the model probes of fluorescent gold-silver nanoclusters and then dried in vacuum on the hydrophobic pattern. On the one hand, here, the hydrophobic constraining forces from the lotus surface-like pattern could control the exterior transport of dispersed nanoclusters on strips leading to the minimized "coffee stains". On the other hand, the vacuum-aided fast solvent evaporation could boost the interior Marangoni flow of probe materials on strips to expect the further improved probe distribution on strips. High aqueous stability and enhanced fluorescence of probes on test strips were realized by the hydrophilic treatment with amine-derivatized silicane. A test strips-based fluorimetry has thereby been developed for probing Hg2+ ions in wastewater, showing the detection performances comparable to the classic instrumental analysis ones. Such a facile and efficient fabrication route for the bio-inspired suppression of "coffee stains" on test strips may expand the scope of applications of test strips-based "point-of-care" analysis methods or detection devices in the biomedical and environmental fields.

Paneth cell ablation in the presence of Klebsiella pneumoniae induces necrotizing enterocolitis (NEC)-like injury in the small intestine of immature mice.

Necrotizing enterocolitis (NEC) is a leading cause of morbidity and mortality in premature infants. During NEC pathogenesis, bacteria are able to penetrate innate immune defenses and invade the intestinal epithelial layer, causing subsequent inflammation and tissue necrosis. Normally, Paneth cells appear in the intestinal crypts during the first trimester of human pregnancy. Paneth cells constitute a major component of the innate immune system by producing multiple antimicrobial peptides and proinflammatory mediators. To better understand the possible role of Paneth cell disruption in NEC, we quantified the number of Paneth cells present in infants with NEC and found that they were significantly decreased compared with age-matched controls. We were able to model this loss in the intestine of postnatal day (P)14-P16 (immature) mice by treating them with the zinc chelator dithizone. Intestines from dithizone-treated animals retained approximately half the number of Paneth cells compared with controls. Furthermore, by combining dithizone treatment with exposure to Klebsiella pneumoniae, we were able to induce intestinal injury and inflammatory induction that resembles human NEC. Additionally, this novel Paneth cell ablation model produces NEC-like pathology that is consistent with other currently used animal models, but this technique is simpler to use, can be used in older animals that have been dam fed, and represents a novel line of investigation to study NEC pathogenesis and treatment.