On-Chip Microdevice Unveils Reactant Enrichment Effect Dominated Electrocatalysis Activity in Molecular-Linked Catalysts.

Molecular functionalization has been intensely studied and artificially constructed to advance various electrocatalytic processes. While there is a widely approved charge-doping effect, the underlying action for reactant distribution/transport remains long neglected. Here an on-chip microdevice unravels that the proton enrichment effect at prototypical methylene blue (MB)/MoS2 interfaces rather than charge doping contributes to the hydrogen evolution reaction (HER) activity. Back-gated electrical/electrochemical tests detect quantitatively a strong charge injection from MB to MoS2 realized over diploid carrier density, but these excess carriers are unqualified for the actual enhanced HER activity (from 32 to 125 mA cm-2 at -0.29 V). On-chip electrochemical impedance further certifies that the proton enrichment in the vicinity of MoS2, which is generated by the nucleophilic group of MB, actually dominates the HER activity. This finding uncovers the leading function of molecular-linked catalysts.

Aged polyamide microplastics enhance the adsorption of trimethoprim in soil environments.

Microplastics (MPs) in the environment typically age. However, the influence of aged MPs on the adsorption of antibiotics in soil remains unknown. In this study, the adsorption behavior of trimethoprim (TMP) on soil and soil containing aged polyamide (PA) was investigated using batch and stirred flow chamber experiments. The adsorption of TMP on the tested soil with and without PA was fast, with the ka values ranging from 50.5 to 55.6 L (mg min)-1. The adsorption of TMP on aged PA was more than 20 times larger than that on the tested soil, which resulted in an "enrichment effect." Furthermore, aged PA altered the pH of the reaction system, thereby enhancing the adsorption of TMP. Consequently, the Kd values of TMP for soil, soil containing 5%, and 10% aged PA were 5.64, 12.38, and 23.65 L kg-1, respectively. The effect of aged PA on the adsorption of TMP on soil depended on pH values. However, TMP adsorption on soil containing 10% aged PA was constantly higher (p < 0.01) than that on soil with NaCl concentrations ranging from 0 to 50 mmol L-1. These findings provide new insights into the effect of environmental MPs on the fate and transport of antibiotics in soil environments.

Atmospheric wet deposition of dissolved organic carbon to a typical anthropogenic-influenced semi-enclosed bay in the western Yellow Sea, China: Flux, sources and potential ecological environmental effects.

Dissolved Organic Carbon (DOC) is a key organic compound in wet precipitation, but few data are available in China marginal seas. To probe the concentration, deposition flux, seasonality, source and potential ecological environmental effects of precipitation DOC, in this study, one-year precipitation samples were collected at Jiaozhou Bay (JZB), a typical anthropogenic-influenced semi-enclosed bay in the western Yellow Sea for the first time from June 2015 to May 2016. The concentrations of DOC in precipitation were highly variable with a volume-weighted mean (VWM) concentration of 3.63 mg C L-1, which was mostly higher than those in other areas. DOC concentrations were lower in wet season than that in dry season due to the dilution from more amount of rainfall. The wet deposition flux of DOC was calculated to be 3.15 g C m-2 yr-1 with 68.7% of which occurred in wet season mainly owing to the promoting of more rainfall amount. Besides, local emissions together with the long-range transport of pollutants were other factors controlling precipitation DOC. Fossil fuel combustion particularly coal burning was considered to be the leading source of precipitation DOC based on correlation analysis with some generally accepted indicators. Wet deposition dominates the external input of DOC at JZB by comparison with riverine input with a percentage of 54%. Heavy storm may exert enrichment effect on DOC levels in the surface water of JZB, and then promote the secondary productivity. This study emphasizes that wet deposition is an important process that should be seriously considered in the models of global/regional carbon biogeochemical cycling.

[Distribution and enrichment characteristics of soil nutrients in the nebkhas profile of Nitraria tangutorum in Gahai Lake Area, Qaidam Basin.] / æŸ´è¾¾æœ¨ç›†åœ°å°•æµ·æ¹–åŒºç™½åˆºçŒä¸›æ²™å †å‰–é¢åœŸå£¤å »åˆ†çš„åˆ†å¸ƒå’Œå¯Œé›†ç‰¹å¾.

As a special bio-geomorphic landscape in the Qaidam desert area, Nitraria tangutorum nebkhas play a critical role in fixing quicksand, improving soil quality, and maintaining the stability of regional ecological environment. Taking the N. tangutorum nebkhas with coverage of approximately 15%, 25%, 45% and 60% in Gahai Lake area of Qaidam Basin as the research objects, we analyzed the vertical distribution and enrichment characteristics of soil organic matter (SOM), total nitrogen (TN), total phosphorus (TP), total potassium (TK), alkali-hydrolyzable nitrogen (AN), available phosphorus (AP) and available potassium (AK). The results showed that the contents of SOM, TN, TP, TK, AN, AP and AK varied in the range of 1.67-10.22 g·kg-1, 0.05-0.42 g·kg-1, 0.31-0.54 g·kg-1, 15.87-18.84 g·kg-1, 2.26-11.68 mg·kg-1, 0.80-15.00 mg·kg-1 and 45-161 mg·kg-1, respectively. Vertically, soil nutrients in the N. tangutorum nebkhas with 15% coverage showed a decreasing trend first then increased, and then decreased again with the increase of soil depth, except for TP, which did not show any significant change. In the nebkhas with 25%, 45% and 60% coverage, SOM, TN, AN, TP and AP all showed a decreasing trend with increasing soil depth ,whereas TK and AK did not change significantly with soil layer. Above the nebkhas ground level of N. tangutorum, SOM, TN, TK, AN, AP and AK were all enriched, especially in the surface layer.Aamong all the nutrients, the enrichment rate of AN reached 5.19. In addition, below the nebkhas ground level of N. tangutorum, TN, AN, TK, AK and AP also showed enrichment. SOM, TN, AN, TP, AP, TK and AK were all significantly positively correlated with soil water content, and negatively correlated with altitude. All nutrients except TP were mainly affected by altitude. In conclusion, soil nutrient content of N. tangutorum nebkhas was the highest in the surface layer, the enrichment effect of which was not only reflected in the interior of the nebkhas, but also below the ground level of the nebkhas. Our results could provide reference for the scientific utilization of N. tangutorum nebkhas and ecological environment protection in Qaidam Basin area.

2D Conductive Covalent Organic Frameworks with Abundant Carbonyl Groups for Electrochemical Sensing.

Due to their permanent porosity, robust chemical stability, and tunable structure, covalent organic frameworks (COFs) are very attractive in the application of energy storage, catalysis, sorption, and sensing. However, the very low conductivity of COFs severely restricts their application in electrochemical sensing. Here, an aza-fused π-conjugated COFs with abundant carbonyl groups (COF1) was synthesized and deployed as electrode materials in electrochemical sensing for the first time. The current response of the acetylcholinesterase biosensor based on COF1 increases three times when compared to the electrode without COF1. The effects of carbonyl groups on signal enhancement were proved in depth by a series of characterization and comparison experiments with the prepared COF2 without carbonyl groups. The results demonstrated that exposed carbonyl active sites of COF1 can promote the effective immobilization and bioactivity preserving of enzyme molecules and contribute to the enrichment of analytes. Together with the good conductivity of COF1 derived from a fully extended 2D aromatized π-conjugated system, all of which improve the biosensor performance. The COF1-based biosensor exhibited fast response speed, high sensitivity, good selectivity and practicability, and robust stability for organophosphorus pesticide detection and proved to be a promising tool for the rapid and onsite detection of organophosphorus pesticides in the environment.

Efficient Electroreduction of Nitrate into Ammonia at Ultralow Concentrations Via an Enrichment Effect.

The electroreduction of nitrate (NO3 - ) pollutants to ammonia (NH3 ) offers an alternative approach for both wastewater treatment and NH3 synthesis. Numerous electrocatalysts have been reported for the electroreduction of NO3 - to NH3 , but most of them demonstrate poor performance at ultralow NO3 - concentrations. In this study, a Cu-based catalyst for electroreduction of NO3 - at ultralow concentrations is developed by encapsulating Cu nanoparticles in a porous carbon framework (Cu@C). At -0.3 V vs reversible hydrogen electrode (RHE), Cu@C achieves Faradaic efficiency for NH3 of 72.0% with 1 × 10-3 m NO3 - , which is 3.6 times higher than that of Cu nanoparticles. Notably, at -0.9 V vs RHE, the yield rate of NH3 for Cu@C is 469.5 µg h-1 cm-2 , which is the highest value reported for electrocatalysts with 1 × 10-3 m NO3 - . An investigation of the mechanism reveals that NO3 - can be concentrated owing to the enrichment effect of the porous carbon framework in Cu@C, thereby facilitating the mass transfer of NO3 - for efficient electroreduction into NH3 at ultralow concentrations.

Influence of the Exclusion-Enrichment Effect on Ion Transport in Two-Dimensional Molybdenum Disulfide Membranes.

Two-dimensional (2D) nanosheet membranes have been widely studied for water and wastewater treatment. However, mass transport inside 2D nanosheet membranes is far from being fully understood, and suitable applications of these membranes are yet to be identified. In this study, we investigate ion transport inside a 2D molybdenum disulfide (MoS2) membrane by combining experimental results with numerical modeling. Specifically, we analyze the influence of the electrical double layer (EDL) extension on ion diffusion in the MoS2 membrane, and a parameter called the exclusion-enrichment coefficient (ß) is introduced to quantify how the electrostatic interaction between the coions and the EDL can affect the ion diffusion. Using the model developed in this study, the ß values under different experimental conditions (feed solution concentration and applied hydraulic pressure) are calculated. The results show that coion diffusion inside the membrane can be retarded since ß is smaller than one. Furthermore, the underlying mechanism is explored by theoretically estimating the radial ion concentration and electrical potential distributions across the membrane nanochannel. In addition, we find that convective mass transport can weaken the exclusion-enrichment effect by increasing ß. Based on the results in this study, the potential applications and feasible membrane design strategies of 2D nanosheet membranes are discussed.

Modulation of Molecular Spatial Distribution and Chemisorption with Perforated Nanosheets for Ethanol Electro-oxidation.

Integrating thermodynamically favorable ethanol reforming reactions with hybrid water electrolysis will allow room-temperature production of high-value organic products and decoupled hydrogen evolution. However, electrochemical reforming of ethanol has not received adequate attention due to its low catalytic efficiency and poor selectivity, which are caused by the multiple groups and chemical bonds of ethanol. In addition to the thermodynamic properties affected by the electronic structure of the catalyst, the dynamics of molecule/ion dynamics in electrolytes also play a significant role in the efficiency of a catalyst. The relatively large size and viscosity of the ethanol molecule necessitates large channels for molecule/ion transport through catalysts. Perforated CoNi hydroxide nanosheets are proposed as a model catalyst to synergistically regulate the dynamics of molecules and electronic structures. Molecular dynamics simulations directly reveal that these nanosheets can act as a "dam" to enrich ethanol molecules and facilitate permeation through the nanopores. Additionally, the charge transfer behavior of heteroatoms modifies the local charge density to promote molecular chemisorption. As expected, the perforated nanosheets exhibit a small potential (1.39 V) and high Faradaic efficiency for the conversion of ethanol into acetic acid. Moreover, the concept in this work provides new perspectives for exploring other molecular catalysts.

Single polydiacetylene microtube waveguide platform for discriminating microRNA-215 expression levels in clinical gastric cancerous, paracancerous and normal tissues.

MicroRNAs (miRNAs) have emerged as novel biomarkers for human early-phase cancer diagnosis and disease prevention recently. Herein, we reported a novel miRNA-215 targeting biosensor, which was based on single polydiacetylene (PDA) microtube waveguide system integrated with sandwich-type hybridization design and condensing enrichment effect. The target miRNA could be captured by oligonucleotides conjugated on the surface of PDA microtube and Au nanorod (AuNR) respectively, resulting in the out-coupled fluorescence of PDA microtube quenching. In this strategy, the formation of a sandwich structure, as a result of co-hybridization of the target miRNA, enabled simplified preparation process, enhanced reaction efficiency, and increased recyclability and stability of the platform. Based on condensing enrichment effect, the co-hybridization reaction could be enriched on the surface of microtube and the proposed platform could easily achieve highly sensitive detection of miRNA-215 in one step. Remarkably, this platform could be directly applied to discriminate the miRNA-215 expression levels in clinical gastric cancerous, paracancerous and normal tissues samples. This assay offers a simple and convenient method for miRNA quantification in clinical samples, even with the potential for invasive, portable equipment for early clinical diagnosis of diseases.