A near infrared fluorescent probe based on ICT for monitoring mitophagy in living cells.

Mitophagy, the process in which cells degrade dysfunctional organelles and recycle their nutrient substances by lysosomes, plays a vital role in cell metabolism and physiology. Herein, we present a highly targeting and near-infrared (NIR) mitochondrion fluorescent probe, which can monitor the process of autophagy. The response mechanism of the probe is based on intramolecular charge transfer (ICT) for the detection of autophagy and real-time imaging of living cells. We designed a primary amine as a pH sensitizing group, and due to the ICT process, the probe exhibits green fluorescence, and when it is protonated the ICT process is broken, and the NIR fluorescence will be restored. Simultaneously, the green fluorescence of the probe disappears. This probe exhibits excellent selectivity, high sensitivity and clean responsiveness, which indicate that it can be applied for high-targeting and high-sensitive imaging of the process of autophagy in living systems.

Removal of uranium(VI) from aqueous solution by Camellia oleifera shell-based activated carbon: adsorption equilibrium, kinetics, and thermodynamics.

Camellia oleifera shell-based activated carbon (COSAC) was prepared by H3PO4 activation method and further used to remove U(VI) from the aqueous solution in a batch system. This research examined the influence of various factors affecting U(VI) removal, including contact time, pH, initial U(VI) concentration, and temperature. The results showed that the U(VI) adsorption capacity and removal efficiency reached 71.28 mg/g and 89.1% at the initial U(VI) concentration of 160 mg/L, temperature of 298 K, pH 5.5, contact time of 60 min, and COSAC dosage of 2.0 g/L. The pseudo-first-order, pseudo-second-order, and intraparticle diffusion equations were used to identify the optimum model that can describe the U(VI) adsorption kinetics. The pseudo-second-order kinetics model performed better in characterizing the adsorption system compared with the pseudo-first-order and intraparticle diffusion models. Isotherm data were also discussed with regard to the appropriacy of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. The Langmuir model described the U(VI) adsorption process the best with a maximum adsorption capacity of 78.93 mg/g. Thermodynamic analysis (ΔG0 < 0, ΔH0 > 0, and ΔS0 > 0) indicated that the U(VI) adsorption process is endothermic and spontaneous. All the results imply that COSAC has a promising application in the removal or recovery of U(VI) from aqueous solutions.

Removal of Cr(VI) and methyl orange by activated carbon fiber supported nanoscale zero-valent iron in a continuous fixed bed column.

The application of activated carbon fiber supported nanoscale zero-valent iron (ACF-nZVI) in the continuous removal of Cr(VI) and methyl orange (MO) from aqueous solution was studied in depth. The breakthrough curves of Cr(VI) in a fixed bed with ACF-nZVI were measured, and compared with those in the fixed bed with ACF. The catalytic wet peroxide oxidation (CWPO) process for MO was also carried out using ACF-nZVI after reacting with Cr(VI) in the same fixed bed. The results showed that the breakthrough time of ACF-nZVI was significantly longer than that of ACF. Higher pH values were unfavorable for the Cr(VI) removal. The breakthrough time increased with decreasing inlet Cr(VI) concentration or increasing bed height. The Yoon-Nelson and bed depth service time (BDST) models were found to show good agreement with the experimental data. The Cr(VI) removal capacity when using ACF-nZVI was two times higher than that when using ACF. Under the optimal empty bed contact time of 1.256 min, the fixed bed displayed high MO conversion (99.2%) and chemical oxygen demand removal ratio (55.7%) with low Fe leaching concentration (<5 mg/L) after continuous running for 240 min. After three cycles, the conversion of MO remained largely unchanged.

Treatment of methyl orange by the catalytic wet peroxide oxidation process in batch and continuous fixed bed reactors using Fe-impregnated 13X as catalyst.

Fe-impregnated 13X (Fe-13X) catalysts were prepared for catalytic wet peroxide oxidation (CWPO) of methyl orange (MO) solution in batch and continuous fixed bed reactors. A systematical study was carried out to investigate the influence of the main operating parameters on the batch reactor performance. The kinetic curves were analyzed by using a pseudo-first-order kinetic equation over the 30-70 °C temperature range. In addition, the effects of catalysts filling amount and feed flow rate on the catalytic performance of Fe-13X catalysts in a fixed bed reactor were studied. The experimental results showed that the Fe-13X catalysts achieved the highest activity (100% MO conversion and 74.5% chemical oxygen demand (COD) elimination ratio, respectively) at 25 min with trace mount of Fe leaching concentration (<2.1 mg/L) at the optimized reaction conditions (namely 1.0 g/L catalyst concentration, pH 2.0, 17.6 mM H2O2, 70 °C) in a batch reactor. Kinetic studies showed that two different reaction regions existed, and an activation energy of 51.9 kJ/mol for the second region was found. Under the optimal operating conditions found (namely, catalysts filling amount of 3.5 g, feed flow rate of 4 mL/min), the Fe-13X catalysts displayed high MO conversion (99.4%) and COD elimination ratio (77.1%) after continuously ran for 200 min in a fixed bed reactor.

Uranium biosorption from aqueous solution by the submerged aquatic plant Hydrilla verticillata.

The biosorption characteristics of U(VI) from aqueous solution onto a nonliving aquatic macrophyte, Hydrilla verticillata (dry powder), were investigated under various experimental conditions by using batch methods. Results showed that the adsorption reached equilibrium within 60 min and the experimental data were well fitted by the pseudo-first-order kinetic model. U(VI) adsorption was strongly pH dependent, and the optimum pH for U(VI) removal was 5.5. Isotherm adsorption data displayed good correlation with the Langmuir model, with a maximum monolayer adsorption capacity of 171.52 mg/g. Thermodynamic studies suggested that U(VI) adsorption onto H. verticillata was an exothermic and spontaneous process in nature. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated that the amino and hydroxyl groups on the algal surface played an important role in U(VI) adsorption. The mechanisms responsible for U(VI) adsorption could involve electrostatic attraction and ion exchange. In conclusion, H. verticillata biomass showed good potential as an adsorption material for the removal of uranium contaminants in aqueous solution.

Removal of Pb(II) by adsorption onto Chinese walnut shell activated carbon.

The excessive discharge of Pb(II) into the environment has increasingly aroused great concern. Adsorption is considered as the most effective method for heavy metal removal. Chinese walnut shell activated carbon (CWSAC) was used as an adsorbent for the removal of Pb(II) from aqueous solution. Batch experiments were conducted by varying contact time, temperature, pH, adsorbent dose and initial Pb(II) concentration. Adsorption equilibrium was established within 150 min. Although temperature effect was insignificant, the Pb(II) adsorption was strongly pH dependent and the maximum removal was observed at pH 5.5. The Pb(II) removal efficiency increased with increasing CWSAC dosage up to 2.0 g/L and reached a maximum of 94.12%. Langmuir and Freundlich adsorption isotherms were employed to fit the adsorption data. The results suggested that the equilibrium data could be well described by the Langmuir isotherm model, with a maximum adsorption capacity of 81.96 mg/g. Adsorption kinetics data were fitted by pseudo-first- and pseudo-second-order models. The result indicated that the pseudo-first-order model best describes the adsorption kinetic data. In summary, CWSAC could be a promising material for the removal of Pb(II) from wastewater.

Investigating Pseudomonas putida-Candida humicola interactions as affected by chelate Fe(III) in soil.

Microcalorimetric technique was applied to assess the toxic effect of EDTA-chelated trivalent iron on Pseudomonas putida (P. putida) (bacterium), Candida humicola (C. humicola) (fungus) and their mixture in sterilized soil. Microbial growth rate constant k, total heat evolution Q T, metabolic enthalpy ∆H met, mass specific heat rate J Q/S, microbial biomass C and inhibitory ratio I were calculated. Results showed that microcalorimetric indexes decreased with the increasing Fe(III)-EDTA complex concentration. Comparing the single and mixed strains, the effect of Fe(III) on bacterium-fungus interaction was dominant at lower dose, whereas, the metal toxicity at high dose of Fe was the main factor affecting P. putida and C. humicola activity. Thus, the mixture had moderate tolerance to the iron overload, and exhibit synergistic interaction in exponential growth phase (0-0.3 mg g(-1)). The results of glucose degradation showed that glucose was consumed totally at the end of exponential phase of microbial growth.

Complexing agent-assisted Cr(VI) removal in a continuous fixed-bed system with nanoscale Fe0/NaA molecular sieve membrane supported on nickel foam.

Complexing agents (CAs) can be used for the removal of Cr(VI) via nanoscale Fe0 (nZVI) reduction in cost-effective manner. However, nZVI is prone to aggregation and passivation, and some conventional CAs are toxic and difficult to biodegrade, potentially causing secondary pollution. Therefore, selecting an environmentally friendly CA for assisting in the removal of Cr(VI) via supported nZVI is imperative. Herein, NaA molecular sieve membrane-supported nZVI (nZVI/NaA-NF) was prepared via the secondary growth and liquid-phase reduction method using nickel foam (NF) as the carrier. The physicochemical characteristics of nZVI/NaA-NF before and after reaction were analysed via SEM, EDS, and XPS. A CA-improved nZVI/NaA-NF was used for the effective removal of Cr(VI) in a continuous fixed-bed system. Furthermore, the influences of various experimental factors including the CA type, CA concentration, solution pH, space velocity, and inlet Cr(VI) concentration on Cr(VI) removal were systematically investigated. The results demonstrated that nZVI particles were homogeneously immobilized on the NaA molecular sieve membrane/NF for fresh nZVI/NaA-NF, and tetrasodium iminidisuccinate (IDS-4Na) inhibited the aggregation of Cr(III)/Fe(III) (hydr)oxide precipitates during the reaction. IDS-4Na demonstrated excellent promotive effect on Cr(VI) removal via nZVI/NaA-NF. The breakthrough time for Cr(VI) in the addition of IDS-4Na was considerably longer than that of nZVI/NaA-NF alone. The breakthrough concentration of Cr(VI) only reached 1.1% and 9.9% of the inlet concentration at 220 and 240 min, with an IDS-4Na concentration of 4 mM, a pH of 2.5, and a space velocity of 0.265 min-1. The Bohart-Adams model was appropriate to predict the initial part of Cr(VI) breakthrough curves in the nZVI/NaA-NF fixed bed. The saturated concentration (N0) increased with an increase in inlet Cr(VI) concentration. The Yoon-Nelson model afforded good fitting results for all breakthrough curves of Cr(VI). The k' value increased with an increase in space velocity, and the τ value decreased.

Carbon nitride quantum dots-modified cobalt phosphate for enhanced photocatalytic H2 evolution.

In the present work, carbon nitride quantum dots (CNQDs)-modified cobalt phosphate (CoPi) composites CNQDs/CoPi-x (x = 1, 2, 3) were prepared at room temperature and characterized by FTIR, XRD, UV-Vis DRS, EIS, SEM, TEM/HR-TEM, XPS, and N2 gas adsorption. The morphologies and surface areas of CNQDs/CoPi-x have no remarkable change after modification of CNQDs, compared with pure CoPi. The obtained CNQDs/CoPi-x shows enhanced activity and stability of photocatalytic H2 evolution compared to pure CoPi using Eosin Y (EY) as a sensitizer and triethanolamine as an electron donor. The CNQDs/CoPi-2 possesses the highest hydrogen evolution rate, 234.5 µmol h-1 g-1 , upon visible light, which outshines that of CoPi by 2.4 times. It was believed that the enhanced photocatalytic performances of the CNQDs/CoPi-2 could result from the boosted electron transfer from radical EY·- to CNQDs/CoPi-2 by the employment of CNQDs; in addition, the visible-light activity of CNQDs contributes to hydrogen evolution. The mechanism of photocatalytic hydrogen production was discussed. This study may contribute toward the development of production of "green hydrogen" using solar.

Facile synthesis of NaA zeolite supported Co2Fe1 for highly efficient degradation of Acid Orange 7 by activation of peroxymonosulfate.

The development of heterogeneous Co-based catalysts with an effective combination mode of Co/Fe and supporter, a facile synthetic method, and a low treatment cost is an important environment challenge for azo dyes degradation by peroxymonosulfate (PMS) activation. In this study, NaA zeolite supported CoxFey with various molar ratio of Fe/Si and Co/Fe was synthesized by a facile hydrothermal process, and used to activate PMS for Acid Orange 7 (AO7) degradation. NaA zeolite supported Co2Fe1 with the Fe/Si molar ratio of 1:10 showed superior catalytic performance compared with other NaA zeolite supported CoxFey. In a system containing 0.6 g/L catalysts, 4 mM PMS, pH 5 and T = 30℃, 95.8% AO7 and 79.1% COD conversion could be achieved at 20 and 60 min, respectively, and the first order kinetic rate constant reached 0.14795 min-1. Moreover, NaA zeolite supported Co2Fe1/PMS system exhibited excellent catalytic effect in a wide pH range of 3-9. Temperature had an obvious effect on AO7 degradation, and the activation energy was 31.36 kJ/mol. HCO3- demonstrated an obvious depression on AO7 degradation, while Cl-, SO42- and H2PO4- had a relatively poor impact. Quenching experiments showed that both sulfate radicals ([Formula: see text]) and hydroxyl radicals (·OH) were generated in the PMS reaction system, and the [Formula: see text] was the dominant active radical. During 3 cycles experiments, an acceptable AO7 conversion ratio (91.8%) within 30 min arrived, suggesting the good stability of NaA zeolite supported Co2Fe1.

Adsorption of U(VI) from aqueous solution by using KMnO4-modified hazelnut shell activated carbon: characterisation and artificial neural network modelling.

This study is based on U(VI) removal from wastewater by KMnO4-modified hazelnut shell activated carbon (KM-HSAC) using adsorption technology. A characterisation study of KM-HSAC was conducted through scanning electron microscope and energy-dispersive X-ray spectroscopy (EDS) analysis. The rough surface of KM-HSAC contains many irregular microspores. The EDS pattern confirmed the U(VI) adsorption on the KM-HSAC. A batch study experiment gave optimum results for U(VI) at pH 6, contact time of 160 min, initial U(VI) concentration of 155.56 mg/L and KM-HSAC dosage of 4 g/L, with a maximum adsorption capacity of 22.27 mg/g. The prediction performance of artificial neural network models was validated through the low values of statistical error (2.708 and 8.241 for RMSE of training and testing data, respectively) and the high determination coefficient value (0.987 and 0.906 for training and testing data, respectively). Experimental results suggest that KM-HSAC has a high potential for the removal of U(VI) from wastewater.

A Simple Ni-based Metal-organic Framework as Catalyst for Dye-sensitized Photocatalytic H2 Evolution from Water Reduction.

Metal-organic frameworks (MOF) are recently developed coordination porous materials, and their unique structures are very conducive to catalytic reactions. In this paper, p-benzenedicarboxylic acid (PBA)-Ni2+ MOF materials (denoted as PBA-Ni-x, where x represents the initial ratio of PBA to Ni2+ ) were synthesized by a hydrothermal method and characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and N2 gas adsorption. H2 gas was produced using the synthesized MOF as a photocatalyst and Eosin Y as a photosensitizer. The dependence of the special surface area and thickness of the nanosheets of Ni-MOF on the initial ratio of PBA to Ni2+ (PBA/Ni2+ ) was investigated. The BET surface areas of PBA-Ni-1 PBA-Ni-2 and PBA-Ni-3 are 11.00, 24.61 and 13.04 m2  g-1 , respectively. And the thicknesses of nanosheets are approximately 600-1000, 200-500 and 300-700 nm. Among the three materials, PBA-Ni-2 has the thinnest sheet-like structure and largest surface area. Thus, it displays the highest H2 evolution rate of 20.0 µmol h-1 . The noble-metal-free hydrogen production system is valuable for the application of MOF materials in photocatalytic water splitting.

Multicarbazole-Based D-π-A Dyes Sensitized Hydrogen Evolution under Visible Light Irradiation.

Donor-π bridge-acceptor (D-π-A) organic dyes, well studied in dye-sensitized solar cells (DSSCs), are found to possess great potential in light-inducing hydrogen evolution due to their distinguished light-harvesting ability and suitable electron energy level. In this work, multicarbazole-based organic dyes (2C, 3C, 4C) were used as photosensitizers of Pt/TiO2 for photocatalytic hydrogen evolution (PHE) from water under visible light irradiation. 3C-Pt/TiO2 shows the best photocatalytic activity among the three dye-sensitized photocatalysts, with a hydrogen evolution rate of 24.7 µmol h-1 and a turnover number of 247 h-1. The activity of 3C-Pt/TiO2 declines significantly after 3 h irradiation. The deactivation was caused by the partial degradation of the electron acceptor, cyanoacrylate moiety, during the photocatalytic process, which was evidenced by UV-vis, Fourier transform infrared spectra (FT-IR), NMR, and mass spectra. This work is expected to contribute toward the understanding of stability issues of organic dyes and the development of more efficient and steady dyes for hydrogen evolution from water splitting.

Visible-light-driven H2 production and decomposition of 4-nitrophenol over nickel phosphides.

Photocatalytic H2 production and photocatalytic decomposition are efficient and economical methods to obtain hydrogen fuel and dispose of organic pollutants. In this paper, amorphous nickel phosphide (Ni2P) is synthesized by an extremely simple precipitation method under low temperature. The prepared nickel phosphide was not only used to produce H2 in the presence of Eosin Y as sensitizer and triethanolamine (TEOA) as a sacrificial electron donor but also to degrade 4-nitrophenol under visible light illumination. The rate of hydrogen evolution is 34.0 µmol h-1 g-1 and the degradation efficiency is 25.5% within 4 h at initial 5.0 mg L-1 4-nitrophenol. Probable photocatalytic mechanisms were discussed. The present work is expected to contribute toward the hydrogen evolution and disposal of highly toxic pollutants by cost-effective photocatalytic means.

Kinetics, equilibrium, and thermodynamics investigation on the adsorption of lead(II) by coal-based activated carbon.

The goal of this research is to investigate the feasibility of using activated coal-based activated carbon (CBAC) to adsorb Pb(II) from aqueous solutions through batch tests. Effects of contact time, pH, temperature and initial Pb(II) concentration on the Pb(II) adsorption were examined. The Pb(II) adsorption is strongly dependent on pH, but insensitive to temperature. The best pH for Pb(II) removal is in the range of 5.0-5.5 with more than 90 % of Pb(II) removed. The equilibrium time was found to be 60 min and the adsorption data followed the pseudo-second-order kinetics. Isotherm data followed Langmuir isotherm model with a maximum adsorption capacity of 162.33 mg/g. The adsorption was exothermic and spontaneous in nature. The Fourier transform infrared spectroscopy and scanning electron microscopy analysis suggested that CBAC possessed a porous structure and was rich in carboxyl and hydroxyl groups on its surface, which might play a major role in Pb(II) adsorption. These findings indicated that CBAC has great potential as an alternative adsorbent for Pb(II) removal.

Uranium biosorption from aqueous solution onto Eichhornia crassipes.

Batch experiments were conducted to investigate the biosorption of U(VI) from aqueous solutions onto the nonliving biomass of an aquatic macrophyte Eichhornia crassipes. The results showed that the adsorption of U(VI) onto E. crassipes was highly pH-dependent and the best pH for U(VI) removal was 5.5. U(VI) adsorption proceeded rapidly with an equilibrium time of 30 min and conformed to pseudo-second-order kinetics. The Langmuir isotherm model was determined to best describe U(VI) biosorption with a maximum monolayer adsorption capacity of 142.85 mg/g. Thermodynamic calculation results indicated that the U(VI) biosorption process was spontaneous and endothermic. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis implied that the functional groups (amino, hydroxyl, and carboxyl) may be responsible for the U(VI) adsorption process, in which the coordination and ion exchange mechanisms could be involved. We conclude that E. crassipes biomass is a promising biosorbent for the removal of uranium pollutants.

Cu and Cr enhanced the effect of various carbon nanotubes on microbial communities in an aquatic environment.

Environmental impacts of carbon nanotubes (CNTs) arise both from the characteristics of CNTs as well as from their sorbed contaminants from aquatic environments. In this work, we employed pristine, carboxyl-, hydroxyl- and amino-functionalized multi-walled CNTs and pristine single-walled CNTs to quantify and compare their impacts on aquatic microbial communities in the absence and presence of Cu or Cr. Aliquots of samples were set up to 10 and 40 days for culture-dependent analyses, namely, quantitative real-time polymerase chain reaction and denaturing gradient gel electrophoresis. Results revealed that the presence of CNTs or the mixture of CNTs and metals transiently affected microbial communities, and toxicity of CNTs was enhanced with the addition of metals. Meanwhile, functionalized CNTs exhibited stronger toxicity. The major impacts were observed after 10 days of exposure, but the microbial community could recover at 40 days to some extent. Though microbial communities recovered, total microbial numbers continued to decrease with contact time. Analysis of sequence cloned 16S rDNA indicated that Bacillus sp. and Acidithiobacillus sp. were the dominant taxa. Overall, CNTs would have more serious risk to an ecosystem in the presence of metals.

Evaluate the heavy metal toxicity to Pseudomonas fluorescens in a low levels of metal-chelates minimal medium.

A 2-(n-morpholino)ethane sulfonic acid (MES)-buffered minimal medium with low levels of metal chelates was used to evaluate the heavy metal (Co+2, Pb+2, Zn+2, Fe+2, Fe+3, Cd+2, Cu+2, and Cr+6) toxicity to Pseudomonas fluorescens through minimizing the limitation of the existing medium. The interaction between bacteria and heavy metals was real-time monitored by microcalorimetry and reflected by thermogenic curves. Compared with the main parameters, microbial growth rate constant k and total heat evolution Q total, a general order of toxicity was found to be Fe+3

Influence of short-time imidacloprid and acetamiprid application on soil microbial metabolic activity and enzymatic activity.

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as Q T (J g(-1) soil), ∆H met (kJ mol(-1)), J Q/S (J g(-1) h(-1)), k (h(-1)), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution Q T (expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. Q T for IMI increases at 0.0-20 µg g(-1) and then decreases at 20-80 µg g(-1), possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC50) of IMI and ACE are 95.7 and 77.2 µg g(-1), respectively. ACE displays slightly higher toxicity than IMI. Plots of k and Q T against microbial biomass-C indicate that the k and Q T are growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.

Sorption of humic acid to functionalized multi-walled carbon nanotubes.

The environmental behavior of carbon nanotubes (CNTs) and humic acid (HA) is a prominent concern, but effect of functionalities on their sorption is not clear yet. Functionalized multi-walled CNTs (MCNT15) and HA were used to study their sorption behavior. Sorption rate of HA to MCNTs was dominantly controlled by its diffusion from liquid-MCNT boundary to MCNT surfaces. The sorption is in the sequence of MCNT15 > MCNT15-NH2 > MCNT15-OH > MCNT15-COOH > MCNT15-Ni, which was dependent on their surface area and meso- and macro-pore volume. The functionalities of MCNTs regulated the sorption by affecting their interaction mechanisms (i.e., H-bonding, π-π, and hydrophobic interaction). Additionally, the amount of these functionalities on the MCNT surface reduced indirectly the sorption sites due to the steric hindrance. Electrostatic repulsion deceased the sorption of HA by MCNTs with increasing pH. This study demonstrated the importance of functionalities on the MCNTs for the sorption of HA.