Local O2 concentrating boosts the electro-Fenton process for energy-efficient water remediation.

The electro-Fenton process is a state-of-the-art water treatment technology used to remove organic contaminants. However, the low O2 utilization efficiency (OUE, <1%) and high energy consumption remain the biggest obstacles to practical application. Here, we propose a local O2 concentrating (LOC) approach to increase the OUE by over 11-fold compared to the conventional simple O2 diffusion route. Due to the well-designed molecular structure, the LOC approach enables direct extraction of O2 from the bulk solution to the reaction interface; this eliminates the need to pump O2/air to overcome the sluggish O2 mass transfer and results in high Faradaic efficiencies (~50%) even under natural air diffusion conditions. Long-term operation of a flow-through pilot device indicated that the LOC approach saved more than 65% of the electric energy normally consumed in treating actual industrial wastewater, demonstrating the great potential of this system-level design to boost the electro-Fenton process for energy-efficient water remediation.

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density.

Developing heterogeneous catalysts with atomically dispersed active sites is vital to boost peroxymonosulfate (PMS) activation for Fenton-like activity, but how to controllably adjust the electronic configuration of metal centers to further improve the activation kinetics still remains a great challenge. Herein, we report a systematic investigation into heteroatom-doped engineering for tuning the electronic structure of Cu-N4 sites by integrating electron-deficient boron (B) or electron-rich phosphorus (P) heteroatoms into carbon substrate for PMS activation. The electron-depleted Cu-N4/C-B is found to exhibit the most active oxidation capacity among the prepared Cu-N4 single-atom catalysts, which is at the top rankings of the Cu-based catalysts and is superior to most of the state-of-the-art heterogeneous Fenton-like catalysts. Conversely, the electron-enriched Cu-N4/C-P induces a decrease in PMS activation. Both experimental results and theoretical simulations unravel that the long-range interaction with B atoms decreases the electronic density of Cu active sites and down-shifts the d-band center, and thereby optimizes the adsorption energy for PMS activation. This study provides an approach to finely control the electronic structure of Cu-N4 sites at the atomic level and is expected to guide the design of smart Fenton-like catalysts.

Coupling of Electric and Flow Fields to Enhance Ion Transport for Energy-Efficient Electrochemical Tap-Water Softening.

Electrochemical-induced precipitation is a sustainable approach for tap-water softening, but the hardness removal performance and energy efficiency are vastly limited by the ultraslow ion transport and the superlow local HCO3-/Ca2+ ratio compared to the industrial scenarios. To tackle the challenges, we herein report an energy-efficient electrochemical tap-water softening strategy by utilizing an integrated cathode-anode-cathode (CAC) reactor in which the direction of the electric field is reversed to that of the flow field in the upstream cell, while the same in the downstream cell. As a result, the transport of ions, especially HCO3-, is significantly accelerated in the downstream cell under a flow field. The local HCO3-/Ca2+ ratio is increased by 1.5 times, as revealed by the finite element numerical simulation and in situ imaging. In addition, a continuous flow electrochemical system with an integrated CAC reactor is operated for 240 h to soften tap water. Experiments show that a much lower cell voltage (9.24 V decreased) and energy consumption (28% decreased) are obtained. The proposed ion-transport enhancement strategy by coupled electric and flow fields provides a new perspective on developing electrochemical technologies to meet the flexible and economic demand for tap-water softening.

DNA and RNA Stability of Marine Microalgae in Cold-Stored Sediments and Its Implications in Metabarcoding Analyses.

The ever-increasing applications of metabarcoding analyses for environmental samples demand a well-designed assessment of the stability of DNA and RNA contained in cells that are deposited or buried in marine sediments. We thus conducted a qPCR quantification of the DNA and RNA in the vegetative cells of three microalgae entrapped in facsimile marine sediments and found that >90% of DNA and up to 99% of RNA for all microalgal species were degraded within 60 days at 4 °C. A further examination of the potential interference of the relic DNA of the vegetative cells with resting cyst detection in sediments was performed via a metabarcoding analysis in artificial marine sediments spiked with the vegetative cells of two Kareniaceae dinoflagellates and the resting cysts of another three dinoflagellates. The results demonstrated a dramatic decrease in the relative abundances of the two Kareniaceae dinoflagellates in 120 days, while those of the three resting cysts increased dramatically. Together, our results suggest that a positive detection of microalgae via metabarcoding analysis in DNA or RNA extracted from marine sediments strongly indicates the presence of intact or viable cysts or spores due to the rapid decay of relic DNA/RNA. This study provides a solid basis for the data interpretation of metabarcoding surveys, particularly in resting cyst detection.

A dissipative particle dynamics simulation of controlled loading and responsive release of theranostic agents from reversible crosslinked triblock copolymer vesicles.

To control the transport stability and release efficiency of loaded theranostic drugs in triblock copolymer carriers, the reversible crosslinking ability is of great significance. A molecular level exploration of such a function is needed to extend existing stabilizing and responsive dissociation mechanisms of carriers. Here, dissipative particle dynamics simulations were used to first demonstrate the formation of triblock copolymer vesicular carriers. Chemical crosslinking was used to strengthen the structural stability of the vesicle shell to avoid drug leakage. Reversible decrosslinking along with dissociation of the vesicle and release of loaded drugs were then explored. The structural, energetic and dynamical properties of the system were discussed at the molecular level. The regulation mechanism of drug release patterns was revealed by systematically exploring the effect of intra and intermolecular repulsive interactions. The results indicate that the chemical crosslinking of copolymers enhanced the compactness of the vesicle shell with a strengthened microstructure, increased binding energy, and limited chain migration, thus achieving more stable delivery of drugs. In terms of drug release, we clarified how the pairwise interactions of beads in the solution system affect the responsive dissociation of the vesicle and associated release patterns (speed and amount) of drugs. More efficient delivery and smart release of theranostic drugs are achieved using such reversible crosslinked triblock copolymer vesicles.

An all-organic conditioning method to achieve deep dewatering of waste activated sludge and the underlying mechanism.

Among the common treatment/disposal routes of excessive activated sludge from municipal wastewater treatment plant, dewatering process functions as an essential pre-/post-treatment for volume minimization and transportation facilitation. Since inorganic coagulants have long been criticized for their high dosage and solid residue in sludge cake, there is an urgent need for investigations regarding the potential of applying organic chemicals as the conditioner. In this study, combined use of poly dimethyldiallylammonium chloride (PDMD) and tannic acid (TA) were investigated as an all-organic co-conditioning method for sewage sludge pre-treatment. Results showed that this all-organic conditioning strategy can effectively improve the dewaterability of sewage sludge. The capillary suction time reduced from 128.8 s to 23.1 s, and the filtration resistance reduced from 1.24 × 1012 cm/g to 7.38 × 1010 cm/g. The moisture content of dewatered sludge cake decreased to as low as 55.83%, showing the highest dewatering efficiency reported so far. In addition, the combination of PDMD and TA maximized the treating efficiency with very limited consumption of conditioners (added up to 4% of total solid). Based on the physic-chemical and rheological property investigation, it was proposed that the intermediate molecular weight polymer-based flocculation process and the TA agent-based protein precipitation process, could remarkably strengthen the compactness and structure robustness of sludge. In all, this PDMD-TA-based conditioning method suggested practical significance in consideration of its cost-effectiveness and disposal convenience of sludge cake.

Combined conditioning of inorganic coagulant and polyamine to improve the dewaterability of municipal sludge, minimize dosage and reduce the influence of filtrate.

Efficient dewatering of sludge is necessary for its cost-effective transportation and final disposal. However, the common method of using polyferric sulfate (PFS) and polyacrylamide (PAM) requires a large amount of dosage and produces high iron ion content in the filtrate. This study examined a solution of applying polyamine (PA) coupled with inorganic coagulant PFS. The results demonstrated that using PFS + PA together could achieve the same or similar filtering rates as using PFS + PAM. The capillary suction time (CST) of PFS + PA (89.0 s) was equivalent to that of PFS (75.1 s) and better than that of PA (117.1 s) and raw sludge (RS, 403.8 s). Compared with PFS + PAM, the combination of PFS and PA efficiently removed Fe ions and chemical oxygen demand (COD) in sludge water content, with Fe ions in the sludge filtrate reduced by 97.8% and COD reduced by 78.9%, respectively. By analyzing the basic physicochemical properties of the sludge system, including the synergistic effect of coagulation and flocculation, sludge hydrolysis and flocculation, it indicated that PA + PFS could reduce bound water. These results demonstrated that combining PFS and PA to improve sludge dewatering performance is more beneficial than utilizing a coagulant or flocculant alone, even PFS + PAM.

Designing polymersomes with inhomogeneous membranes by co-assembly of block copolymers for controlled morphological reversibility.

Polymersomes with inhomogeneous membranes in composition and structure have generated widespread interest for the preparation of functionalized nanocarriers. We propose a simple but versatile strategy to manipulate inhomogeneous subdomains on polymersome membranes by the co-assembly of block copolymer blends with varied molecular architectures and chemistries. Both binary and ternary copolymer blends are considered to construct polymersomes, and the subdomains of the membranes are formed by controlling the difference in the flexibility and rigidity of different blocks. This difference contributes to the formation of disk-like domains (by rigid blocks) and soft domains (by flexible blocks) on the membrane. An interesting effect of this structure is that in response to external stimuli, the soft membrane domain becomes worm-like or porous to "open" the polymersome for matter exchange, while the rigid domain stays undecomposed and acts like an anchor binding all flexible copolymers. Once the external stimuli disappear, all flexible copolymers can be pulled back to restore the original polymersome morphology (i.e., "close" the polymersome). The specific morphological reversibility of hybrid polymersomes holds great potential for practical applications where changeable membrane permeability or shape under environmental stimuli is highly needed.

Characterizing the Status of Energetic Metabolism of Dinoflagellate Resting Cysts under Mock Conditions of Marine Sediments via Physiological and Transcriptional Measurements.

Similar to the seeds of higher plants, resting cysts, a non-motile, benthic, and dormant stage in the life history of many dinoflagellate species, play vital roles via germination in the seasonal dynamics and particularly the initiation of harmful algal blooms (HABs) of dinoflagellates. It is thus crucial for resting cysts to balance between the energetic catabolism for viability maintenance and the energy preservation for germination during their dormancy. Despite this importance, studies on how resting cysts of dinoflagellates accomplish energetic metabolism in marine sediment have been virtually absent. In this study, using the cosmopolitan HABs-causing species Scrippsiella acuminata as a representative, we measured the transcriptional activity of the most efficient pathway of the energy catabolism tricarboxylic acid (TCA) cycle, cell viability (via neutral red staining), and the cellular ATP content of resting cysts under a set of mock conditions in marine sediments (e.g., 4 °C, darkness, and anoxia) for a maximum period of one year. Based on the correlation analyses among the expression levels of genes, cyst viability, and ATP content, we revealed that the TCA cycle was still a crucial pathway of energetic catabolism for resting cysts under aerobic conditions, and its expression was elevated at higher temperatures, light irradiation, and the early stage of dormancy. Under anaerobic conditions, however, the TCA cycle pathway ceased expression in resting cysts, as also supported by ATP measurements. Our results have laid a cornerstone for the comprehensive revelation of the energetic metabolism and biochemical processes of dormancy of resting cysts in marine sediments.

Expression Patterns of the Heat Shock Protein 90 (Hsp90) Gene Suggest Its Possible Involvement in Maintaining the Dormancy of Dinoflagellate Resting Cysts.

Heat shock protein 90 (Hsp90) is a highly conserved molecular chaperone functioning in cellular structural folding and conformational integrity maintenance and thus plays vital roles in a variety of biological processes. However, many aspects of these functions and processes remain to be fully elucidated, particularly for non-model organisms. Dinoflagellates are a group of eukaryotes that are exceedingly important in primary production and are responsible for the most harmful algal blooms (HABs) in aquatic ecosystems. The success of dinoflagellates in dominating the plankton community is undoubtedly pertinent to their remarkable adaptive strategies, characteristic of resting cyst production and broad tolerance to stresses of temperature and others. Therefore, this study was conducted to examine the putative roles of Hsp90 in the acclimation to temperature stress and life stage alterations of dinoflagellates. Firstly, we isolated the full-length cDNA of an Hsp90 gene (StHsp90) via RACE from the cosmopolitan HAB species Scrippsiella trochoidea and tracked its transcriptions in response to varied scenarios via real-time qPCR. The results indicated that StHsp90 displayed significant mRNA augment patterns, escalating during 180-min treatments, when the cells were exposed to elevated and lowered temperatures. Secondly, we observed prominently elevated StHsp90 transcriptions in the cysts that were stored at the cold and dark conditions compared to those in newly formed resting cysts and vegetative cells. Finally, and perhaps most importantly, we identified 29 entries of Hsp90-encoding genes with complete coding regions from a dinoflagellate-specific environmental cDNA library generated from marine sediment assemblages. The observed active transcription of these genes in sediment-buried resting cysts was fully supported by the qPCR results for the cold-stored resting cysts of S. trochoidea. Hsp90s expressions in both laboratory-raised and field-collected cysts collectively highlighted the possible involvement and engagement of Hsp90 chaperones in the resting stage persistence of dinoflagellates.

Probing the Energetic Metabolism of Resting Cysts under Different Conditions from Molecular and Physiological Perspectives in the Harmful Algal Blooms-Forming Dinoflagellate Scrippsiella trochoidea.

Energetic metabolism is essential in maintaining the viability of all organisms. Resting cysts play important roles in the ecology of dinoflagellates, particularly for harmful algal blooms (HABs)-causative species. However, the energetic metabolism underlying the germination potency maintenance of resting cysts of dinoflagellate have been extremely scarce in studies from physiological and, particularly, molecular perspectives. Therefore, we used the cosmopolitan Scrippsiella trochoidea as a representative of HABs-forming and cyst-producing dinoflagellates in this work to obtain novel insights into the molecular mechanisms, regulating the energetic metabolism in dinoflagellate resting cysts, under different physical condition. As the starting step, we established a cDNA subtractive library via suppression subtractive hybridization (SSH) technology, from which we screened an incomplete sequence for the ß subunit of ATP synthase gene (ß-F1-ATPase), a key indicator for the status of cell's energetic metabolism. The full-length cDNA of ß-F1-ATPase gene from S.trochoidea (Stß-F1-ATPase) was then obtained via rapid amplification of cDNA ends (RACE) (Accession: MZ343333). Our real-time qPCR detections, in vegetative cells and resting cysts treated with different physical conditions, revealed that (1) the expression of Stß-F1-ATPase in resting cysts was generally much lower than that in vegetative cells, and (2) the Stß-F1-ATPase expressions in the resting cysts under darkness, lowered temperature, and anoxia, and during an extended duration of dormancy, were significantly lower than that in cysts under the condition normally used for culture-maintaining (a 12 h light:12 h dark cycle, 21 °C, aerobic, and newly harvested). Our detections of the viability (via Neutral Red staining) and cellular ATP content of resting cysts, at the conditions corresponding to the abovementioned treatments, showed that both the viability and ATP content decreased rapidly within 12 h and then maintained at low levels within the 4-day experimentation under all the three conditions applied (4 °C, darkness, and anoxia), which are well in accordance with the measurements of the transcription of Stß-F1-ATPase. These results demonstrated that the energy consumption of resting cysts reaches a low, but somehow stable, level within a short time period and is lower at low temperature, darkness, and anoxia than that at ambient temperature. Our work provides an important basis for explaining that resting cysts survive long-term darkness and low temperature in marine sediments from molecular and physiological levels.

Host-Guest Interaction Modulation in Porous Coordination Polymers for Inverse Selective CO2 /C2 H2 Separation.

Controlling gas sorption by simple pore modification is important in molecular recognition and industrial separation processes. In particular, it is challenging to realize the inverse selectivity, which reduces the adsorption of a high-affinity gas and increases the adsorption of a low-affinity gas. Herein, an "opposite action" strategy is demonstrated for boosting CO2 /C2 H2 selectivity in porous coordination polymers (PCPs). A precise steric design of channel pores using an amino group as an additional interacting site enabled the synergetic increase in CO2 adsorption while suppressing the C2 H2 adsorption. Based on this strategy, two new ultramicroporous PCP physisorbents that are isostructural were synthesised. They exhibited the highest CO2 uptake and CO2 /C2 H2 volume uptake ratio at 298 K. Origin of this specific selectivity was verified by detailed density functional theory calculations. The breakthrough separation performances with remarkable stability and recyclability of both the PCPs render them relevant materials for C2 H2 purification from CO2 /C2 H2 mixtures.

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework.

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (Edef ) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control Edef to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an Edef -modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced Edef of PCP enables a selective gate-opening behavior toward CHCl3 over CH2 Cl2 by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.

Retrosynthesis of Tunable Fluorescent Carbon Dots for Precise Long-Term Mitochondrial Tracking.

Mitochondria play a significant role in many cellular processes. Precise long-term tracking of mitochondrial status and behavior is very important for regulating cell fate and treating mitochondrial diseases. However, developing probes with photostability, long-term tracking capability, and tunable long-wavelength fluorescence has been a challenge in mitochondrial targeting. Carbon dots (CDs) as new fluorescent nanomaterials with low toxicity and high stability show increasing advantages in bioimaging. Herein, the mitochondria tracking CDs (MitoTCD) with intrinsic mitochondrial imaging capability and tunable long-wavelength fluorescence from green to red are synthesized where the lipophilic cation of rhodamine is served as the luminescent center of CDs. Due to the excellent photostability, superior fluorescence properties and favorable biocompatibility, these MitoTCD are successfully used for mitochondrial targeting imaging of HeLa cells in vitro and can be tracked as long as six passages, which is suitable for long-term cell imaging. Moreover, these MitoTCD can also be used for zebrafish imaging in vivo.

Leaching potential of stabilized fly ash from the incineration of municipal solid waste with a new polymer.

The presence of toxic metals in municipal solid waste incineration fly ash is of great concern due to their leaching potential in landfills. To prevent groundwater or soil contamination caused by metal leaching from fly ash, recently the Chinese government began to require that the leachate concentrations of toxic metals not only satisfied the GB 16889-2008 criteria prior to landfilling but also introduced a series of measures to monitor the groundwater quality in the landfill site and its adjacent areas (GB/T 18772-2017). The stringent hazardous waste measures for pollution control on landfill sites of municipal solid waste demand the development of more efficient chemical stabilizers. To this end, a novel type of chemical stabilizer, a dithiocarboxylate functionalized polymer (TEM_CSSNa) was fabricated. Its efficiency for stabilizing toxic metals was evaluated at different dosages over a range of pH values. To compare with traditional stabilizers, sodium sulfide (Na2S) and thiourea (Tu) were also studied. The results showed that TEM_CSSNa-stabilized fly ash could satisfy the criteria at a dosage of only 3%, while those for Na2S and Tu were around 10%. In addition, this new polymer retained its stabilizing efficiency over a broad pH range. After TEM_CSSNa stabilization treatment, approximately 40-65% of the metals existed in the residual fraction, whereas only 35-55% were converted to the residual fraction using Na2S and Tu stabilization. The formation of a geochemically stable phase reduced the mobility of toxic metals and therefore diminished their leaching potential in landfills.

Sensitive electrochemical detection of DNA damage based on in situ double strand growth via hybridization chain reaction.

Detection of DNA damage caused by ∙OH or radiation has led to rapidly growing interest in the fields of drug development, biochemistry, clinic diagnostics, and environmental evaluation. Electrochemical methods have been applied for DNA damage detection because of their fast and sensitive response. However, most of the electrochemical methods for DNA damage detection commonly require immobilization of the strands on the electrode surface. In the present work, sensitive electrochemical monitoring of DNA damage was realized successfully on the basis of in situ DNA chain growth by use of a hybridization chain reaction (HCR) technique. By use of [Ru(NH3)6]3+ as the signal probe and the Fenton reaction as the ∙OH generator, ultrasensitive detection of DNA damage induced by ∙OH was realized successfully through differential pulse voltammetry with a linear relationship of ∙OH concentration from 15 to 750 pM and a detection limit of 12 pM. Furthermore, environmental DNA-damaging UV light was tested as the lesion source to demonstrate the practicability and reliability of the proposed HCR-based amplified signal method for DNA damage detection. By integrating the HCR technique with an electrochemical method, we provide a promising alternative approach to extend the applications of electrochemical methods in bioanalytical detection of DNA damage. Graphical abstract Sensitive electrochemical monitoring of DNA damage has been realized successfully on the basis of in situ DNA chain growth by use of hybridization chain reaction (HCR). Detection of DNA damage caused by ∙OH was realized successfully through differential pulse voltammetry with a linear relationship of ∙OH concentration from 15 to 750 pM and a detection limit of 12 pM.

Evaluating climatic and non-climatic stresses for declining surface water quality in Bagmati River of Nepal.

Both climatic and non-climatic factors affect surface water quality. Similar to its effect across various sectors and areas, climate change has potential to affect surface water quality directly and indirectly. On the one hand, the rise in temperature enhances the microbial activity and decomposition of organic matter in the river system and changes in rainfall alter discharge and water flow in the river ultimately affecting pollution dilution level. On the other hand, the disposal of organic waste and channelizing municipal sewage into the rivers seriously worsen water quality. This study attempts to relate hydro-climatology, water quality, and impact of climatic and non-climatic stresses in affecting river water quality in the upper Bagmati basin in Central Nepal. The results showed that the key water quality indicators such as dissolved oxygen and chemical oxygen demand are getting worse in recent years. No significant relationships were found between the key water quality indicators and changes in key climatic variables. However, the water quality indicators correlated with the increase in urban population and per capita waste production in the city. The findings of this study indicate that dealing with non-climatic stressors such as reducing direct disposal of sewerage and other wastes in the river rather than emphasizing on working with the effects from climate change would largely help to improve water quality in the river flowing from highly populated urban areas.

Controllable Modular Growth of Hierarchical MOF-on-MOF Architectures.

Fabrication of hybrid MOF-on-MOF heteroarchitectures can create novel and multifunctional platforms to achieve desired properties. However, only MOFs with similar crystallographic parameters can be hybridized by the classical epitaxial growth method (EGM), which largely suppressed its applications. A general strategy, called internal extended growth method (IEGM), is demonstrated for the feasible assembly of MOFs with distinct crystallographic parameters in an MOF matrix. Various MOFs with diverse functions could be introduced in a modular MOF matrix to form 3D core-satellite pluralistic hybrid system. The number of different MOF crystals interspersed could be varied on demand. More importantly, the different MOF crystals distributed in individual domains could be used to further incorporate functional units or enhance target functions.

The metal-organic framework MIL-53(Al) constructed from multiple metal sources: alumina, aluminum hydroxide, and boehmite.

Three aluminum compounds, namely alumina, aluminum hydroxide, and boehmite, are probed as the metal sources for the hydrothermal synthesis of a typical metal-organic framework MIL-53(Al). The process exhibits enhanced synthetic efficiency without the generation of strongly acidic byproducts. The time-course monitoring of conversion from different aluminum sources into MIL-53(Al) is achieved by multiple characterization that reveals a similar but differentiated crystallinity, porosity, and morphology relative to typical MIL-53(Al) prepared from water-soluble aluminum salts. Moreover, the prepared MIL-53(Al) constructed with the three insoluble aluminum sources exhibit an improved thermal stability of up to nearly 600 °C and enhanced yields. Alumina and boehmite are more preferable than aluminum hydroxide in terms of product porosity, yield, and reaction time. The adsorption performances of a typical environmental endocrine disruptor, dimethyl phthalate, on the prepared MIL-53(Al) samples are also investigated. The improved structural stability of MIL-53(Al) prepared from these alternative aluminum sources enables double-enhanced adsorption performance (up to 206 mg g(-1)) relative to the conventionally obtained MIL-53(Al).