One-step preparation of cobalt phosphate at room temperature for effective photocatalytic H2 evolution.

Cobalt phosphate materials were prepared in the present work in one step at room temperature using different raw materials and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and N2 gas adsorption. Cobalt phosphates exhibit 3D flower-like structures, and the assembly of nanosheets (petals of the "flowers") of cobalt phosphate prepared with sodium phosphate and cobalt acetate as raw materials (denoted as Co-P(A)) is more incompact than that of cobalt phosphate prepared with diammonium hydrogen phosphate and cobalt nitrate as raw materials (denoted as Co-P(B)) due to the former's mildly basic environment. The cobalt phosphates show relatively high photocatalytic activity for H2 evolution reaction (HER) in the presence of Eosin Y as a sensitizer in an aqueous triethanolamine solution. The activity of Co-P(A) (0.40 mmol h-1 g-1) exceeds that of Co-P(B) (0.19 mmol h-1 g-1), which can be attributed to a more dispersive nanosheet and larger BET-specific surface area of Co-P(A). The mechanisms of photocatalytic HER and the formation of flower-like Co3(PO4)2 were discussed. The present system comprising of only abundant elements contributes toward the development of cost-efficient solar HER to achieve sustainable development.

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.

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.

Construction of a novel fluorescent probe for sensitive determination of glyphosate in food and imaging living cells.

Glyphosate is a widely used broad-spectrum herbicide in agriculture and horticulture to control a variety of weeds and undesirable plants. However, the excessive use of glyphosate has raised a number of environmental and human health concerns. It is urgent to develop tools to detect glyphosate. Herein, a novel dual-signal probe CCU-Cu2+ was designed and synthesized on the basis of CCU. CCU exhibited excellent selectivity and great sensitivity for Cu2+ which were based on both fluorescence "turn-off" reaction and comparative color visualisation methods. Due to the strong chelating ability of glyphosate on Cu2+, the CCU-Cu2+ complex was applied to glyphosate detection in practical samples. The experimental results in vitro showed that the CCU-Cu2+ complex was highly selective and rapid, with a low detection limit (1.6 µM), and could be recognised by the naked eye in the detection of glyphosate. Based on the excellent properties of the CCU-Cu2+ complex, we also constructed a smartphone-assisted detection sensing system for glyphosate detection, which has the advantages of precision, sensitivity, and high interference immunity. Moreover, the CCU-Cu2+ complex was also successfully employed for exogenous glyphosate imaging in living cells. These characteristics demonstrated that CCU-Cu2+ holds significant potential for detection and imaging of glyphosate in bio-systems.

Near-infrared fluorescent probe for sensitive detection and imaging of DNA G4s in living cells.

G-quadruplexs (G4s), four-stranded nucleic acid secondary structures, which formed by guanine-rich sequences play a vital role in human biological systems. Studies have shown that the formation of G4s is closely related to tumor development and apoptosis, which is considered as a new target for the development of anti-tumor drugs. Therefore, it is important to develop novel probes for G4s imaging. In this article, we engineered a near-infrared fluorescent probe (TOH) which can be activated by DNA G4s in living cells and tumor. TOH exhibits high selectivity to the structure of DNA G4s with the limit of detection for DNA G4s (Mito-0.5-2) is calculated to be 0.43 nM. Imaging studies of different cell lines revealed that the brighter fluorescence in cancer cell lines than in normal, indicating that DNA G4s maybe highly express in tumor cell lines. Simultaneously, TOH is also introduced into live tumor tissue imaging and found that the fluorescence intensity of tumor is the brightest relative to normal tissue, further validating the high expression of DNA G4s structures in tumor tissue. These features demonstrate TOH not only have the ability to image DNA G4 structures in real time, but also may have tumor diagnostic capabilities.

Efficiency Recycling and Utilization of Phosphate from Wastewater Using LDHs-Modified Biochar.

The excessive application of phosphate fertilizers easily causes water eutrophication. Phosphorus recovery by adsorption is regarded as an effective and simple intervention to control water bodies' eutrophication. In this work, a series of new adsorbents, layered double hydroxides (LDHs)-modified biochar (BC) with different molar ratios of Mg2+ and Fe3+, were synthesized based on waste jute stalk and used for recycling phosphate from wastewater. The prepared LDHs-BC4 (the molar ratio of Mg/Fe is 4:1) has significantly high adsorption performance, and the recovery rate of phosphate is about 10 times higher than that of the pristine jute stalk BC. The maximum adsorption capacity of LDHs-BC4 for phosphate was 10.64 mg-P/g. The main mechanism of phosphate adsorption mainly includes electrostatic attraction, ion exchange, ligand exchange, and intragranular diffusion. Moreover, the phosphate-adsorbed LDHs-BC4 could promote mung bean growth, which indicated the recovery phosphate from wastewater could be used as a fertilizer.

An aggregation-induced emission fluorescent probe for highly sensitive and selective detection and imaging of Hg2+ in living cells.

Mercury ions (Hg2+), as one of heavy transition metals (HTM), is a highly toxic metal that is hazardous to human health. Here an aggregation-induced emission (AIE) fluorescent probe is designed for the highly sensitive and selective detection of Hg2+. The probe is engineered with a tetraphenylethene (TPE) derivative as the fluorophore and thiopropionic acid as the site of recognition for Hg2+. Due to the different solubilities of the probe AIE-COOH and its corresponding product after reaction with Hg2+. The probe demonstrates a maximum detection limit of 22 nM and a fast response time of âˆ¼100 s. Simultaneously, AIE-COOH exhibits outstanding detectivity and hypersensitivity for the detection of Hg2+ in aqueous solutions. These characteristics demonstrate that AIE-COOH hold a great potential in environmental, food and biological systems. Moreover, we have also successfully applied it to Hg2+ fluorescence imaging in in living cells.

Environmental-friendly hydrochar-montmorillonite composite for efficient catalytic degradation of dicamba and alleviating its damage to crops.

In recent years, carbon-based materials catalyzing peroxymonosulfate (PMS) for green degradation of persistent organic pollutants have attracted increasing attention. However, PMS activation by hydrochar composite (e.g. hydrochar-montomorillonite) has rarely been investigated. Herein, a simple preparation, low-cost and eco-friendly catalyst of hydrochar-montmorillonite composite (HC-Mt) was prepared to firstly catalyze PMS for the degradation of dicamba (DIC). The as-prepared HC-Mt showed a remarkably better catalyzing performance for PMS than pure hydrochar (HC) due to its good physicochemical characteristics and abundant oxygen-containing groups. Furthermore, the electron spin resonance (ESR) and quenching tests revealed that active species such as SO4-, OH and O2- all participated in the degradation process. DIC sites on C6, Cl 10, and O15 exhibited higher reactivity according to the density functional theory (DFT) calculation, which were easily attacked by active species. The DIC degradation mainly occurred via hydroxyl substitution, decarboxylation, oxidation and ring-cleavage and finally most of the intermediates were mineralized into CO2 and H2O. Finally, the phytotoxicity assessment was measured by the germination growth situation of tobacco and mung beans in the presence of DIC (with or without treatment by HC-Mt/PMS). The result showed that HC-Mt/PMS could significantly reduce the phytotoxicity of DIC to crops, suggesting that catalyzing PMS using HC-Mt was environmentally friendly. Therefore, this work did not only provide a novel catalyzing PMS strategy using hydrochar composite for wastewater treatment, but also give a new idea for herbicide phytotoxicity management.

Efficient adsorption of Pb(II) by sodium dodecyl benzene sulfonate intercalated calcium aluminum hydrotalcites: kinetic, isotherm, and mechanisms.

Two novel adsorbents of CaAl-LDHs and sodium dodecyl benzene sulfonate (SDBS) intercalated CaAl-LDHs (SDBS-CaAl-LDHs) were successfully prepared by co-precipitation. The main composition and physical properties of two samples were characterized by XRD, XPS, FT-IR, TG, and SEM. Batch adsorption experiments were conducted to study the effect of pH, adsorption time, and initial concentration of Pb2+. The results showed that the prime adsorption conditions obtained were pH of 5.2 after 60 min with the initial concentration of 300 mg g-1 for CaAl-LDHs and 350 mg g-1 for SDBS-CaAl-LDHs. At 303 K, the adsorption capacities and removal rates of CaAl-LDHs and SDBS-CaAl-LDHs were found to be 456.05 mg g-1, 91.21% and 682.26 mg g-1, 97.47%, respectively. For CaAl-LDHs, the kinetic data for Pb2+ was best fitted with pseudo-2nd-order model, and the adsorption isotherms followed Langmuir and Freundlich isotherm model. The adsorption data of SDBS-CaAl-LDHs can be best described by the pseudo-second-order kinetic and Langmuir model. The Pb2+ adsorption mechanism on SDBS-CaAl-LDHs was explored by XRD, XPS, and SEM, and the important roles of the electrostatic attraction, precipitation, complexation, and ion exchange were demonstrated. The Langmuir adsorption capacities for SDBS-CaAl-LDHs were 797.63, 828.76, and 854.29 mg g-1 at 293 k, 303 k, and 313 k, respectively. Thus, SDBS-CaAl-LDHs may be a highly economical adsorbent for the treatment of contaminated water.

[TDHF study of electronic absorption spectrum of (mu-L1) (mu-L2)-decacarbonyl triosmium].

Ab initio method was used to optimize the molecular geometry for a series of clusters (mu-L1) (mu-L2)- decacarbonyltri-osmium [L1, L2 = H, Cl, Br, I] at HF/CEP-4G level. The related chemical properties of clusters, in particular, the regularities of the bridge halogen effects on spectroscopic properties and bonding properties were discussed. The calculation results of the frontier molecular orbital showed that M-M bonds were mainly composed of s and d atomic orbitals. From Cl to I, with the atom number of bridge ligand increasing, HOMO and NHOMO orbitals on the Os3(CO)10 (mu-L)2 clusters and HOMO on the Os3 (CO)10 (mu-H) (mu-L) clusters become higher, while deltaepsilonL-H and deltaepsilon-NH energies become lower, so the authors predicted that the electronic absorption bands of clusters are shifted to infrared region. Excited states of clusters calculated with TDHF show that the transition of cluster Os3(CO)10 (mu-H)2 (I) is mainly 7 --> sigma* and sigma --> sigma*, while the electronic absorption of other clusters Os3 (CO)10 (mu-H) (mu-L) [L = Cl, Br, I] and Os3(CO)10 (mu-L)2 [-L = Cl, Br] is mainly from sigma --> sigma* transition. From Cl to I, with the atom number of bridge ligand increasing, the electronic absorption band of cluster is shifted to infrared region, and also the absorption becomes weaker.

[Theoretical calculation of vibrational frequencies for clusters of (1,2-micro2-L1)(1,2-micro2-L2)-decacarbonyltriosmium [L1, L2=H, Cl, Br, I]].

Density functional theory (DFT) and ab initio method have been employed to optimize the molecular geometry of (1,2-micro2-H) (1, 2-micro2-L) Os3 (CO)10 (L: Cl, Br, I) at B3LYP/CEP-4G, B3LYP/LanL2DZ, RHF/CEP-4G and RHF/LanL2DZ levels, respectively. By using ab initio method, the authors have optimized the molecular geometry of (1,2-t12 -L)2 Os3 (CO)20 (L: H, Cl, Br, I). The calculations showed that the charge was translated from Os(CO)3 to Os(CO)4. Harmonic vibrational analysis was performed at the RHF/CEP-4G levels, and according to the frequencies and intensities of the equilibrium structure obtained by using ab initio method, the IR spectra of structure have been simulated. The calculated results were compared with each other and with available experimental data, and were discussed in detail.

Electrochemical behavior and voltammetric determination of vanillin based on an acetylene black paste electrode modified with graphene-polyvinylpyrrolidone composite film.

The graphene-polyvinylpyrrolidone composite film modified acetylene black paste electrode (GR-PVP/ABPE) was fabricated and used to determine vanillin. In 0.1M H3PO4 solution, the oxidation peak current of vanillin increased significantly at GR-PVP/ABPE compared with bare ABPE, PVP/ABPE and GR/ABPE. The oxidation mechanism was discussed. The experimental conditions that exert influence on the voltammetric determination of vanillin, such as supporting electrolytes, pH values, accumulation potential and accumulation time, were optimized. Besides, the interference, repeatability, reproducibility and stability measurements were also evaluated. Under the optimal experimental conditions, the oxidation peak current was proportional to vanillin concentration in the range of 0.02-2.0 µM, 2.0-40 µM and 40-100 µM. The detection limit was 10nM. This sensor was used successfully for vanillin determination in various food samples.

Voltammetric determination of In3+ based on the bifunctionality of a multi-walled carbon nanotubes-nafion modified electrode.

Due to the strong cation-exchange ability of Nafion and the excellent properties of multi-walled carbon nanotubes (MWCNTs), a highly sensitive and mercury-free method of determining trace levels of In(3+) has been established based on the bifunctionality of a MWCNTs/Nafion modified glassy carbon electrode (GCE). The MWCNTs/Nafion modified GCE detects In(3+) in a 0.01 M HAc-NaAc buffer solution at pH 5.0 using anodic stripping voltammetry (ASV). The experimental results suggest that a sensitive anodic stripping peak appears at -0.58 V on anodic stripping voltammograms, which can be used as an analytical signal for the determination of In(3+). A good linear relationship between the stripping peak currents and the In(3+) concentration is obtained, covering the concentration range from 5.0 x 10(-10) to 2.0 x 10(-7) M, with a correlation coefficient of 0.999; the detection limit is 1.0 x 10(-11) M. This proposed method has been applied to detect In(3+) as a new way.