Superior capacity and easy separation of zirconium functionalized chitosan melamine foam for antimony(III/V) removal.

Nowadays, highly toxic antimony has severely posed threat to water sources and jeopardized human health. Fabricating adsorbents with the capability of easy separation, high efficiency and large adsorption capacity remains a major challenge. In this paper, zirconium functionalized chitosan melamine foam (ZCMF) was fabricated with zirconium and chitosan crosslinked onto melamine foam, then utilized for the removal of antimony(III/V) in water. The characterization of SEM and EDS collectively showed that ZCMF has a porous structure which could boost the mass transfer rate and zirconium ions on the surface could provide plentiful active adsorption sites. Systematic adsorption experiments demonstrated that the experimental data of Sb(III) and Sb(V) were consistent with the pseudo-second-order and Elovich kinetic models, respectively, and the Langmuir maximum adsorption capacities were separately 255.35 mg g-1 (Sb(III)) and 414.41 mg g-1 (Sb(V)), which displayed prominent performance among adsorbents derived from biomass. Combining the XPS and FTIR characterization with experimental data, it is rational to speculate that ZCMF could remove Sb from aqueous solution through ligand exchange, electrostatic attraction, and surface complexation mechanisms. ZCMF exhibited excellent performance, including large adsorption capacity, easy separation, facile preparation and eco-friendliness. It could be a promising new adsorbent for the treatment of antimony-containing wastewater.

A novel sponge composite of chitosan-sodium tripolyphosphate-melamine for anionic dye Orange II removal.

Since the potential carcinogenic, toxic and non-degradable dyes trigger serious environmental contamination by improper treatment, developing novel adsorbents remains a major challenge. A novel high efficiency and biopolymer-based environmental-friendly adsorbent, chitosan­sodium tripolyphosphate-melamine sponge (CTS-STPP-MS) composite, was prepared for Orange II removing with chitosan as raw material, sodium tripolyphosphate as cross-linking agent. The composite was carefully characterized by SEM, EDS, FT-IR and XPS. The influence of crosslinking conditions, dosage, pH, initial concentration, contacting time and temperature on adsorption were tested through batch adsorption experiments. CTS-STPP-MS adsorption process was exothermic, spontaneous and agreed with Sips isotherm model accompanying the maximum adsorption capacity as 948 mg∙g-1 (pH = 3). Notably, the adsorption performance was outstanding for high concentration solutions, with a removal rate of 97 % in up to 2000 mg∙L-1 OII solution (100 mg sorbent dosage, 50 mL OII solution, pH = 3, 289.15 K). In addition, the adsorption efficiency yet remained 97.85 % after 5 repeated adsorption-desorption cycles. The driving force of adsorption was attributed to electrostatic attraction and hydrogen bonds which was proved by adsorption results coupled with XPS. Owing to the excellent properties of high-effective, environmental-friendly, easy to separate and regenerable, CTS-STPP-MS composite turned out to be a promising adsorbent in contamination treatment.

Engineered Bacillus subtilis Biofilm@Biochar living materials for in-situ sensing and bioremediation of heavy metal ions pollution.

The simultaneous sensing and remediation of multiple heavy metal ions in wastewater or soil with microorganisms is currently a significant challenge. In this study, the microorganism Bacillus subtilis was used as a chassis organism to construct two genetic circuits for sensing and adsorbing heavy-metal ions. The engineered biosensor can sense three heavy metal ions (0.1-75 µM of Pb2+ and Cu2+, 0.01-3.5 µM of Hg2+) in situ real-time with high sensitivity. The engineered B. subtilis TasA-metallothionein (TasA-MT) biofilm can specifically adsorb metal ions from the environment, exhibiting remarkable removal efficiencies of 99.5% for Pb2+, 99.9% for Hg2+and 99.5% for Cu2+ in water. Furthermore, this engineered strain (as a biosensor and absorber of Pb2+, Cu2+, and Hg2+) was incubated with biochar to form a hybrid biofilm@biochar (BBC) material that could be applied in the bioremediation of heavy metal ions. The results showed that BBC material not only significantly reduced exchangeable Pb2+ in the soil but also reduced Pb2+ accumulation in maize plants. In addition, it enhanced maize growth and biomass. In conclusion, this study examined the potential applications of biosensors and hybrid living materials constructed using sensing and adsorption circuits in B. subtilis, providing rapid and cost-effective tools for sensing and remediating multiple heavy metal ions (Pb2+, Hg2+, and Cu2+).

Designing of 3D MnO2-graphene catalyst on sponge for abatement temperature removal of formaldehyde.

The Mn-based catalysts, with low cost and high activity, are believed to be the effective composites for eliminating in-door formaldehyde (HCHO), while the powdered form nanosized catalysts are hardly to apply for practical application. Herein, hetero-structure of nanosheets manganese oxide (MnO2) encapsulating N-doping graphene sphere (GS) were deposited in network-like sponge for constructing 3D catalyst. The prepared MnO2-GS-Sponge composite catalyst exhibited excellent performance for removing HCHO at room temperature compared with GS and commercial MnO2. The MnO2-GS with larger specific surface area (209.1 m2·g-1) was dispersed evenly in 3D network of sponge, which facilitated exposing more activate sites and achieving fast transport kinetics accelerating catalytic reaction for converting 97.1 % of 100 ppm of HCHO continuously to CO2 for 120 h. Moreover, rely on the chemisorption of amino groups on N-doping GS surface, HCHO could be enriched even at low concentrations and efficient elimination (from 1000 ppb to12 ppb, at 35 â„ƒ in 48 h). The average oxidation state and infrared spectra analysis suggested that abundant oxygen vacancies on MnO2-GS-Sponge could be identified as surface-active sites of converting HCHO into the intermediates of dioxymethylene and formate. This work might inspire the designing 3D composite material for potential application in other fields of environmental engineering or energy industrial.

Enhanced removal of methylene blue from wastewater by alginate/carboxymethyl cellulose-melamine sponge composite.

Industrial dye wastewater poses a threat to human health due to its harmful effects, and the treatment of related wastewater is receiving increasing attention. In this paper, the melamine sponge with high porosity and convenient separation was selected as matrix material, and alginate/carboxymethyl cellulose-melamine sponge composite (SA/CMC-MeS) was prepared through crosslinking strategy. Not only does the composite cleverly combined the merits of alginate and carboxymethyl cellulose, it also enhanced the adsorption performance for methylene blue (MB). The adsorption data manifested that the adsorption process of SA/CMC-MeS agreed with the Langmuir model and pseudo-second-order kinetic model, and theoretical maximum adsorption capacity was 230 mg/g (pH 8). The characterization results demonstrated that the adsorption mechanism was attributed to the electrostatic attraction between the carboxyl anions on the composite and the dye cations in solution. Importantly, SA/CMC-MeS could selectively separate MB from binary dye system and had positive anti-interference ability in the face of coexisting cations. After 5 times of cycles, the adsorption efficiency remained above 75 %. Based on these outstanding practical properties, this material has a potential to solve dye contamination.

Assessing the rainfall infiltration on FOS via a new NSRM for a case study at high rock slope stability.

Assessing the stability characteristics of high rock slope under rainfall via theoretical research, numerical simulation, and field monitoring is of great implications for safety construction in open-pit mine engineering. Thus, based on the Hoke-Brown criterion, instantaneous internal friction angle and cohesion of high-slope rock mass under high stress conditions were deduced, and a nonlinear strength reduction method for high rock slope was established. The safety factors of the open-pit mine were calculated by COMSOL Multiphysics, which considering the high rock southwest slope and detected rainfall in Dagushan Open-pit Mine, China. The results showed that high rock slope stability could be more accurately analyzed by the proposed method due to its full consideration of slope stress state effect compared with the equivalent Mohr- Coulomb method. When the slope is low, the difference between the calculation results of the equivalent Mohr- Coulomb method and the proposed method is small, but with the increase of the slope height, the difference between the two calculation results gradually increases. When the transient saturated is formed in the slope surface layer and gradually increases, the reduction rate of the factor of safety (FOS) gradually increases. When the total rainfall is the same, the effect of short-term heavy rainfall on slope stability is less than that of long-term ordinary rainfall. The results obtained form this work provided important insights into the stability of high rock slope and rainfall infiltration in open-pit mine, and the safety factor is crucial for guiding the mining process design.

A precise self-built secondary mass database for identifying red dyes and dyeing techniques with UPLC-MS/MS.

Dyes on ancient silks have been a worth studying field through human's history, although current reports ignore the connection between natural dyes origin and relevant colour reduction methods, which poses an insurmountable obstacle for restoration of historical silks. In this paper, a series of 12 red hue silks from six natural dyes (sappanwood, Chinese madder, safflower, lac, cochineal, dragon's blood) via three different dyeing techniques were used to establish a self-built precise tandem mass spectrometry (MS/MS) database. With organic solvent extracting on those manual-dyed silks, ultraperformance liquid chromatography - electrospray ionization - quadrupole time of flight mass spectrometry (UPLC-ESI-QTOF-MS) was utilized to form preliminary MS database for screening and identifying of the potential dyes compounds without standard references. Furthermore, combining the targeted MS/MS mode and the matching threshold of 70.00, a self-built secondary MS/MS database was successfully established, which contains 33 compounds, 32 chromatograms and 32 MS/MS fragments. As for real sample application, the self-built precise MS/MS database had revealed that the dyes on two historical silks (Shanghai Museum, China) belong to Chinese madder just with different mordant dyeing ordinal. Additionally, by experimental restoration, visually indistinguishable silks (ΔEab * < 1.5 NBS) were successfully restored. This explorative methodology can further inspire the traceability of biological dyestuffs, which lays instructive foundation on protection and restoration of artefacts, connecting the archaeological science and human art.

Enhanced removal of As(III) and As(V) from water by a novel zirconium-chitosan modified spherical sodium alginate composite.

Most nano-scaled adsorbents have trouble in separating from aqueous solution, thus, a need for new materials of facile separation and predominant adsorption performance has arisen. This present study focused on a novel segregative zirconium-chitosan modified sodium alginate (Zr-CTS/SA) composite preparation and its performance for As(III/V) removal from aqueous solution. The obtained composite presented a spherical structure with a diameter of 2.0-3.0 mm and favorable thermal stability. Experimental data showed that Zr-CTS/SA had considerable adsorbability for As(III) and As(V), the adsorption capacities were enhanced about at least 20 and 6 times separately compared with pristine SA beads. The adsorption processes of As(III) and As(V) could both be described with Langmuir isotherm model and the maximum adsorption capacities reached 43.19 and 76.78 mg g-1, respectively. The kinetic data of As(III) followed the intra-particle diffusion model while As(V) fitted the pseudo-first-order model. Moreover, the adsorption mechanisms of As(III/V) involved ligand exchange with Cl on the surface of Zr-CTS/SA, another reaction pathway for As(V) was the electrostatic attraction with protonated -OH and -NH2 groups. Note that the employment of Zr-CTS/SA in low-concentration arsenic solution exhibited a residue concentration as low as the 10 µg L-1 WHO guideline for drinking water.

Fast and efficient phosphate removal on lanthanum-chitosan composite synthesized by controlling the amount of cross-linking agent.

In the present study, non-crosslinked lanthanum-chitosan (La-CTS-0X) and crosslinked lanthanum-chitosan (La-CTS-1X/2X) composites were prepared as new complex biosorbents for effective phosphate removal from wastewater. Batch adsorption experiments were investigated by varying the influencing parameters, viz., pH, initial concentration of phosphate ions, contact time, temperature and co-existing anions. Experimental data were well fitted to the Langmuir isotherm model (R2 = 0.9998) as well as the pseudo-second-order model (R2 = 1.000), indicating that the phosphate adsorption process was homogeneous, mono-layered and chemisorption dominated. Besides, the maximum phosphate adsorption capacity for La-CTS-0X/1X/2X was 47.28, 57.84 and 31.01 mg g-1 at pH 6, respectively. Thermodynamic parameters including ΔH° (-43.7 kJ mol-1), ΔS° (-132 J mol-1 K-1) and ΔG° (-4.60 kJ mol-1) revealed that the essence of adsorption was spontaneous and exothermic. The regenerated materials could be repeatedly used for three cycles without obvious degradation of performance. Characterization of the adsorbent using FTIR, SEM, EDS and XPS techniques suggested that the possible adsorption mechanisms were electrostatic attraction as well as ligand exchange. More importantly, the La-CTS-1X had rapid removal rate for phosphate within 10 min and the remained P concentration met the permissible limit by the U.S. Environmental Protection Agency (EPA).

Synthesis of spherical magnetic calcium modified chitosan micro-particles with excellent adsorption performance for anionic-cationic dyes.

In this present study, spherical magnetic calcium modified chitosan micro-particles (MG-Ca-CMPs) were synthesized by using embedding/cross-linking method and employed as an efficient adsorbent for Orange II (OII) in single system and coexisted with methylene blue (MB) in binary system. The obtained MG-Ca-CMPs were characterized by fourier transform infrared spectrometer, transmission electron microscopy, scanning electron microscope, X-ray diffraction and magnetic property measurement system analyses, which demonstrated that the MG-Ca-CMPs possessed core-shell structure and excellent superparamagnetic property. The adsorption behaviors for OII in single system and coexisted with MB in binary system were systematically studied. Adsorption experiments data showed that MG-Ca-CMPs presented an excellent high affinity to acid dye OII (qmax = 962 mg·g-1) in single system, which followed the Langmuir isotherm model and pseudo-second order kinetics model. Interestingly, MB, hardly adsorbed in acidic solution, had effective adsorption performance (increased from 20 mg·g-1 to 350 mg·g-1) in binary system by MG-Ca-CMPs. This result was attributed to the synergistic effect caused by the positive and negative charge attraction between OII and MB, forming the positive-negative-positive adsorption mechanism. It is believed that MG-Ca-CMPs could be used as a potential adsorbent for the adsorption and separation of coexisting anionic-cationic dyes from dye wastewater.

Adsorption of Cr(VI) on cerium immobilized cross-linked chitosan composite in single system and coexisted with Orange II in binary system.

In this work, cerium immobilized cross-linked chitosan (CTS-Ce) composite, employed as an efficient adsorbent for Cr(VI) in single system and coexisted with Orange II (OII) in binary system, was prepared by co-precipitation method. The as-obtained adsorbent was characterized by FTIR, SEM, EDS and XPS before and after adsorption. The adsorption behaviors of Cr(VI) in single and binary system were systematically studied. The maximum adsorption capacity of Cr(VI) on CTS-Ce (202.8mg/g) was calculated by Langmuir equation in single metal system, but it decreased to 112.9mg/g with initial concentration of 100mg/L OII in binary system at pH 2 and 293K. The adsorption data for Cr(VI) followed the Langmuir model in single system, while fitted Temkin model well in binary system. In both single and binary system, the kinetics of adsorption exhibited pseudo-second order behavior and adsorption capacity increased with increasing temperature. Moreover, the data of thermodynamic parameters (ΔG°<0, ΔH°>0) indicated that the adsorption was a spontaneous and endothermic process. Besides, |ΔGCr|>|ΔGCr-OII| at the same temperature further suggested that Cr(VI) was adsorbed on the CTS-Ce composite faster in binary system than in single system.

Simultaneous oxidation and adsorption of As(III) from water by cerium modified chitosan ultrafine nanobiosorbent.

Since most existing arsenic removal adsorbents are difficult to effectively remove arsenite (As(III)), an urgent need is to develop an efficient adsorbent for removing As(III) from contaminated water. In this study, a novel ultrafine nanobiosorbent of cerium modified chitosan (Ce-CNB) with simultaneous oxidation and adsorption As(III) performance has been successfully developed. The resulting Ce-CNB with or without As(III) adsorption was characterized by FTIR, XRD, SEM, EDS, TEM, EMI and XPS analysis. Batch of adsorption experiments were performed to investigate the effects of various conditions on the As(III) adsorption. The adsorption behaviors were well described by the Langmuir isotherm and the pseudo-second-order kinetic model, with the maximum adsorption capacities of 57.5 mg g(-1). The adsorption mechanisms for As(III) were (i) formed monodentate and bidentate complexes between hydroxyl groups and arsenite; and (ii) partial As(III) oxidized to As(V) followed by simultaneously adsorbed on the surface of Ce-CNB. This novel nanocomposite can be reused while maintaining a high removal efficiency and can be applied to treat 5.8L of As(III)-polluted water with the effluent concentration lower than the World Health Organization standard, which suggests its great potential to remove As(III) from contaminated water.

Highly specific phosphopeptide enrichment by titanium(IV) cross-linked chitosan composite.

Natural chitosan was applied as supporting material for Ti(IV) based immobilized metal ion affinity chromatographic (IMAC) material (Ti-CTS). Compared with other polymer based IMAC, Ti-CTS can save the cockamamie synthesis procedures and be easy to obtain. The morphology, surface area, pore volume and elemental composition of Ti-CTS were revealed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) method and X-ray photoelectron spectroscopy (XPS). Tryptic digest products from several standard proteins and two real samples (non-fat milk and serum) were enriched using Ti-CTS to demonstrate the efficiency of this method. The results showed that this composite enables high sensitive and selective phosphopeptide enrichment from casein variants, non-fat milk and human serum. Furthermore, multi-phosphorylated peptides with three serine phospholated sites (S*S*S*) demonstrated high affinity to Ti-CTS. Hence, this method had great potential for future studies of complex phosphoproteomes and especially multi-phosphorylated peptides.

Insight into the adsorption mechanisms of vanadium(V) on a high-efficiency biosorbent (Ti-doped chitosan bead).

In this present study, a new chitosan bead modified with titanium ions (TiCB) was prepared and employed for the adsorption of vanadium ions from aqueous solutions. Batch adsorption experiments were performed to research the effect of various factors, including pH, temperature, contact time and initial concentration of vanadium(V) ions. The adsorption of vanadium was followed by the pseudo second-order kinetic and the Langmuir isotherm model, with a remarkable maximum adsorption capacity of 210 mg/g. The analysis of thermodynamic parameters (ΔG°, ΔH° and ΔS°) revealed that the nature of adsorption was feasible, spontaneous (ΔG°<0) and endothermic (ΔH°>0) process. FTIR, EDS, EMI and XPS studies suggested that the mechanisms of adsorption were possibly attributed to electrostatic attraction, ligand-exchange and redox reaction between TiCB and vanadium ions.

Preparation and characterization of chitosan-zirconium(IV) composite for adsorption of vanadium(V).

In this present study, an inorganic-biopolymer composite based on chitosan-zirconium(IV) was prepared and investigated as a biosorbent for the removal of vanadium(V) ions from aqueous solution. The resulting composite before and after adsorbed V(V) were characterized by using FT-IR, XRD, SEM and EDS, respectively. Various relevant parameters affecting the adsorption capacity such as pH, initial concentration, contact time, temperature and co-existing ions were evaluated. The results demonstrated that the optimum pH was found to be 4.0 and the equilibrium was achieved after 4h for V(V) adsorption. The Langmuir isotherm model could be well described the adsorption of V(V), with the maximum adsorption capacity of 208 mg g(-1) at 30 °C. The kinetics data were well fitted to pseudo-second-order equation, indicating that chemical sorption as the rate-limiting step of adsorption mechanism. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° indicated that the adsorption process was feasible, spontaneous and endothermic in nature. Moreover, co-existing ions including nitrate, chloride and sulfate had a certain effect on the uptake of V(V). The V(V) loaded chitosan-zirconium(IV) composite could be regenerated by 0.01 mol L(-1) sodium hydroxide, with efficiency greater than 95%.

Fabrication of biocompatible and mechanically reinforced graphene oxide-chitosan nanocomposite films.

BACKGROUND: Graphene oxide (GO)can be dispersed through functionalization, or chemically converted to make different graphene-based nanocomposites with excellent mechanical and thermal properties. Chitosan, a partially deacetylated derivative of chitin, is extensively used for food packaging, biosensors, water treatment, and drug delivery. GO can be evenly dispersed in chitosan matrix through the formation of amide linkages between them, which is different from previous reports focusing on preparing GO/chitosan nanocomposites through physical mixing. RESULTS: In this study, free-standing graphene oxide-chitosan (GO-chitosan) nanocomposite films have been prepared. The GO-chitosan films are biologically compatible and mechanically reinforced. Through the formation of amide linkages between GO's carboxylic acid groups and chitosan's amine groups, GO could be evenly dispersed within the chitosan matrix. We also characterized the GO-chitosan composite films using element analysis, Fourier transform infrared spectroscopy, X-ray photo electron spectroscopy, differential scanning calorimetry, and thermo gravimetric analysis. Compared to pristine chitosan film, the tensile strength of GO-chitosan film is improved by 2.5 folds and Young's modulus increases by nearly 4.6 folds. The glass transition temperature of GO-chitosan composite film shifts from 118°C to 158°C compared to the pristine chitosan, indicating its enhanced thermal stability. GO-chitosan composite film was also evaluated for its biocompatibility with C3H10T1/2 cells by in vitro fluorescent staining. The graphene oxide-reinforced chitosan composite films could have applications in functional biomaterials. CONCLUSION: The present study describes a useful and simple method to chemically attach biocompatible chitosan onto graphene oxide. We envision that the GO-chitosan film will open avenues for next-generation graphene applications in the realm of functional biomaterial.

Electrochemical detection of DNA hybridization by using a zirconia modified renewable carbon paste electrode.

A simple, polishable and renewable DNA biosensor was fabricated based on a zirconia modified carbon paste electrode. Zirconia was mixed with graphite powder and paraffin wax to produce the paste for the electrode, and response-optimized at 56% graphite powder, 19% ZrO(2) and 25% paraffin wax. An oligonucleotide probe with a terminal 5'-phosphate group was attached to the surface of the electrode via the strong affinity of zirconia for phosphate groups. DNA immobilization and hybridization were characterized by cyclic voltammetry and differential pulse voltammetry, using methylene blue as indicator. Examination of changes in response with complementary or non-complementary DNA sequences showed that the developed biosensor had a high selectivity and sensitivity towards hybridization detection (< or =2x10(-10) M complementary DNA detectable). The surface of the biosensor can be renewed quickly and reproducibly (signal RSD+/-4.6% for five successive renewals) by a simple polishing step.