Immobilization of Pb in waste water and soil by tourmaline-biochar composites (TBs): Characteristics and mechanisms.

Novel tourmaline-biochar composites (TBs) were synthesized by introducing tourmaline (TM) into pomelo peel biochar (BC). The surface properties of TBs and BC were studied and the adsorption performances for Pb2+ were investigated. Compared to pristine BC, the adsorption ability for Pb2+ on TBs was enhanced with the increase of TM in TBs, and up to 514.62 mg/g on 5%TB. The enrichment of inorganic metals caused by TM in TBs made the precipitation and cation ion exchange become the main mechanisms in adsorbing Pb2+, and the amounts of adsorbing Pb2+ by those two mechanisms on TBs were 1.10-1.48 times and 1.20-1.30 times those of BC, respectively. Furthermore, applying TBs to practical contaminated soil increased the soil pH and electrical conductivity (EC) after 15 days of incubation. The increased content of residual-Pb and reduced exchangeable-Pb and DTPA-Pb indicated that TBs were favorable for the immobilization of Pb in soil. This study gives a new perspective on the synthesis of tourmaline-biochar composite and their application in Pb-polluted water and soil.

Regulation of tourmaline-mediated Fenton-like system by biochar: Free radical pathway to non-free radical pathway.

The heterogeneous Fenton-like systems induced by Fe-containing minerals have been largely applied for the degradation of organic pollutants. However, few studies have been conducted on biochar (BC) as an additive to Fenton-like systems mediated by iron-containing minerals. In this study, the addition of BC prepared at different temperatures was found to significantly enhance the degradation of contaminants in the tourmaline-mediated Fenton-like system (TM/H2O2) using Rhodamine B (RhB) as the target contaminant. Furthermore, the hydrochloric acid-modified BC prepared at 700 °C (BC700(HCl)) could achieve complete degradation of high concentrations of RhB in the BC700(HCl)/TM/H2O2 system. Free radical quenching experiments showed that TM/H2O2 system removed contaminants mainly mediated by the free radical pathway. After adding BC, the removal of contaminants is mainly mediated by the non-free radical pathway in BC700(HCl)/TM/H2O2 system which was confirmed by the Electron paramagnetic resonance (EPR) experiments and electrochemical impedance spectroscopy (EIS). In addition, BC700(HCl) had broad feasibility in the degradation of other organic pollutants (Methylene Blue (MB) 100%, Methyl Orange (MO) 100%, and tetracycline (TC) 91.47%) in the tourmaline-mediated Fenton-like system. Possible pathways for the degradation of RhB by the BC700(HCl)/TM/H2O2 system were also proposed.

Elaborating the mechanism of lead adsorption by biochar: Considering the impacts of water-washing and freeze-drying in preparing biochar.

This paper examined the impacts of different pretreatments on the characteristics of biochar and its adsorption behavior for Pb2+. Biochar with combined pretreatment of water-washing and freeze-drying (W-FD-PB) performed a maximum adsorption capacity for Pb2+ of 406.99 mg/g, higher than that of 266.02 mg/g on water-washing pretreated biochar (W-PB) and 188.21 mg/g on directly pyrolyzed biochar (PB). This is because the water-washing process partially removed the K and Na, resulting in the relatively enriched Ca and Mg on W-FD-PB. And the freeze-drying pretreatment broke the fiber structure of pomelo peel, favoring the development of a fluffy surface and large specific surface area during pyrolysis. Quantitative mechanism analysis implied that cation ion exchange and precipitation were the driving forces in Pb2+ adsorption on biochar, and both mechanisms were enhanced during Pb2+ adsorption on W-FD-PB. Furthermore, adding W-FD-PB to Pb-contaminated soil increased the soil pH and significantly reduced the availability of Pb.

Metabolomics investigation on the volatile and non-volatile composition in enzymatic hydrolysates of Pacific oyster (Crassostrea gigas).

To investigate the differences of volatile and non-volatile metabolites between oyster enzymatic hydrolysates and boiling concentrates, molecular sensory analysis and untargeted metabolomics were employed. "Grassy," "fruity," "oily/fatty," "fishy," and "metallic" were identified as sensory attributes used to evaluate different processed oyster homogenates. Sixty-nine and 42 volatiles were identified by gas chromatography-ion mobility spectrometry and gas chromatography-mass spectrometry, respectively. Pentanal, 1-penten-3-ol, hexanal, (E)-2-pentenal, heptanal, (E)-2-hexenal, 4-octanone, (E)-4-heptenal, 3-octanone, octanal, nonanal, 1-octen-3-ol, benzaldehyde, (E)-2-nonenal, and (E, Z)-2,6-nonadienal were detected as the key odorants (OAV > 1) after enzymatic hydrolysis. Hexanal, (E)-4-heptenal, and (E)-2-pentenal were significantly associated with off-odor, and 177 differential metabolites were classified. Aspartate, glutamine, alanine, and arginine were the key precursors affecting the flavor profile. Linking sensory descriptors to volatile and nonvolatile components of different processed oyster homogenates will provide information for the process and quality improvement of oyster products.

Improving the humification by additives during composting: A review.

Humic substances (HSs) are key indicators of compost maturity and are important for the composting process. The application of additives is generally considered to be an efficient and easy-to-master strategy to promote the humification of composting and quickly caught the interest of researchers. This review summarizes the recent literature on humification promotion by additives in the composting process. Firstly, the organic, inorganic, biological, and compound additives are introduced emphatically, and the effects and mechanisms of various additives on composting humification are systematically discussed. Inorganic, organic, biological, and compound additives can promote 5.58-82.19%, 30.61-50.92%, 2.3-40%, and 28.09-104.51% of humification during composting, respectively. Subsequently, the advantages and disadvantages of various additives in promoting composting humification are discussed and indicated that compound additives are the most promising method in promoting composting humification. Finally, future research on humification promotion is also proposed such as long-term stability, environmental impact, and economic feasibility of additive in the large-scale application of composting. It is aiming to provide a reference for future research and the application of additives in composting.

Surface modification of cellulose via photo-induced click reaction.

To pursue highly functional ecologically friendly materials, functionalized cellulose has gained increasing number of research interests within the last decades. Compared with other cellulose modification approaches, surface modification of cellulose via photo-induced click reaction is a particular attractive cellulose modification strategy as it integrates the advantages of photochemistry, click reaction and surface modification. High efficiency, quantitative conversion and spatial temporal control are achieved. The physical and chemical properties of various cellulose surfaces are also effectively regulated by using this strategy, which significantly expands their applications. In this mini-review, we summarized the recent progress in cellulose surface modification via photo-induced click reactions. The principles and the merits of photo-induced thiol-X and cycloaddition reactions were compared and highlighted. Photo-induced thiol-ene reaction, thiol-yne reaction, tetrazole-ene cycloaddition, Diels-Alder cycloaddition, and azide-alkyne cycloaddition applied in modification of various cellulose surfaces were introduced in order. At last, the challenges and outlook of photo-induced click reaction in cellulose surface modification were discussed. We hope this review will provide insights into photo-induced click chemistry, cellulose surface modification and novel sustainable materials.

A frameshift mutation of TMPRSS3 in a Chinese family with non-syndromic hearing loss.

Background: Deafness is the most common sensory defect in humans worldwide. Approximately 50% of cases are attributed to genetic factors, and about 70% are non-syndromic hearing loss (NSHL). Objectives: To identify clinically relevant gene variants associated with NSHL in a Chinese family using trio-based whole-exome sequencing (WES). Materials and methods: WES was performed on the 18-month-old female proband, and her parents. Gene variants specific to the family were identified by bioinformatics analysis and evaluated for their relevance to NSHL. We verified the novel variant in this family by the next-generation sequencing.In order to elucidate the frameshift mutation of TMPRSS3 in a Chinese family, we used the Mass spectrometry to detect the gene from 1,010 healthy subjects. Results: We identified a novel homozygous deletion (c.51delA) in exon 2 of the type II transmembrane serine protease 3 gene TMPRSS3, which resulted in a frameshift mutation just before the protein transmembrane domain (p.Q17fs). The deletion was present in the proband and her father, but not in her mother and the healthy controls. We also found mutations with potential relevance to hearing loss in DCAF17, which encodes a protein of unknown function (c. T555A: p.H185Q), and ZNF276, which encodes zinc finger protein 276 (c.1350-2A > G). Conclusions and significance: We shown a novel frameshift mutation in TMPRSS3 associated with autosomal recessive NSHL in a Han Chinese family.

Fabrication, application, and mechanism of metal and heteroatom co-doped biochar composites (MHBCs) for the removal of contaminants in water: A review.

The potential risk of various contaminants in water has recently attracted public attention. Biochars and modified biochars have been widely developed for environmental remediation. Metal and heteroatom co-doped biochar composites (MHBCs) quickly caught the interest of researchers with more active sites and higher affinity for contaminants compared to single-doped biochar by metal or heteroatoms. This study provides a comprehensive review of MHBCs in wastewater decontamination. Firstly, the main fabrication methods of MHBCs were external doping and internal doping, with external doping being the most common. Secondly, the applications of MHBCs as adsorbents and catalysts in water treatment were introduced emphatically, which mainly included the removal of metals, antibiotics, dyes, pesticides, phenols, and other organic contaminants. Thirdly, the removal mechanisms of contaminants by MHBCs were deeply discussed in adsorption, oxidation and reduction, and degradation. Furthermore, the influencing factors for the removal of contaminants by MHBCs were also summarized, including the physicochemical properties of MHBCs, and environmental variables of pH and co-existing substance. Finally, futural challenges of MHBCs are proposed in the leaching toxicity of metal from MHBCs, the choice of heteroatoms on the fabrication for MHBCs, and the application in the composite system and soil remediation.

Effects of CaO2 based Fenton - like reaction on heavy metals and microbial community during co-composting of straw and sediment.

In this study, a Fenton-like system was constructed by CaO2 and nano-Fe3O4 in the co-composting system of straw and sediment. Its effect on the passivation of heavy metals and the evolution of microbial community were investigated. The results showed that the establishment of CaO2-Fenton-like system increased the residual Cu and residual Zn by 27.62% and 16.80%, respectively. In addition, the CaO2-Fenton-like system facilitated the formation of humic acid (HA) up to 20.84 g·kg-1. Redundancy analysis (RDA) showed that the CaO2-Fenton-like system accelerated bacterial community succession and promoted the passivation of Cu and Zn. Structural equation models (SEMs) indicated that Fenton reaction affected Cu and Zn passivation by affecting pH, bacterial communities, and HA. This study shows that the CaO2-Fenton-like system could promote the application of composting in the remediation of heavy metals contamination in sediment.

Effect of attapulgite on heavy metals passivation and microbial community during co-composting of river sediment with agricultural wastes.

This paper investigated the effects of attapulgite addition on the physicochemical processes, heavy metal transformation, and microbial community during the composting of agricultural wastes and sediment. In addition, the correlation between environmental factors, heavy metals (HMs), and microbial community was also assessed by redundancy analysis (RDA). The results showed that pile B with attapulgite addition entered the thermophilic phase earlier and lasted longer than pile A as the control group. The reduction in the bioavailability of HMs (Cr, Cd, and Zn) was also greater in pile B, and the passivation of HMs was ranked as Cd > Zn > Cr. The relative abundance of phylum Proteobacteria, Firmicutes, Bacteroidetes, and Actinobacteria was the highest throughout the composting process. Furthermore, the RDA showed that the bacterial community composition was significantly correlated with temperature and C/N ratio in pile A, while significantly correlated with organic matter and pH in pile B. And the addition of attapulgite facilitated the conversion of HMs into more stable fractions by Pseudomonas. The study would provide a reference for the application of attapulgite to remediate the river sediment polluted by HMs.

Evolution of humic substances and the forms of heavy metals during co-composting of rice straw and sediment with the aid of Fenton-like process.

The Fenton-like process was established by Fe3O4 nanomaterials (NMs) and Phanerochaete chrysosporium or oxalate, and applied to the co-composting of rice straw and sediment to study its effect on the formation of humic substance and the bioavailability of Cd, Cu, and Pb. Results shown that the application of Fenton-like process significantly promoted the passivation of Cd and Cu, while not shown obvious enhancement for Pb. The decrease of exchangeable fraction Cd (EXC-Cd) and the humic acid (HA) content in pile B with Fe3O4 NMs and oxalate were highest, which were 22.35% and 20.3 g/kg, respectively. Redundancy analyses (RDA) manifested that the Fenton-like process enhanced the influence of humus substance on the bioavailability of Cd, Cu, and Pb. Excitation-emission matrix (EEM) fluorescence spectra analysis suggested that Fenton-like process could obviously enhance the generation of humic substance. This research provides a new perspective and way for composting to remediate heavy metals pollution.

Advances, Challenges, and Opportunities of Poly(γ-butyrolactone)-Based Recyclable Polymers.

The discovery and prosperous growth of synthetic polymers have presented both significant advantages and daunting challenges in the last century. To address the issues of environmental pollution and fossil consumption, recyclable, degradable, and/or biobased polymers have been given much attention in the polymer science community. This viewpoint focuses on the emerging fully chemical recyclable poly(γ-butyrolactone)-based polymers. The breakthrough from nonpolymerizable to efficient polymerization is highlighted by the benefits of the development of a series of catalysis for ring-opening polymerization of γ-butyrolactone. Subsequently, the design of γ-butyrolactone derivatives and synthesis of more recyclable polymers are summarized together with the discussions about the structure and property relationship. Finally, the remaining challenges and promising opportunities are suggested in order to provide insights into the further direction for sustainable polymers.

Hydroxyapatite modified sludge-based biochar for the adsorption of Cu2+ and Cd2+: Adsorption behavior and mechanisms.

This study prepared sewage sludge, a municipal solid waste, into a biochar modified by hydroxyapatite (HAP) as a new and efficient absorbent (HAP-SSBC) for removal of Cu2+ and Cd2+ from aqueous solution. Adsorption experiment revealed that HAP-SSBC exhibited significantly higher adsorption performance than raw sludge-based biochar (SSBC). At 298.15 K, the maximum adsorption capacity of Cu2+ and Cd2+ via Langmuir model were 89.98 and 114.68 mg/g, respectively. Adsorption kinetic experiment revealed that chemisorption was the main reaction. Analysis of X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectrum (XPS) further confirmed that the main mechanisms were ion exchange with Ca2+, complexion by -OH and -COOH, and forming Cu-π or Cd-π binding with aromatic CC on HAP-SSBC surface. Overall, combing HAP and SSBC to be a new adsorbent is beneficial to the resource utilization of sludge and shows a good prospect for heavy metal removal in aqueous solution.

Preparation of a double-network hydrogel based on wastepaper and its application in the treatment of wastewater containing copper(ii) and methylene blue.

To reclaim and utilize wastepaper (WP), a WP/acrylamide double-network hydrogel (WP/PAM) was prepared to transform WP into efficient adsorbent for heavy metals and dye wastewater treatment. The structure and properties of the WP/PAM were characterized systematically by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), swelling performance (SR), Fourier transform infrared spectrum (FTIR), and X-ray photoelectron spectroscopy (XPS). Batch experiments showed that the adsorption process of Cu(ii) and MB followed the pseudo-second-order kinetic model and the Langmuir model. The maximum adsorption capacities of the WP/PAM for Cu(ii) and MB were 142.2 mg g-1 and 1714.5 mg g-1, respectively. The adsorption mechanism of Cu(ii) on the WP/PAM was related to ion exchange and complexation, while MB adsorption was driven by hydrogen bonding and electrostatic interaction. Besides, the WP/PAM performed well in treating simulated wastewater. The regeneration test indicated that the WP/PAM could be successfully reused after 6 cycles. This work provided an alternative choice for the recycling of WP and produced a potential adsorbent for the dye and heavy metals wastewater treatment.

Functional wastepaper-montmorillonite composite aerogel for Cd2+ adsorption.

In this study, a composite aerogel (WP-MMT) composed of wastepaper (WP) and montmorillonite (MMT) was prepared by ambient pressure drying technology to adsorb Cd2+. The study of compression performance indicated that the composite aerogel had ideal mechanical strength when the mass ratio of WP to MMT was 1:1. The specific surface areas of the aerogels modified by hydrogen peroxide (WP-MMT-H2O2) and sodium hydroxide (WP-MMT-NaOH) were increased greatly. The sorption isotherms and kinetics of Cd2+ sorption on WP-MMT-H2O2 and WP-MMT-NaOH were investigated. The Cd2+ sorption data could be well described by a simple Langmuir model, and the pseudo-second-order kinetic model best fitted the kinetic data. The maximum sorption capacity obtained from the Langmuir model was 232.50 mg/g for WP-MMT-NaOH. The adsorption mechanism of WP-MMT was chemical adsorption of a single-molecule layer. In general, it was proved that the composite aerogel with high adsorption capacity of Cd2+ could be synthesized from modified WP and MMT by ambient pressure drying. The composite aerogel fabricated by wastepaper and montmorillonite showed bright application prospect in the aqueous heavy metal pollution control.

Adsorption of Pb(II) by tourmaline-montmorillonite composite in aqueous phase.

In this study, a tourmaline-montmorillonite composite (TMMs) was synthesized by vacuum sintering to adsorb Pb(II) from aqueous phase. Different sintering temperature and proportion of tourmaline (TM) were first investigated by evaluating the adsorption capacity for Pb(II). The results indicated that the proper sintering temperature of the synthesis process and proportion of TM were 800 °C and 30.7% respectively. Batch experiments indicated Pseudo-second-order kinetic model and Freundlich adsorption isotherms fitted well with the adsorption characteristics of Pb(II) on TMMs, indicating that the adsorption progress of Pb(II) on TMMs related to chemical absorption and the maximum adsorption capacity was 303.21 mg/g. The background electrolyte concentration and solution pH have little effect on the adsorption behavior of TMMs. Adsorption mechanism of Pb(II) on TMMs might attribute to the electrostatic and complexation processes such as dissociation of metal ion bonds on the surface, hydroxylation on the surface of minerals, and self-polarization. The structure of TMMs was tested by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). This work provided a good reference for the application of tourmaline on treatment of heavy metals pollution in water.

Glucose enhanced the oxidation performance of iron-manganese binary oxides: Structure and mechanism of removing tetracycline.

In this work, iron-manganese binary oxides (FMO) modified with different proportions of glucose addition (FMOCx) by co-precipitation method showed good activity in activating hydrogen peroxide (H2O2) for tetracycline degradation. The structure and surface characterizations of the FMO and FMOCx were measured by XRD, FTIR, TEM, BET and XPS. With increased glucose addition, FMOCx has more surface functional groups such as -OH and -COOH, particle size decreases, surface area gradually increases, and the ratio of high valence iron and manganese also increases. In addition, the glucose might be oxidized by KMnO4 to form amorphous carbon on the catalyst surface. Glucose modified iron-manganese binary oxides FMOC3 (with 0.003 mol glucose added) showed the highest efficiency removal capability for tetracycline up to 85%, which attribute to it has a larger surface area, more surface functional groups and higher surface active Mn(IV) site content. The results also demonstrated that FMOC3 could efficiently activate hydrogen peroxide. This study proves that glucose modified iron-manganese binary oxides (FMOCx) can offered a possibility of degradation of refractory organic pollutants as an environmentally friendly catalyst in the absence of H2O2 or not.

Amplification of oxidative stress via intracellular ROS production and antioxidant consumption by two natural drug-encapsulated nanoagents for efficient anticancer therapy.

Cancer cells are commonly characterized by high cellular oxidative stress and thus have poor tolerance to oxidative insults. In this study, we developed a nano-formulation to elevate the level of reactive oxygen species (ROS) in cancer cells via promoting ROS production as well as weakening cellular anti-oxidizing systems. The nanoagent was fabricated by encapsulating two natural product molecules, cinnamaldehyde (CA) and diallyl trisulfide (DATS), in PLGA-PEG copolymer formulated nanoparticles. CA promotes ROS generation in cancer cells and DATS depletes cellular glutathione. CA and DATS exhibited a synergistic effect in amplifying the ROS levels in cancer cells and further in their combined killing of cancer cells. The in vivo experiments revealed that the CA and DATS-encapsulated nanoagent suppressed tumors more efficiently as compared with the single drug-loaded ones, and the tumor-targeted delivery further enhanced the therapeutic efficacy. This study suggests that the combined enhancement of oxidative stress by CA and DATS could be a promising strategy for cancer therapy.

The differential neuroprotection of HSP70-hom gene single nucleotide polymorphisms: In vitro (neuronal hypoxic injury model) and in vivo (rat MCAO model) studies.

To investigate the effect of HSP70-hom+2437 single nucleotide polymorphisms (SNPs) on hypoxia and ischemia condition, we constructed the neuronal hypoxic injury model and the rat middle cerebral artery occlusion (MCAO) model to compare the inhibition rate of neurons and detect the infarct volume as well as the expression of related apoptotic proteins in order to explore the possible mechanisms. The neuroblastoma cells SHSY5Y were divided into the OE (transfected with the C allele) group, OEmu (transfected with the T allele) group and negative control (NC, transfected with the empty lentiviral vector CON195) group. Varying degrees of hypoxia were induced by deferoxamine (DFO). The inhibition rate of hypoxic neurons and the expression of related apoptotic proteins were detected in the three genotype groups. While in the rat MCAO model, we built five groups including the sham group, the blank control group (injected with physiological saline), the negative control group (injected with lentivirus and physiological saline), the C allele group and the T allele group (injected with lentivirus overexpressing C and T allele). The MCAO model operation was then underwent in all five groups, the infarct volume by TTC staining and the expression of related apoptotic proteins were detected after 24 h. The results in neuronal hypoxic injury model showed a significant difference in the inhibition rate between the three groups (P < 0.05), and the average inhibition rates for the OEmu, OE and NC groups were 13.2%, 19.2% and 23.3%, respectively. The inhibition rates also differed between lower and higher DFO concentrations (P < 0.05). Compared with the NC group, Bax decreased significantly in the OE and OEmu groups, whereas PI3K and HSPA1L (HSP70-hom) increased. However, the expression of Bax in the OEmu group decreased significantly more than in the OE group, whereas PI3K and HSPA1L levels showed no difference between the two groups. Corresponding with the results above, overexpressing HSP70-hom could reduce the infarct volume of ischemic injury by TTC staining in rat MCAO model and the T allele group also had less infarct volume than C allele group. Compared with the sham group, blank control group and negative control group, Bax decreased significantly in the C and T allele groups, while HSPA1L and p- AKT increased. Furthermore, the expression of Bax in the T allele group decreased significantly more than that in the C allele group, while there were no significant differences in HSPA1L and p-AKT levels between the two groups. Therefore, the overexpression of HSP70-hom+2437 could play a protective role in hypoxic neurons and ischemic brain tissue by upregulating the expression of HSPA1L and PI3K/p-AKT and downregulating the expression of BAX. The neuroprotective effect of the T allele was stronger than that of the C allele, which may be related to the strengthened downregulation of BAX.

Organocatalyzed chemoselective ring-opening polymerizations.

A novel metal-free and protecting-group-free synthesis method to prepare telechelic thiol-functionalized polyesters is developed by employing organocatalysis. A scope of Brønsted acids, including trifluoromethanesulfonic acid (1), HCl.Et2O (2), diphenyl phosphate (3), γ-resorcylic acid (4) and methanesulfonic acid (5), are evaluated to promote ring-opening polymerization of ε-caprolactone with unprotected 6-mercapto-1-hexanol as the multifunctional initiator. Among them, diphenyl phosphate (3) exhibits great chemoselectivity and efficiency, which allows for simply synthesis of thiol-terminated poly(ε-caprolactone) with near-quantitative thiol fidelity, full monomer conversion, controlled molecular weight and narrow polydispersity. Kinetic study confirms living/controlled nature of the organocatalyzed chemoselective polymerizations. Density functional theory calculation illustrates that the chemoselectivity of diphenyl phosphate (3) is attributed to the stronger bifunctional activation of monomer and initiator/chain-end as well as the lower energy in hydroxyl pathway than thiol one. Moreover, series of tailor-made telechelic thiol-terminated poly(δ-valerolactone) and block copolymers are efficiently generated under mild conditions.