An Activatable NIR Fluorescent Probe for NAD(P)H and Its Application to the Real-Time Monitoring of p53 Abnormalities In Vivo.

NAD(P)H is crucial for biosynthetic reactions and antioxidant functions. However, the current probes developed for detecting NAD(P)H in vivo require intratumoral injection, which limited their application for animal imaging. To address this issue, we have developed a liposoluble cationic probe, KC8, which exhibits excellent tumor-targeting ability and near-infrared (NIR) fluorescence after reaction with NAD(P)H. By using KC8, it was demonstrated for the first time that the level of NAD(P)H in the mitochondria of living colorectal cancer (CRC) cells was highly related to the abnormality of the p53. Furthermore, KC8 was successfully used to differentiate not only between tumor and normal tissue but also between tumors with p53 abnormality and normal tumors when administered intravenously. Finally, we evaluated tumor heterogeneity through two fluorescent channels after treating a tumor with 5-Fu. This study provides a new tool for real-time monitoring of the p53 abnormality of CRC cells.

Novel heterostructured metal doped MgFe2O4@g-C3N4 nanocomposites with superior photo-Fenton preformance for antibiotics removal: One-step synthesis and synergistic mechanism.

A novel metal doped MgFe2O4@g-C3N4 (m-MF@CN) nanocomposite was synthesized by one-pot method using saprolite laterite nickel ore and urea as raw materials. The heterostructure was verified as an effective heterogeneous Fenton-like catalyst for degrading antibiotics including tetracycline, oxytetracycline and chlortetracycline hydrochloride, and the related catalytic mechanism was elaborated in detail. Under the optimum conditions, the m-MF@CN/H2O2/vis system exhibited superior photo-Fenton property (degradation efficiency of 93.15% within 30 min, TOC removal efficiency was as high as 60.54% within 120 min) and cycle stability for tetracycline removal. The combination of MgFe2O4 and g-C3N4 enhanced the absorption of visible light, and the energy level matched heterojunction promoted the separation of photogenerated electron-holes to accelerate the redox cycle of ≡Fe3+/≡Fe2+. Free radical quenching and electron spin resonance (ESR) analysis confirmed that O2- was the main active species, h+ and OH also played a synergistic role in the degrading reactions. Notably, a possible degradation pathway of tetracycline was proposed according to the intermediates produced in the reaction process. The one-step synthesized m-MF@CN nanocomposite catalysts possessed high catalytic performance, good stability and recoverability, which not only realized the high-value utilization of ore raw materials, but also provided a potential practical way for efficient treatment of antibiotic wastewater.

An efficient and low-cost magnetic heterogenous Fenton-like catalyst for degrading antibiotics in wastewater: Mechanism, pathway and stability.

Metal-doped MgFe2O4 spinel ferrite synthesized from saprolite laterite nickel ore was verified as an efficient heterogeneous Fenton-like catalyst for degrading antibiotics including tetracycline (TC) and metronidazole (MNZ) in a "catalyst/oxalic acid (H2C2O4)/visible light (vis)" system. The degradation efficiencies reached over 95% and total organic carbon (TOC) removal efficiencies were nearly 50% of the two antibiotics within 210 min, under the optimal conditions, especially 90% catalytic activity of the fresh catalyst was maintained after five cycles, suggesting the ferrite possessed excellent degrading performance, cycling stability and applicability. Moreover, the degradation mechanism and pathway of TC were elucidated in detail. Results revealed that the [≡Fe(C2O4)3]3- complex ions formed by octahedral Fe3+ in spinel ferrite with oxalate ions on the surface of MgFe2O4, played the key role in production of ·OH radicals which decomposed antibiotic TC into small molecules even mineralized in three pathways. Cost-effective preparation, high catalytic performance and long cycle life may accelerate the practical application of the heterogeneous Fenton-like catalyst.

Effects of solid waste-based soil conditioner and arbuscular mycorrhizal fungi on crop productivity and heavy metal distribution in foxtail millet (Setaria italica).

Shanxi is a large coal-producing province, and it also produces a lot of solid waste. Solid waste can leach heavy metals, which can harm soil and affect food security at the beginning of the food chain. To investigate the impacts of solid waste-based soil conditioner (SWSC) and arbuscular mycorrhizal fungi (AMF) on millet safety and crop production, a field experiment with foxtail millet (Setaria italica) was conducted in Tunliu. The results of this study demonstrate that SWSC + AMF, SWSC and AMF can increase millet yield by 28.0%, 27.1% and 19.5%, respectively, compared with CK. This is mainly due to increased mycorrhizal infection. Besides, the pollution index (Pi) and the Nemerow-integrated pollution index (PN) of the soil with SWSC and AMF were both below 0.7, indicating safe pollution levels. The application of AMF and SWSC inhibits plants from absorbing heavy metals from the soil and reduces the TFroot/soil of the millet. SWSC + AMF application inhibited the transfer of heavy metals from the roots to the upper part of the ground and reduced the TFshoot/root of the millet. The TFgrain/soil of the millet was below 1. The HQ and HI of the millet grains did not exceed 1, indicating the absence of a potential health risk. Therefore, SWSC combined with AMF is applicable for millet production in Tunliu, and the combined treatment can decrease heavy metal phytoavailability and post-harvest transfer risks. This work provides a way to utilize solid waste while also improving millet yields in dry farming. Based on the review, we suggested future researches to better understand the mechanisms of SWSC + AMF long-term application to promote awareness on its role over time through alterations in its surface chemistry, soil microbial community and environmental implications.

Research on the mechanism of sodium separation in bauxite residue synergy preparation of potassium-containing compound fertilizer raw materials by the hydrothermal method.

Bauxite residue poses an increasingly serious ecological safety problem in the alumina industry. A novel process for removing sodium in bauxite residue synergistic preparation of potassium-containing compound fertilizer raw materials was proposed to relieve pressure on the fertilizer industry. In this paper, synthetic sodalite and katoite were used to simulate the main mineral phases of bauxite residue to determine the suitable conditions for the method, and the transformation mechanism of the process was researched by analyzing the phase structure and microscopic morphology of the samples using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and specific surface area detection. The results show that the ideal reaction condition is 320 g/L K2O with solid reactants at 200 °C for 1 h. The separation rate of Na in the sodalite-katoite mixture reached 93.60%, with potassium aluminum silicate and katoite being the primary phases of the product, with a mesoporous structure and easy to be absorbed by crops. The bauxite residue transformation residue consisted of katoite and kaliophilite. With a total effective K2O, CaO, and SiO2 content of 38.22%, the Na2O content was 0.54%, meeting the requirements of compound fertilizer content on the market. The transformation mechanism is a dissolution-precipitation controlled sodium-potassium ion replacement reaction. This study provides theoretical guidance for the preparation of mineral fertilizer from bauxite residue and has practical production potential, opening up a new perspective for bauxite residue resource usage in the agricultural field.

Enhanced heterogeneous Fenton-like degradation of refractory organic contaminants over Cu doped (Mg,Ni)(Fe,Al)2O4 synthesized from laterite nickel ore.

The heterogeneous Fenton-like catalyst (Mg,Cu,Ni)(Fe,Al)2O4 was synthesized via a coprecipitation method using laterite nickel ore leaching solution as raw material. The effects of CuCl2·2H2O addition and calcination temperature on the microstructures and degradation properties of the obtained products were investigated. Results showed that higher calcination temperature could promote the migration of Cu2+ ions from CuO to the spinel ferrite lattice and occupied octahedral sites. The degradation efficiencies (η) of various types of low-concentration dyes and tetracycline were higher than 95%, which was mainly due to the accelerated generation of OH radicals by the synergistic effect of Fe3+ and Cu2+ ions in octahedral sites of the formed (Mg,Cu,Ni)(Fe,Al)2O4. Moreover, after five consecutive degradation cycles, the η of RhB was still close to 100%, TOC removal efficiency was maintained around 40% and the concentrations of metallic ions in degraded solutions were all lower than the national effluent discharge standard (GB8978-1996), confirming the as-obtained (Mg,Cu,Ni)(Fe,Al)2O4 was an eco-friendly heterogeneous Fenton-like catalyst with excellent stability and reusability. This study may provide an effective reference for large scale preparing efficient heterogeneous Fenton-like catalysts from natural minerals in treating the wastewater contaminated by refractory organics.

Zinc-bearing dust derived non-toxic mixed iron oxides as magnetically recyclable photo-Fenton catalyst for degradation of dye.

In this paper, comprehensive utilization of hazardous zinc-bearing dust for preparation of non-toxic mixed iron oxides as a magnetically recyclable photo-Fenton catalyst for degradation of dye by a facile solid state reaction process was proposed. The as-prepared samples were characterized by X-ray diffraction (XRD), Raman spectra, ultraviolet and visible (UV-Vis) spectra and Physical Property Measurement System (PPMS), and the degradation performance of as-prepared catalysts was also tested and analyzed. The results show that spinel ferrite coexisting with or without Fe2O3 was the predominant phase in the as-prepared samples, which were confirmed by Raman analysis. The as-prepared samples presented high degradation efficiency (about 90%) of rhodamine B (RhB) in the presence of hydrogen peroxide (H2O2) with visible light irradiation, owing to the synergistic effect of photocatalyst reaction and Fenton-like catalyst reaction during the degradation process. The mixed iron oxides also presented stable structure and exhibited excellent reusability with a degradation efficiency of 87% after the fifth cycle of reuse. Importantly, the heavy metals in the zinc-bearing dust could be fixed in the stable spinel structure. This paper could provide a simple approach for comprehensive utilization of zinc-bearing dust to synthesize non-toxic mixed iron oxides as a magnetically recyclable photo-Fenton catalyst for degradation of dye.

Employing an ICT-FRET Integration Platform for the Real-Time Tracking of SO2 Metabolism in Cancer Cells and Tumor Models.

Glutathione (GSH) mediates a wide variety of biological events and human diseases. Although it has been the subject of intense study in recent years, a further understanding of its molecular mechanisms and metabolism routes in living cells has remained limited due to a lack of appropriate analytical tools. Sulfur dioxide (SO2), an important metabolite of GSH, is usually associated with the symptoms of neurological disorders, cardiovascular diseases, and lung cancer. Herein, a novel multisignal fluorescent probe was rationally designed and exploited for the simultaneous detection of GSH and its metabolite SO2 via an ICT-FRET synergetic mechanism. The probe shows completely reversed fluorescence responses toward GSH (enhanced red emission) and SO2 (annihilated red fluorescence) with high selectivity and sensitivity. In particular, the probe displayed completely different fluorescent signals (blue-shift) with SO2 in the presence of GSH, thereby allowing the imaging of the metabolism process of GSH to SO2 in two independent channels without spectral cross interference. Given these advantages, this probe has been successfully applied to the real-time monitoring of the SO2 metabolic process in living cells and mice models, and it has thus been found that GSH can metabolize SO2 by enzymatic reaction with TST (thiosulfate sulphurtransferase); additionally, SO2 was transformed into sulfate under SUOX (sulfite oxidase). We anticipate that this research will provide a convenient and efficient tool for understanding the interrelated physiological functions of GSH and SO2 in more biosystems.

A New Strategy: Distinguishable Multi-substance Detection, Multiple Pathway Tracing Based on a New Site Constructed by the Reaction Process and Its Tumor Targeting.

In recent years, it has become a trend to employ organic molecular fluorescent probes with multireaction sites for the distinguishable detection and biological imaging of similar substances. However, the introduction of multireaction sites brought great challenges to organic synthesis, and at the same time, often destroyed the conjugated structure of the molecules, leading to an unsatisfactory fluorescence emission wavelength not conducive to practical application. As the eternal theme of life, metabolism goes on all the time. Metabolism is a series of ordered chemical reactions that occurs in the organism to maintain life. Chemical reactions in metabolism can be summarized as metabolic pathways. Simultaneous monitoring of different metabolic pathways of the same substance poses a lofty challenge to the probe. Here, we developed a new strategy: to construct new sites through the preliminary reactions between probes and some targets, which can be used to further distinguish among targets or detect their metabolites, so as to realize the simultaneous visualization tracer of multiple metabolic pathways. By intravenous injection, it revealed that the probe containing benzopyrylium ion can target tumors efficiently, and thiols are highly expressed in tumors compared to other tissues (heart, lung, kidney, liver, etc.). The consumption of thiols by the probe could not prevent tumor growth, suggesting that the tumor cure was not correlated with thiol concentration. The construction of new sites in the reaction process is a novel idea in the pursuit of multiple reaction sites, which will provide more effective tools for solving practical problems.

Heat Stroke in Cell Tissues Related to Sulfur Dioxide Level Is Precisely Monitored by Light-Controlled Fluorescent Probes.

Heat stroke (HS) can cause serious organism damage or even death. Early understanding of the mechanism of heat cytotoxicity can prevent or treat heat stroke related diseases. In this work, probe Ly-NT-SP was synthesized, characterized, and used for sulfur dioxide (SO2) detection in lysosomes. PBS solutions of probe Ly-NT-SP at pH 5.0 present a marked broad emission band in the green zone (535 nm). After UV irradiation, the spiropyran group in Ly-NT-SP isomerizes to the merocyanine form (Ly-NT-MR), which presented a weak red-shifted emission at 630 nm. In addition, photocontrolled isomerization of Ly-NT-SP to Ly-NT-MR generated a C═C-C═N+ fragment able to react, through a Michael addition, with SO2 to yield a highly emissive adduct with a marked fluorescence in the green channel (535 nm). In vitro studies showed a remarkable selectivity of photoactivated Ly-NT-MR to SO2 with a limit of detection as low as 4.7 µM. MTT viability assays demonstrated that the Ly-NT-SP is nontoxic to HeLa cells and can be used to detect SO2 in lysosomes. Taking advantage of this, the sensor is successfully applied to image increasing SO2 values in lysosomes during heat shock for the first time. Moreover, we also confirmed that the increased SO2 can protect the small intestine against damage induced by heat shock through regulating oxidative stress in cells and mice.

Low-Temperature Highly Efficient and Selective Removal of H2S over Three-Dimensional Zn-Cu-Based Materials in an Anaerobic Environment.

In this study, novel three-dimensional ribbon-like composite materials have been introduced for selectively capturing H2S in a low-temperature dry anaerobic environment. First, a ribbon-like basic copper carbonate precursor with Zn doping supported on the activated semicoke (ASC) was successfully synthesized in situ by a two-step hydrothermal method for the first time. The porous Zn-Cu materials obtained after calcination were applied as a sorbent to remove H2S under anaerobic conditions at a low temperature. Effects of the heat treatment temperature, Cu loading content, and Zn doping content on the anaerobic desulfurization performance of Zn-doped CuOx/ASC sorbents were investigated. The optimal Zn-doped CuOx/ASC sorbent showed a satisfactory activity and selectivity to capture H2S efficiently with a breakthrough capacity of 126 mg/g. Further mechanism study demonstrates that the super desulfurization performance of this sorbent is mainly attributed to abundant pore distribution, the synergistic effect between copper and zinc, the extensive surface active oxygen, and so forth.

Correction: Functional synthetic probes for selective targeting and multi-analyte detection and imaging.

Correction for 'Functional synthetic probes for selective targeting and multi-analyte detection and imaging' by Yongkang Yue et al., Chem. Soc. Rev., 2019, DOI: 10.1039/c8cs01006d.

Functional synthetic probes for selective targeting and multi-analyte detection and imaging.

In contrast to the classical design of a probe with one binding site to target one specific analyte, probes with multiple interaction sites or, alternatively, with single sites promoting tandem reactions to target one or multiple analytes, have been developed. They have been used in addressing the inherent challenges of selective targeting in the presence of structurally similar compounds and in complex matrices, as well as the visualization of the in vivo interaction or crosstalk between the analytes. Examples of analytes include reactive sulfur species, reactive oxygen species, nucleotides and enzymes. This review focuses on recent innovations in probe design, detection mechanisms and the investigation of biological processes. The vision is to promote the ongoing development of fluorescent probes to enable deeper insight into the physiology of bioactive analytes.

Hybrid microbial electrolytic/UV system for highly efficient organic pollutants removal.

This study for the first time proposed an efficient microbial electrolyte/UV system for Methyl Orange decomposition. With an external applied voltage of 0.2 V and cathode aeration of 20 mL/min, H2O2 could be in-situ generated from two-electron reduction of oxygen in cathode, reaching to 8.1 mg/L in 2 hr and continued to increase. The pollutant removal efficiency of approximate 94.7% was achieved at initial neutral pH, with the activation of •OH in the presence of UV illumination. Although the nature of its guiding principles remain on the vista of practical exploration, this proof-of-concept study provides an alternative operation pattern of solar-microbial hybrid technology for future wastewater treatment from a basic but multidisciplinary view.

High mercury leachate containing HgS22- complex ion: Detoxifying solidification and high efficiency Hg extraction.

Clean and efficient treatment of high-mercury leachate produced from remediation of mercury-polluted soil has become a huge challenge for environmental scientists. In this work, cement solidification was firstly adopted to treat the high-concentration mercury leachate, which had high alkalinity. Different mercury concentrations, namely 3.120mg/L Hg mercury leachate and 9.243mg/L Hg mercury concentrated leachate, were separately solidified by Portland cement. The results indicated that simply using the cement can properly solidify both the leachates to meet the waste landfill standard, with liquid (mL)/solid (g) ratio (L/S ratio) of 4:10-6:10. In order to make full use of mercury in the leachates, a Hg extraction method was subsequently carried out under different experimental parameters, such as temperature and pH value. It was shown that the Hg extraction ratio could reach as high as 99.84% and almost all the mercury in the leachate could be transformed to HgS precipitate; moreover, the Hg concentration in the treated leachate was reduced from 3.120 to 0.005mg/L at pH2.98 and 30°C, which was much less than the limit of the national standard, indicating that the leachate had been completely cleaned and could be discharged freely. Hence, simple cement solidification renders high-mercury leachate nontoxic, and the Hg extraction method can successfully recover the Hg and enable the residual leachate to be discharged safely.

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

A Dual Colorimetric/Fluorescence System for Determining pH Based on the Nucleophilic Addition Reaction of an o-Hydroxymerocyanine Dye.

Owing to their ability to monitor pH in a precise and rapid manner, optical probes have widely been developed for biological and nonbiological applications. The strategies thus far employed to determine pH rely on two types of processes including reversible protonation of amine nitrogen atoms and deprotonation of phenols. We have developed a novel dual, colorimetric/fluorescence system for determining the pH of a solution. This system utilizes an o-hydroxymerocyanine dye that undergoes a nucleophilic addition reaction that subsequently causes reversible structural changes interconverting a merocyanine to a spirocyanine and a spirocyanine to a spiropyran. It was demonstrated that the dye can be employed to measure the pH of solutions in the 2.5-5.75 and 9.6-11.8 ranges with color changes from yellow to dark blue and then to lavender. Moreover, the fluorescence response associated with the spirocyanine-spiropyran transformation of the dye occurring in alkaline solutions provides a precise method.

Modification of waste coal gangue and its application in the removal of Mn(2+) from aqueous solution.

We developed a new calcination method to convert coal gangue (CG), a common waste generated from coal production process, into a modified form, which could be used as an adsorbent to remove Mn(2+) from aqueous solution. Sodium tetraborate (Na2B4O7·10H2O) was added into the CG calcination process as an additive, and the concentrations of Na2B4O7·10H2O were optimized along with the calcination temperature to obtain the best adsorbent capacity of modified coal gangue (MCG). We applied multiple analytical methods such as scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller analysis to characterize the MCG. The results showed it had a smaller particle size and a larger specific surface area and pore volume after modification. It also indicated that the phase of CG transformed from kaolinite to metakaolinite after calcination. Moreover, a new substance was generated with two new peaks at 1,632 cm(-1) and 799 cm(-1). The Mn(2+) absorption capacity of MCG was evaluated using a series of experiments with different adsorbent doses, pH values and initial Mn(2+) concentrations during the adsorption process. We found that Mn(2+) adsorbent capacity of MCG increased by more than seven-fold compared to that of CG. The Langmuir isotherm model and the pseudo-second-order kinetic model provided the best fit to the adsorption processes.

pH-Responsive Gas-Water-Solid Interface for Multiphase Catalysis.

Despite their wide utility in laboratory synthesis and industrial fabrication, gas-water-solid multiphase catalysis reactions often suffer from low reaction efficiency because of the low solubility of gases in water. Using a surface-modification protocol, interface-active silica nanoparticles were synthesized. Such nanoparticles can assemble at the gas-water interface, stabilizing micrometer-sized gas bubbles in water, and disassemble by tuning of the aqueous phase pH. The ability to stabilize gas microbubbles can be finely tuned through variation of the surface-modification protocol. As proof of this concept, Pd and Au were deposited on these silica nanoparticles, leading to interface-active catalysts for aqueous hydrogenation and oxidation, respectively. With such catalysts, conventional gas-water-solid multiphase reactions can be transformed to H2 or O2 microbubble reaction systems. The resultant microbubble reaction systems exhibit significant catalysis efficiency enhancement effects compared with conventional multiphase reactions. The significant improvement is attributed to the pronounced increase in reaction interface area that allows for the direct contact of gas, water, and solid phases. At the end of reaction, the microbubbles can be removed from the reaction systems through changing the pH, allowing product separation and catalyst recycling. Interestingly, the alcohol oxidation activation energy for the microbubble systems is much lower than that for the conventional multiphase reaction, also indicating that the developed microbubble system may be a valuable platform to design innovative multiphase catalysis reactions.

An effective utilization of the slag from acid leaching of coal-waste: preparation of water glass with a low-temperature co-melting reaction.

This paper presents an effective utilization of slag from acid leaching of coal-waste with a novel approach, namely low-temperature co-melting method, for preparation of sodium silicate (Na2O x nSiO2) using slag from acid leaching of coal-waste as feedstock. It is very interesting that the co-melting reaction temperature of the mixture of Na2CO3 and the feedstock (50-100 microm) was as low as 850 degrees C, which was significantly lower than the temperature used in traditional sodium silicate production (1400 degrees C). The optimum SiO2/Na2O ratio was identified as 7:3 according to the results of thermogravimetry-differential scanning calorimetry (TGA-DSC), ICP-AES, and X-ray diffraction (XRD) analyses. In this condition, the main product was sodium disilicate (Na2O x 2SiO2), with water solubility of 85.0%. More importantly, the impurities such as aluminum in the feedstock, which had adverse effect on subsequent treatment, were concentrated almost completely in the filter residue as insoluble sodium alumunosilicates, i.e., Na(Si2Al)O6 x H2O. The lower co-melting temperature of this process demonstrates a significant energy-saving opportunity and thus a promising approach for highly effective utilization of coal-waste. Implications: Recently, alumina extraction from coal-waste has been extensively investigated and industrial applied in China. However, the slag-containing silica generated from the acid leaching process of coal-waste led to a secondary pollution, which hindered large-scale production. The proposed low-temperature co-melting method for preparation of sodium silicate (Na2O x nSiO2) using slag from acid leaching of coal-waste as feedstock indicated that it is an efficient approach for the recovery of silica from the acid-leached slag of coal-waste with minimal environmental impact.