A Nanofilm-Based Fluorescent Sensor toward Highly Efficient Detection of Ethephon.

Ethephon (ETH) is widely used to promote fruit ripening and improve fruit quality. However, improper use is harmful to human health and to the environmental safety. Therefore, development of the techniques for on-site and at real-time monitoring of ETH is of importance for its safe use. In this work, we developed a nanofilm-based fluorescence film sensor (FFS) and realized highly efficient detection of ETH in vapor phase, where the detection limit (DL) is <0.2 ppb, the response time is less than 10 s, and the interference is almost free. The unusual sensing performance of the sensor was ascribed to the specific binding of the nanofilm to ETH and to its great porosity, which enables efficient adlayer mass transfer, a requirement for high signal-to-noise ratio. Moreover, visualization-based qualitative sensing is also realized. The nanofilm, a key component of the sensor, was prepared at the humid air/DMSO interface. The building blocks used were a specially designed fluorescent o-carborane derivative (CB-2CHO) and a cross-linker BTN possessing three acylhydrazine groups. The nanofilm as prepared is flexible, uniform, thickness tunable, and photochemically super stable. We believe our effort not only addresses the challenging issue of on-site and at real-time detection of ETH but also provides another route for developing new FFSs via sensing film innovation.

Enhancing Signal Output and Avoiding BOD/Toxicity Combined Shock Interference by Operating a Microbial Fuel Cell Sensor with an Optimized Background Concentration of Organic Matter.

In the monitoring of pollutants in an aquatic environment, it is important to preserve water quality safety. Among the available analysis methods, the microbial fuel cell (MFC) sensor has recently been used as a sustainable and on-line electrochemical microbial biosensor for biochemical oxygen demand (BOD) and toxicity, respectively. However, the effect of the background organic matter concentration on toxicity monitoring when using an MFC sensor is not clear and there is no effective strategy available to avoid the signal interference by the combined shock of BOD and toxicity. Thus, the signal interference by the combined shock of BOD and toxicity was systematically studied in this experiment. The background organic matter concentration was optimized in this study and it should be fixed at a high level of oversaturation for maximizing the signal output when the current change (ΔI) is selected to correlate with the concentration of a toxic agent. When the inhibition ratio (IR) is selected, on the other hand, it should be fixed as low as possible near the detection limit for maximizing the signal output. At least two MFC sensors operated with high and low organic matter concentrations and a response chart generated from pre-experiment data were both required to make qualitative distinctions of the four types of combined shock caused by a sudden change in BOD and toxicity.

Preparation of novel W/O gel-emulsions and their application in the preparation of low-density materials.

A series of novel and stable water in oil (W/O) gel-emulsions was created by utilizing a new cholesteryl derivative, a low-molecular mass gelator (LMMGs), as a stabilizer. In the emulsions, n-heptane, n-octane, n-nonane, n-decane, tertiary butyl methacrylate (t-BMA), methyl methacrylate (MMA), or styrene can be used as a continuous phase, water as a dispersed phase, and the stabilizer in the continuous phase is only 2% (w/v). Importantly, the gel-emulsions could be prepared by simple agitation of the mixtures at room temperature, while heating, cooling, and addition of a cosolvent or other additional component are unnecessary. SEM and optical microscopy studies revealed the foam-like structures of the gel-emulsions. Rheological measurements demonstrated that the gel-emulsions are mechanically stable and exhibit typical viscoelastic properties. Surprisingly, the storage modulus, G', and the yield stress of the gel-emulsions with the alkanes as continuous phase decrease along with increasing the volume ratio of the dispersed phase, water, a property different from those of conventional gel-emulsions reported in the literature. From the viewpoint of application, the gel-emulsions as prepared are superior to others due to their simplicity in preparation, less amount of stabilizer needed, and the nonionic nature of the stabilizer, which must benefit practical applications. Furthermore, porous polymer monoliths could be prepared by polymerizing gel-emulsions with organic monomers as a continuous phase.

Conformationally tunable calix[4]pyrrole-based nanofilms for efficient molecular separation.

Preparation of nanofilms which are able to reject water-soluble low molecular weight organic compounds in nanofiltration remains to be a challenge. Herein, we report a new kind of self-standing, defect-free, robust, centimeter-sized and thickness controllable calix[4]pyrrole (C[4]P)-based nanofilms with excellent molecular sieving performance in nanofiltration. The nanofilms were prepared via confined dynamic condensation of the tetra-benzoyl-hydrazine derivative of calix[4]pyrrole (CPTBH) with 1,3,5-benzenetricarboxaldehyde (BTC) at the air/dimethyl sulfoxide (DMSO) interface. Nanofiltration tests under 2 bar pressure with porous polyethylene terephthalate (PET) as the support and a CsF treated CPTBH-BTC nanofilm (∼100 nm) as the selective layer depicted a water permeance of 15 L m-2h-1 bar-1 and a methanol permeance of 45 L m-2h-1 bar-1. High rejection rates (>95%) were found in aqueous solution for most of the tested dyes and pharmaceuticals. Remarkably, the composite membrane also demonstrated good separation performance in aqueous phase to some amino acids and organic dyes with molecular weights around 200 g/mol. High-performance nanofiltration in methanol was also realized. In this case, the molecular weight cutoff value is âˆ¼ 800 g/mol. These findings showed that introduction of macrocyclic hosts is an effective way to develop nanofilms with high solvent permeance but low molecular weight cutoff value.

Glucose-based fluorescent low-molecular mass compounds: creation of simple and versatile supramolecular gelators.

Five novel glucose-based naphthalene derivatives with linkers containing hydrazine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,6-hexanediamine, respectively (1, 2, 3, 4, and 5) were designed and prepared. The gelation test revealed the following points: (1) within the 30 solvents tested, 1 gels water only; (2) in contrast, 2 gels not only water, but also 11 of the organic solvents tested, a typical "ambidextrous gelator"; (3) 3, 4, and 5, however, gel organic solvents only, and the numbers of solvents gelled are 11, 11 and 13, respectively. Clearly, these compounds are effective low-molecular mass gelators, and show transitions from a low-molecular mass hydrogelator to an ambidextrous gelator and then to low-molecular mass organogelators with a slight increase in the length of the spacers. Interestingly, 5 is a super gelator to acetonitrile, of which the minimum gelation concentration is only 0.07%, w/v. The morphology, microstructure and molecular aggregation of the system strongly depend on the transition, as revealed by SEM, contact angle, energy dispersive X-ray spectroscopy, and XRD measurements. More interestingly, an aggregation-induced enhanced emission was observed along with gelation. Furthermore, the system appeared as a supramolecular chiroptical switch in the sol-gel process that is the chirality disappeared when the gel was heated to solution, whereas it reappeared when cooled to a gel.

Hydrogen peroxide generation in microbial fuel cells using graphene-based air-cathodes.

Utilization of two-electron oxygen reduction reaction (ORR) in bioelectrochemical systems (BES) is a novel way to generate H2O2 from wastewater, and cathode catalyst is a key factor affecting ORR performance. Here, the catalytic performance of plain graphene, oxidized graphene and graphene oxide (GO) in microbial fuel cells (MFCs) and the influence of oxygen-containing functional groups are reported. Oxidized graphene air-cathode had 78% and 131% higher H2O2 productions than plain graphene cathode respectively in an abiotic reactor and an MFC. GO showed nearly no H2O2 production in the tests. XPS revealed that oxygen atomic fraction of oxidized graphene reached 5.7%, mostly in the form of COC. These results show that oxidized graphene had good catalytic performance for H2O2 production, and oxygen-containing functional groups, especially COC could significantly enhance its performance, but overoxidation worked adversely. Meanwhile, using oxidized graphene air-cathode could realize simultaneous wastewater treatment, power output and H2O2 generation in MFCs.