In situ measurement of the three-dimensional distribution of labile copper in sediment pore water using a microneedle sensor with nanoporous structure.

Conventional ex situ analytical methods for sediment pore water are susceptible to disruptions in the speciation equilibrium of metals due to changes in external conditions. This study introduced an innovative in situ method for detecting the three-dimensional distribution of labile copper (CuLabile) in sediment pore water with high spatial resolution using a highly stable microneedle electrochemical sensor. The sensor featured a nanoporous tip structure and embedded gold nanomaterials with excellent electrocatalytic performance. The nanoporous structure could prevent the nanomaterials from falling off because of friction during the in situ detection process in sediments. The sensor exhibited good detection performance under different salinity conditions with a detection limit of 0.2 nM. Vertical and three-dimensional distributions of CuLabile in sediment pore water were successfully obtained using the in situ microneedle sensor. The results showed that the concentration of CuLabile was in the range of 5.2-43.5 nM, with a maximum value at a depth of approximately 4 cm, while there was almost no difference in the horizontal direction of a specific sediment sample column. Furthermore, this functional sensor could be extended to the in situ detection of other labile metals in sediment pore water.

Microfluidic fabrication of monodisperse microcapsules with gas cores.

A facile strategy for efficient and continuous fabrication of monodisperse gas-core microcapsules with controllable sizes and excellent ultrasound-induced burst performances is developed based on droplet microfluidics and interfacial polymerization. Monodisperse gas-in-oil-in-water (G/O/W) double emulsion droplets with a gas core and monomer-contained oil layer are fabricated in the upstream of a microfluidic device as templates, and then water-soluble monomers are added into the aqueous continuous phase in the downstream to initiate rapid interfacial polymerization at the O/W interfaces to prepare monodisperse gas-in-oil-in-solid (G/O/S) microcapsules with gas cores. The sizes of both microbubbles and G/O/W droplet templates can be precisely controlled by adjusting the gas supply pressure and the fluid flow rates. Due to the very thin shells of G/O/S microcapsules fabricated via interfacial polymerization, the sizes of the resultant G/O/S microcapsules are almost the same as those of the G/O/W droplet templates, and the microcapsules exhibit excellent deformable properties and ultrasound-induced burst performances. The proposed strategy provides a facile and efficient route for controllably and continuously fabricating monodisperse microcapsules with gas cores, which are highly desired for biomedical applications.

A thermo-responsive hydrogel for body temperature-induced spontaneous information decryption and self-encryption.

A thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) hydrogel, exhibiting an interesting phenomenon of an opaque-transparent-opaque transition in the successive processes of heating and cooling, is reported. It is fabricated by means of both the porogenic effect of hydroxypropyl cellulose and the cononsolvency effect of PNIPAM in a mixed solvent of dimethyl sulfoxide and water. After being mildly triggered by body temperature, the hydrogel is used to spontaneously decrypt the quick response code within 4 min and then autonomously encrypts the code again within 10 min at room temperature. The mechanism for the transient transparency of hydrogels during the quenching process has been elucidated.

The influences of Yellow River input and nutrient dynamics on colloidal Fe migration in the Bohai Sea, China.

The coupling relationship between the <1 kDa, 1-3 kDa, 3-10 kDa, 10-100 kDa, and 100 kDa-0.45 µm Fe fractions and the environmental factors in the Bohai Sea (BS) was investigated. The 1-100 kDa Fe in the surface water exhibited a non-conservative phenomenon during the river-sea mixing process, which was related to the removal of colloidal Fe via flocculation during this process. For the bottom water, the ligands released by the sediments may form additions to the <100 kDa Fe. The COC and DOC were mainly closely related to the behavior of the Fe in the bottom water. The <1 and 3-10 kDa Fe was mainly significantly positively correlated with the DOC, while the <100 kDa-0.45 µm Fe was significantly negatively correlated with the DOC. <100 kDa LMW colloidal Fe exhibited more synergistic behavior with easily absorbed ammonium salts.

Spatial distribution, compositional pattern, and source apportionment of colloidal trace metals in the coastal water of Shandong Peninsula, northeastern China.

The Shandong Peninsula (SP) is the largest peninsula in China hosting rich economic and agricultural activities. In this study, we investigated the behavior of dissolved Mn, Fe, Cu, Zn, Cd, and Pb and their colloidal phases in the coastal and estuarine areas of SP. Pb and Zn had the highest contamination factors of 0.22-10.15 and 0.90-4.41, respectively. The <1 kDa accounted for 23-57 % of the total dissolved phase. Mn, Fe, Cu, Zn, Cd, and Pb were more likely to bind to 100 kDa-0.45 µm colloids (21-57 %). For colloidal Fe and Cu, the adsorption-release behavior had more significant effects on their dynamics. In contrast, the changes in colloidal Mn, Cd, and Pb were mainly controlled by the combined influence of temperature, dissolved oxygen, and microbial activity. However, the 1-3 kDa Zn exhibited a greater pH-dependent dispersion and was significantly positively correlated with it.

Prediction of multiple types of drug interactions based on multi-scale fusion and dual-view fusion.

Potential drug-drug interactions (DDI) can lead to adverse drug reactions (ADR), and DDI prediction can help pharmacy researchers detect harmful DDI early. However, existing DDI prediction methods fall short in fully capturing drug information. They typically employ a single-view input, focusing solely on drug features or drug networks. Moreover, they rely exclusively on the final model layer for predictions, overlooking the nuanced information present across various network layers. To address these limitations, we propose a multi-scale dual-view fusion (MSDF) method for DDI prediction. More specifically, MSDF first constructs two views, topological and feature views of drugs, as model inputs. Then a graph convolutional neural network is used to extract the feature representations from each view. On top of that, a multi-scale fusion module integrates information across different graph convolutional layers to create comprehensive drug embeddings. The embeddings from the two views are summed as the final representation for classification. Experiments on two real-world datasets demonstrate that MSDF achieves higher accuracy than state-of-the-art methods, as the dual-view, multi-scale approach better captures drug characteristics.

New insights into estimation of bioavailable inorganic phosphorus in natural coastal seawater.

Considering the impact of the high salinity and high turbidity of coastal seawater on phosphorus forms, a new method was proposed to determine bioavailable inorganic phosphorus (BIP). The phosphorus most relevant to eutrophication is BIP, and traditional analysis methods may underestimate the degree of eutrophication. In this study, a microelectrode of multigold (AuµE) was fabricated for direct voltammetric determination of BIP without filtration, and BIP environmental characteristics including distribution and correlation relationships with environmental factors in typical coastal seawater of Northern China were analyzed. The proposed AuµE showed a low detection limit of 0.03 µM. The surface and bottom BIP concentrations ranged from 1.00 to 2.13 and from 0.88 to 2.05 µM, respectively. BIP dominated the total P (TP) accounting for 48.5-67.5 % in the surface layer samples, and 32.6-92.7 % in the bottom layer samples, respectively. The concentrations of BIP were obviously higher than those of DIP, indicating that DIP may underestimate the probability of eutrophication occurring. And BIP was positively correlated with dissolved oxygen (DO) (P < 0.05). BIP may be a promising indicator of eutrophication potential in coastal areas with high salinity and high turbidity. The proposed reliable voltammetry method provides a new indicator for environmental assessment and represents a significant step in the comprehensive analysis of P species.

Dissolving microneedle system containing Ag nanoparticle-decorated silk fibroin microspheres and antibiotics for synergistic therapy of bacterial biofilm infection.

Most cases of delayed wound healing are associated with bacterial biofilm infections due to high antibiotic resistance. To improve patient compliance and recovery rates, it is critical to develop minimally invasive and efficient methods to eliminate bacterial biofilms as an alternative to clinical debridement techniques. Herein, we develop a dissolving microneedle system containing Ag nanoparticles (AgNPs)-decorated silk fibroin microspheres (SFM-AgNPs) and antibiotics for synergistic treatment of bacterial biofilm infection. Silk fibroin microspheres (SFM) are controllably prepared in an incompatible system formed by a mixture of protein and carbohydrate solutions by using a mild all-aqueous phase method and serve as biological templates for the synthesis of AgNPs. The SFM-AgNPs exert dose- and time-dependent broad-spectrum antibacterial effects by inducing bacterial adhesion. The combination of SFM-AgNPs with antibiotics breaks the limitation of the antibacterial spectrum and achieves better efficacy with reduced antibiotic dosage. Using hyaluronic acid (HA) as the soluble matrix, the microneedle system containing SFM-AgNPs and anti-Gram-positive coccus drug (Mupirocin) inserts into the bacterial biofilms with sufficient strength, thereby effectively delivering the antibacterial agents and realizing good antibiofilm effect on Staphylococcus aureus-infected wounds. This work demonstrates the great potential for the development of novel therapeutic systems for eradicating bacterial biofilm infections.

Field determination and ecological health risk assessment of trace metals in typical mariculture area of China.

Field determination of dissolved trace metals (Cu, Pb and Cd) by using automated electrochemical system had been done in three typical mariculture areas of Yellow Sea (YS), East China Sea (ECS) and South China Sea (SCS) in China. Higher concentrations of Cu and Pb were found in ECS while the Cd concentration showed a decreasing trend from north to south of China. The metal distribution and ecological health risk assessments were also conducted. Cu and Pb in the YS and Cu in SCS were moderately contaminated. ECS had considerable Cu contamination and very high Pb contamination. Compared with other coastal areas, mariculture affected the concentration and spatial distribution of trace metals, but it was not a necessarily dominant factor. Overall, the results contribute to the further development of field and on-board metal detection technology and lay a foundation for the realization of field ecological health risk assessments of mariculture waters.

Microfluidic Controllable Preparation of Iodine-131-Labeled Microspheres for Radioembolization Therapy of Liver Tumors.

Transcatheter arterial radioembolization (TARE) is of great significance for the treatment of advanced hepatocellular carcinoma (HCC). However, the existing radioembolic microspheres still have problems such as non-degradability, non-uniform size, and inability to directly monitor in vivo, which hinders the development of TARE. In this paper, a novel radioembolic agent, 131 I-labeled methacrylated gelatin microspheres (131 I-GMs), is prepared for the treatment of HCC. Water-in-oil (W/O) emulsion templates are prepared by a simple one-step microfluidic method to obtain methacrylated gelatin microspheres (GMs) after UV irradiation. A series of GMs with uniform and controllable size is obtained by adjusting the flow rate of each fluid. Both air-dried and freeze-dried GMs can quickly restore their original shape and size, and still have good monodispersity, elasticity, and biocompatibility. The radiolabeling experiments show that 131 I can efficiently bind to GMs by chloramine-T method, and the obtained 131 I-GMs have good radioactive stability in vitro. The results of in vivo TARE treatment in rats show that 131 I-GMs can be well retained in the hepatic artery and have a good inhibitory effect on the progression of liver cancer, showing the potential for the treatment of HCC.

Ultrasensitive hydrogel grating detector for real-time continuous-flow detection of trace threat Pb2.

Ultrasensitive real-time detection of trace Pb2+ in continuous flow is vital to effectively and timely eliminate the potential hazards to ecosystem health and sustainability. This work reports on a micro-structured smart hydrogel grating with ultra-sensitivity, high selectivity, good transparency and mechanical property for real-time detection of Pb2+ in continuous flow. The hydrogel grating possesses uniform surface relief microstructures with periodic nano-height ridges made of poly(acrylamide-co-benzo-18-crown-6-acrylamide) networks that crosslinked by tetra-arm star poly(ethylene glycol)acrylamide. The hydrogel grating with good optical transparency and mechanical property can change its height via selective host-guest complexation with Pb2+ to output a changed diffraction efficiency. Meanwhile, the periodic nano-ridges with large specific area benefit the contact with Pb2+ for fast Pb2+-induced height change. Thus, with such rationally designed molecular structures and surface relief microstructures, the hydrogel grating integrated in a glass-based mini-chip allows real-time detection of Pb2+ in continuous flow with ultra-sensitivity and high selectivity. The hydrogel grating detector can achieve ultralow detection limit (10-9 M Pb2+), fast response (2 min), and selective detection of Pb2+ from dozens of interfering ions even with high concentrations. This high-performance hydrogel grating detector is general and can be extended to detect many analytes due to the wide choice of responsive hydrogels, thus opening new areas for creating advanced smart detectors in analytical science.

An antifouling gel-protected iridium needle sensor: Long-term, on-site monitoring of copper in seawater.

Copper (Cu), a natural micronutrient with ecotoxicological significance, is involved in the carbon and nitrogen cycles occurring in marine ecosystems. Here, we developed a novel, antifouling gel-protected iridium (Ir) needle electrode modified with gold nanoparticles (G-IrNS) for long-term continuous and steady Cu monitoring. The gel formed an efficient membrane that effectively prevented the fouling of the sensing surface and displayed anti-convective properties, ensuring that mass transport toward the sensor surface was wholly controlled via diffusion. The repeatability, reproducibility, and stability of G-IrNS showed that it was suitable for long-term and on-site monitoring of Cu in seawater. Cu concentrations were successfully measured via fixed-point continuous monitoring for >2 weeks and onboard continuous monitoring in Bohai Sea using one sensor. Moreover, the relationship between Cu concentrations measured on-site via G-IrNS and its dissolved concentration in Bohai Sea was evaluated. G-IrNS can be applied to other metal ions as well, especially for long-term automatic on-site monitoring, thereby providing a basis for further research.

Tip-porous microneedle: A highly stable sensing platform for direct determination of labile metals in natural seawater.

Nanomaterial-functionalized voltammetric microsensors are promising tools for detecting trace metals at low concentrations in the complex environment of natural seawater. However, the sensitivity reduction caused by the loss of modified nanomaterials in the detection process has always been a major problem. Herein, to fabricate a highly stable sensing platform, a microneedle electrode with a hierarchical porous tip was prepared through electrochemical etching technology to firmly embed nanoparticles. Using copper (Cu) as a model trace metal, a micro-cluster needle sensor based on a gold nanoparticle (AuNP)-embedded tip-porous microneedle electrode (P-MNE) was fabricated for the direct voltammetric determination of labile Cu in natural seawater. The porous structure of P-MNE not only provided a larger specific surface area and active sites for AuNPs which had excellent electrocatalytic performance for Cu2+ determination, but also protected from their loss during the detection process in seawater. Therefore, this novel micro-cluster needle sensor exhibited significantly improved stability with a relative standard deviation (RSD) of 1.5% for 30 detections. The linear range of Cu2+ on this micro-cluster needle sensor was from 0.1 to 1000 nM with a detection limit of 0.03 nM. More importantly, this micro-cluster needle sensor was successfully used for directly detecting labile Cu in natural seawater samples without any preaccumulation treatment or reagent addition to obtain the contribution proportions of the labile fraction in total dissolved Cu. Furthermore, this sensing platform might also be extended to the reliable determination of other labile metals in seawater by changing the functional nanoparticles embedded in the nanopores.

Designable microfluidic ladder networks from backstepping microflow analysis for mass production of monodisperse microdroplets.

Controllable mass production of monodisperse droplets plays a key role in numerous fields ranging from scientific research to industrial application. Microfluidic ladder networks show great potential in mass production of monodisperse droplets, but their design with uniform microflow distribution remains challenging due to the lack of a rational design strategy. Here an effective design strategy based on backstepping microflow analysis (BMA) is proposed for the rational development of microfluidic ladder networks for mass production of controllable monodisperse microdroplets. The performance of our BMA rule for rational microfluidic ladder network design is demonstrated by using an existing analogism-derived rule that is widely used for the design of microfluidic ladder networks as the control group. The microfluidic ladder network designed by the BMA rule shows a more uniform flow distribution in each branch microchannel than that designed by the existing rule, as confirmed by single-phase flow simulation. Meanwhile, the microfluidic ladder network designed by the BMA rule allows mass production of droplets with higher size monodispersity in a wider window of flow rates and mass production of polymeric microspheres from such highly monodisperse droplet templates. The proposed BMA rule provides new insights into the microflow distribution behaviors in microfluidic ladder networks based on backstepping microflow analysis and provides a rational guideline for the efficient development of microfluidic ladder networks with uniform flow distribution for mass production of highly monodisperse droplets. Moreover, the BMA method provides a general analysis strategy for microfluidic networks with parallel multiple microchannels for rational scale-up.

Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions.

An electrochemical sensor constructed by intercalated composites was developed for determination of heavy metal ions. The intercalated composites were composed of hydrosulphonyl functional covalent organic frameworks (COF-SH) and graphene (G). The presence of numerous adsorption sites, such as 18 sulfur atoms and 30 nitrogen atoms per big circle of COFs on COF-SH, was beneficial for the accumulation of heavy metals, while the graphene enhanced the electrical conductivity. The obtained sensor under the optimal conditions successfully detected the presence of heavy metal ions in coastal water samples at concentrations ranging from 1 to 1000 µg L-1. The detection limits of Cd (II), Pb (II), Cu (II), and Hg (II) were 0.3, 0.2, 0.2, and 1.1 µg L-1, respectively. Furthermore, the sensor still exhibited good stability after multiple uses less than 5%. When it is used in the analysis of actual samples, the recovery of standard addition is higher than 95%. In sum, the combination of hydrosulphonyl functional COFs with graphene looks very promising for the assembly of sensors with high sensitivity toward the determination of heavy metal ions for coastal environmental monitoring.

Study on anti-scaling of landfill leachate treated by evaporation method.

In the mechanical vapor recompression (MVR) treatment of landfill leachate, scaling in the evaporator and heat exchanger poses a serious problem. This study explored the reasons for such scaling and proposed acid or ion-exchange pre-treatments to reduce the alkalinity of the landfill leachate nanofiltration concentrate (LLNC) to prevent scaling. The feasibility of these two methods was evaluated and the technical and economic parameters for application were obtained via experiments. A large amount of HCO3- in the LLNC was the main cause of scaling. The acid addition experiment and field application demonstrated that this method could prevent fouling problems. The cost of acid addition was USD 0.18/t. LLNC pre-treatment by ion-exchange showed that a weakly acidic cation-exchange resin performed better than a strongly acidic cation-exchange resin did. The amount of solid residue under an alkalinity of 0 mg/L could be decreased by 92.9% compared with that of raw LLNC during evaporation. Both methods could alleviate scaling and enable the wide application of the MVR evaporation process in landfill leachate treatment.

On-site electrochemical determination of phosphate with high sensitivity and anti-interference ability in turbid coastal waters.

Phosphate is considered to be an important biogenic element and responsible for eutrophication in aquatic ecosystems, existing in both dissolved and absorbed forms. Due to the complex matrix of coastal seawater, a high sensitivity and anti-interference method for phosphate detection is required for environmental protection. In this study, a novel electrochemical method was proposed based on reduced graphene oxide-ordered mesoporous carbon screen-printed electrode (rGO-OMC/SPE) analysis, allowing sensitivity and reliable determination of phosphate in turbid coastal waters. Combining the good absorption capacity of OMC with the excellent electroconductivity of rGO, the fabricated electrode exhibits improved signal responses, enhanced by up to 43-fold. The platform was evaluated using turbidity interference test with good recovery percentages comprised between 96% and 105% in different phosphate concentration, and salinity interference test between 92% and 105%, respectively. A linear range from 0.2 to 150 µM phosphate was achieved, with a detection limit of 0.05 µM (s/n = 3). The fabricated platform was successfully used for on-site analysis of phosphate in turbid coastal waters. This reliable and effective method for the analysis of phosphate in turbid coastal waters allows for sensitivity and anti-interference determination, while also representing a significant step towards comprehensive and convenient analysis of phosphorus species.

Fabrication of Polymer Composite Fibers Embedding Ultra-Long Micro/Nanowires.

Fabrication of polymer composite fibers embedding ultra-long micro/nanowires via an iterative melt co-drawing and bundling technique is reported in this study. The poly(methyl methacrylate) (PMMA) porous array templates were prepared with section-cutting the PMMA/polystyrene (PS) (shell/core) composite fibers and dissolution of inner PS. The results showed that the PS cores or pores in the PMMA matrix are regularly arranged with hexagonal, and their diameter and spacing exhibits a uniform distribution. Especially, the core diameter can be precisely controlled from millimeter-scale to nanometer-scale by multi-step melt co-drawing. Based on the PMMA porous array templates, the Cu nanowires were successfully prepared by electrochemical deposition. Moreover, to fabricate PMMA ultra-long micro/nanowires, the composite fibers with converse shell/core component of PS/PMMA were initially prepared, and then the outer PS was dissolved. The obtained PMMA micro/nanowires were characterized with smooth complete orientation structure. The study provides an experimental basis for fabricating such polymer composite fibers, micro/nano porous array templates, and micro/nanowires with precise and controllable manner to meet the real application requirements.

Spatial and environmental characteristics of colloidal trace Cu in the surface water of the Yellow River Estuary, China.

Dynamic variations in chemical composition and size distribution of dissolved copper (Cu) along the river-sea interface in the Yellow River Estuary (China) were investigated. On average, ~64% and ~8% of bulk dissolved Cu (<0.45 µm) were partitioned in the <1 kDa fraction and 1-100 kDa, respectively. The other 28% were in the 100 kDa-0.45 µm colloids, which indicates that this fraction may dominate the overall morphology of colloidal Cu. The <3 kDa Cu fraction was susceptible to environmental parameters and the >3 kDa fraction was related to the behavior of dissolved organic carbon. 1-100 kDa Cu migrated more violently than >100 kDa Cu and tended to be a stable polymer, with stability increasing towards the sea. The source of <1 kDa Cu was complex and may be supplemented by the decomposition of small molecular colloids and the addition of the sediments or particles ligands.

Highly Efficient Silver Catalyst Supported by a Spherical Covalent Organic Framework for the Continuous Reduction of 4-Nitrophenol.

Developing new materials and novel technologies for the highly efficient treatment of toxic organic pollutants is highly desirable. Chemical reduction based on heterogeneous substrate/noble metal catalysts and the reducing agent NaBH4 has become an effective method in recent years. Here, a spherical covalent organic framework (SCOF) was designed to provide basic sites for Ag ions, by which small Ag NPs were immobilized on the SCOF to form Ag NPs@SCOF microspheres. The prepared microspheres exhibited a high catalytic reduction ability toward 4-nitrophenol (4-NP). An optimized permeation flux of 2000 L m-2 h-1 (LMH) and a more than 99% 4-NP reduction efficiency were obtained with flow-through experiments, which are far better than the reported results (below 200 LMH). Moreover, the microspheres could maintain stable catalytic performance under a continuous flow-through process. Our work provides an efficient material and technology that can be applied to easily treat toxic organic pollutants.