Removal of Cd(II) and Fe(III) from DMSO by silica gel supported PAMAM dendrimers: Equilibrium, thermodynamics, kinetics and mechanism.

A series of silica gel supported amino-terminated PAMAM dendrimers (SG-G1.0 - SG-G3.0) were used for the removal of Cd(II) and Fe(III) from dimethylsulfoxide (DMSO). Various parameters that influence adsorption behaviors including temperature, contact time, and initial metal ion concentration were studied. The adsorption mechanism was revealed by combining the results of experiment and density functional theory (DFT) calculation. It indicates that the adsorption capacities for Cd(II) and Fe(III) are largest among the metal ions tested. The adsorption capacity of SG-G1.0 - SG-3.0 for Cd(II) and Fe(III) follows the order of SG-G2.0 > SG-3.0 > SG-G1.0. The adsorption isotherm shows the adsorption capacities for both metal ions increases with raising the temperature and initial metal ion concentration. The adsorption isotherm is consistent with Langmuir model and the adsorption process is dominated by chemical adsorption mechanism. Thermodynamic parameters indicates that the adsorption for both Cd(II) and Fe(III) is spontaneous and endothermic. Kinetic adsorption indicates that the adsorption equilibrium times for Cd(II) and Fe(III) is about 200 and 350 min, respectively, which can be described by a pseudo-second-order model and controlled by film diffusion process. FTIR analysis and theoretical calculation revealed that the carbonyl O atoms, secondary amine N atoms, and primary amine N atoms are the primary factor responsible for PAMAM adsorption by forming tetra- and penta-coordinated chelates with metal ions.

Pore structure control factors of polyamine-bridged polysilsesquioxanes by sol-gel method and their structure-adsorption properties for Au(III).

A series of bridged polysilsesquioxane (BPS) materials was synthesized by the sol-gel method from 3-chloropropyl trimethoxysilane, diethylenetriamine (DETA) or ethylenediamine. Tetraethyl orthosilicate (TEOS) and/or one of the two templates, hexadecyl trimethyl ammonium bromide (CTAB) or P123, were used in the co-condensation process to construct some of the porous adsorbents. The adsorption of Au(III) was the highest for samples without TEOS, especially for the DETA series with CTAB template. This study elucidates the synthesis and applications of BPS materials.

Hg(II) adsorption using amidoximated porous acrylonitrile/itaconic copolymers prepared by suspended emulsion polymerization.

Initially, porous acrylonitrile/itaconic acid copolymers (AN/IA) were prepared by suspended emulsion polymerization. Successively, the cyano groups in AN/IA copolymers were converted to amidoxime (AO) groups by the reaction with hydroxylamine hydrochloride. The structures of the AN/IA and amidoximated AN/IA (AO AN/IA) were characterized by infrared spectroscopy, scanning electron microscopy, and porous structural analysis. The adsorption properties of AO AN/IA for Hg(II) were investigated. The results show that AO AN/IA has mesopores and macropores, and surface area of 11.71 m(2) g(-1). It was found that AO AN/IA has higher affinity for Hg(II), with the maximum adsorption capacity of 84.25 mg g(-1). The AO AN/IA also can effectively remove Hg(II) from different binary metal ion mixture systems. Furthermore, the adsorption kinetics and thermodynamics were studied in detail. The adsorption equilibrium can quickly be achieved in 4 h determined by an adsorption kinetics study. The adsorption process is found to belong to the second-order model, and can be described by the Freundlich model.

Preparation and Mechanical Properties of UV-Curable Epoxy Acrylate/Modified Aramid Nanofiber Nanocomposite Films.

In order to enhance the mechanical properties of UV-curable epoxy acrylate (EA)-based coatings, 3-(trimethoxysilyl)propyl methacrylate modified aramid nanofibers (T-ANFs) were synthesized and used as nanofillers to prepare EA/T-ANF nanocomposite films. The morphology of T-ANFs was characterized by transmission electron microscopy. The chemical structure of T-ANFs was analyzed via infrared spectroscopy, confirming successful grafting of methyl methacryloyloxy groups onto the surface of aramid nanofibers (ANFs). Real-time infrared spectroscopy was employed to investigate the influence of ANFs and T-ANFs on the photopolymerization kinetics of the EA film. The results revealed that the addition of ANFs and T-ANFs led to a decrease in the photopolymerization rate during the initial stage but had little impact on the final double bond conversion, with all samples exhibiting a conversion rate of over 83%. The incorporation of ANFs improved the tensile strength of the films while significantly reducing their Young's modulus. In contrast, the addition of T-ANFs led to a substantial increase in both tensile stress and Young's modulus of the films. For instance, the tensile strength and Young's modulus of the 0.1 wt% of T-ANF film increased by 52.7% and 41.6%, respectively, compared to the pure EA film. To further study the dispersion morphology and reinforcement mechanism, the cross-sectional morphology of the films was characterized by scanning electron microscopy.

Preparation and Properties of UV-Curable Waterborne Polyurethane Acrylate/MXene Nanocomposite Films.

In this study, waterborne polyurethane acrylate (WPUA)/MXene nanocomposite films with varying MXene loadings were fabricated using UV-curing technology, where MXene (Ti3C2Tx) was employed as a nanofiller. The microstructure and chemical structure of the WPUA/MXene nanocomposite films were examined by XRD and FTIR, respectively. The water contact angle testing demonstrated that the incorporation of MXene into the nanocomposite films led to an increase in their hydrophilic properties. The tensile strength, the elongation at break, and Young's modulus of the WPUA/MXene nanocomposite coatings exhibited an initial increase followed by a decrease with increasing MXene loadings. Compared to the pure WPUA film, the tensile strength and elongation at break of nanocomposites with 0.077 wt% MXene loading reached their maximum values, which increased by 39.9% and 38.5%, respectively. Furthermore, the glass transition temperature and the thermal stability were both enhanced by MXene to some extent. This study introduces a novel method for utilizing MXene in UV-curable waterborne coatings.

Conductive Aramid Fibers from Electroless Silver Plating of Crosslinked HPAMAM-Modified PPTA: Preparation and Properties.

Conductive aramid (PPTA) fibers are highly needed for making flexible conductive materials, antistatic materials, and electromagnetic shielding materials. In this work, silver-plated conductive PPTA fibers with high conductivity and excellent mechanical properties were prepared by the electroless plating of PPTA fibers modified with crosslinked hyperbranched polyamide-amine (HPAMAM). The crosslinked HPAMAM creates a stable interface between the PPTA fibers and the silver plating. The morphology and physicochemical properties of the modified and the silver-plated fibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Three epoxy crosslinking agents with different chain lengths were used to crosslink HPAMAM, and the effects of HPAMAM concentration, crosslinking agent dosage, and crosslinking time on the resistance of the fibers were studied. The long chain crosslinking agent appears to be beneficial to silver plating. The lowest resistance (0.067 Ω/cm) was attained when HPAMAM was modified by diethylene glycol diglycidyl ether (1:1 molar ratio), and 20 g/L HPAMAM was used to modify the PPTA fibers. The tensile strength of the original PPTA fibers decreased by only 3% or less after silver plating.

Facile Synthesis of Cross-linked Hyperbranched Polyamidoamines Dendrimers for Efficient Hg(â ¡) Removal From Water.

Dendrimers as commonly used metal ions adsorption materials have the advantages of good adsorption performance and high reuse rate, but the high cost limits its extensive use. Compared with dendrimers, hyperbranched dendrimers have similar physical and chemical properties and are more economical. Therefore, hyperbranched dendrimers are more suitable for industrial large-scale adsorption. The hyperbranched polyamidoamine (HPAMAM) gels were prepared by cross-linking hyperbranched polyamidoamine (HPAMAM-ECH-x and HPAMAM-EGDE-x) with different amounts of epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE), respectively. The as-synthesized adsorbents were characterized by FT-IR, SEM and XPS. The prepared adsorbents were used to adsorb Hg(Ⅱ) in aqueous solution, and the effects of solution pH, contact time, temperature and initial concentration of metal ion on the adsorption capacity were investigated. The effect of solution pH indicated that the optimum condition to Hg(Ⅱ) removing was at pH 5.0. The adsorption kinetic curves of the two kinds of materials were in accordance with the pseudo-second-order model. For the HPAMAM-ECH samples, the adsorption thermodynamic curves fitted the Langmuir model, while for the HPAMAM-EGDE samples, both Langmuir and Freundlich equations fitted well. The maximum adsorption capacity of HPAMAM-ECH-3 obtained from Langmuir model toward Hg(Ⅱ) was 3.36 mmol/g at pH 5.0 and 35°C.

Comparison of synthesis of chelating resin silica-gel-supported diethylenetriamine and its removal properties for transition metal ions.

Four kinds of silica-gel (SG)-supported diethylenetriamine (DETA) chelating resins SG-DETA-1, SG-DETA-2, SG-DETA-3, and SG-DETA-4 were prepared by functionalization of silica-gel via so-called "heterogeneous-direct-amination" (hetero-DA), "homogeneous-direct-amination" (homo-DA), "heterogeneous end-group protection" (hetero-EGP), and "homogeneous end-group protection" (homo-EGP) routes, respectively. These functionalized reactions on silica-gel were confirmed through elemental analysis, infrared spectroscopy, X-ray diffractometry, porous analysis, and thermogravimetry. Element analysis revealed that the direct-amination routes and homogeneous condition were more beneficial than the corresponding end-group protection routes and heterogeneous condition to the syntheses of chelating resins with high N content. Several metal ions, such as Ag(+), Cu(2+), Ni(2+), Hg(2+), Zn(2+) and Pb(2+), were chosen as representatives to investigate the relationship between adsorption capacities and N content of ligands onto the surface of silica-gel. The experiments results showed that all resins, SG-DETA-1, SG-DETA-2, SG-DETA-3 and SG-DETA-4, had a better adsorption for Hg(2+) and Cu(2+) than others. One conclusion should be drawn from the above compared experiments, that is, higher N content of silica-gel resins does not ensure a higher utilization ratio of N.

Fabrication of Triethylenetetramine Terminal Hyperbranched Dendrimer-Like Polymer Modified Silica Gel and Its Prominent Recovery Toward Au (III).

To further increase the quantity and density of functional groups on adsorbent, terminal triethylenetetramine hyperbranched dendrimer-like polymer modified silica-gel (SG-TETA and SG-TETA2) was synthesized. The hyperbranched dendrimer-like polymer was successfully introduced onto silica gel and new cavities were formed, which was demonstrated by FTIR, SEM, and BET. The highest adsorption capacities of SG-TETA and SG-TETA2 obtained from Langmuir model toward Au(III) were 2.11, and 2.27 mmol g-1, respectively, indicating that SG-TETA2 possessing more functional groups had a better adsorption ability. Moreover, the adsorbents combined with Au(III) ion through chelation and electrostatic attraction mechanism, after which reduction reactions for Au(III) ion loaded on adsorbents proceeded. SG-TETA2 had better adsorption selectivity than SG-TETA in removing Au(III) in Au-existed ion solution systems. SG-TETA2 had higher overall adsorption capacities compared to silica-gel-based hyperbranched polymers functionalized by diethylenetriamine. Therefore, the effective recovery makes SG-TETA2 a practical adsorbent in removing Au(III) ion from e-wastes and industrial effluents with much prospect.

Amino- and Thiol- Polysilsesquioxane Simultaneously Coating on Poly(p-Phenylenetherephthal Amide) Fibers: Bifunctional Adsorbents for Hg(II).

A double reagents simultaneous functionalization (DRSF) was used to prepare porous polysilsesquioxane with NH2 and SH bifunctional groups (PAMPSQ) coated poly(p-phenylenetherephthal amide) (PPTA) fibers adsorbents (PPTA-AM), via in situ condensations with aminopropyltriethoxysilane (APTES) and mercaptopropyltriethoxysilane (MPTES). The PAMPSQ coated on the PPTA surface was in the form of nanoparticles and its morphology varied with the proportion of the reactants. The PAMPSQ exhibited loose open meso- or macroporous features. The functional groups utilization of PAMPSQ was much higher than those of polysilsesquioxane on the mono-functional adsorbents with thiol or amino groups. The selective adsorption of PPTA-AM adsorbents for Hg(II) in binary component metal ion systems indicated their potential application in environmental remediation. The adsorption mechanism of Hg(II) onto PPTA-AM was proposed.

Aramid Nanomaterials of Various Morphologies: Preparation and Mechanical Property Enhancement.

Aramid nanofibers (ANFs) are a novel type of promising nanoscale building blocks for high-performance nanocomposites. Conventionally, ANFs are used to composite with polymers containing polar groups such as -OH and -NH2 since those polymers can interact with the amide groups in ANFs through polar-polar interaction such as hydrogen bonding. In this study, ANFs were derivatized with non-polar alkyl groups including ethyl, octyl and dodecyl groups and used as a performance-enhancing additive to polyvinyl chloride (PVC) with weak polarity. Interestingly, it was observed that the morphologies of the resulting alkyl-derivatized aramid nanomaterials (R-ANMs) varied significantly including nanofibers, nanobranches, nanosheets, and nanospheres, all of which depended on the degree of substitution (DS) and the chain length of the alkyl group. As an additive, R-ANMs improved the Young's modulus, toughness and yield strength of the PVC films. This study proves the concept that ANFs can be used to composite weakly polar or non-polar polymers.

Preparation and metal-binding behaviour of chitosan functionalized by ester- and amino-terminated hyperbranched polyamidoamine polymers.

A series of insoluble chitosan (CTS) derivatives were prepared by grafting ester- and amino-terminated dendrimer-like polyamidoamine (PAMAM) into CTS using a divergent method by repeating two processes: (1) Michael addition of methyl acrylate (MA) to surface amino groups, and (2) amidation of the resulting esters with ethylenediamine (EDA). Their structures were characterized by infrared spectra (IR) and wide-angle X-ray diffraction (WAXD). The adsorption capabilities of the products for Au(3+), Pd(2+), Pt(4+), Ag(+), Cu(2+), Zn(2+), Hg(2+), Ni(2+), and Cd(2+) were studied. The results showed that the products exhibited better adsorption capabilities for Au(3+) and Hg(2+) than for other metal ions, and the adsorption capabilities of amino-terminated products were higher than those of ester-terminated ones. Also it was observed that a high percentage of grafting of PAMAM into CTS does not ensure a high adsorption capacity.

Degradation behavior of chitosan chains in the 'green' synthesis of gold nanoparticles.

The degradation behavior of chitosan chains in the synthesis of Au nanoparticles by a 'green' method was investigated in this paper for the first time. UV-vis absorption spectra suggested the formation of Au nanoparticles and TEM images showed that their sizes were between 10 and 50nm. During the process of synthesis, the intrinsic viscosity [eta] of chitosan was observed to decrease gradually, implying that the chitosan chains degraded under the reaction conditions. Further studies showed that the degree of degradation of the chitosan chains was changed with different reaction temperatures, reactant ratios, and the molecular weights of chitosan.

A density functional theory study on the role of His-107 in arylamine N-acetyltransferase 2 acetylation.

Arylamine N-acetyltransferases (NATs, EC 2.3.1.5) catalyze an acetyl group transfer from acetyl coenzyme A (AcCoA) to primary arylamines, and are responsible for the biotransformation and metabolism of drugs, carcinogens, etc. Structure analysis revealed that His-107 was likely the residue accountable for mediating acetyl transfer. We have examined the full catalytic mechanism of this system by means of DFT method. The results indicate that if the acetyl group directly transferred from the donor, p-nitrophenyl acetate, to the acceptor, cysteine, the high activation energy will be a great hindrance. These energies have dropped a little in a range of 20-25 kJ/mol when His-107 is assisting the transfer process. However, when protonated His-107 is mediating the reaction, the activation energies have dropped about 70-85 kJ/mol. Our calculations strongly support an enzymatic acetylation mechanism that experiences a thiolate-imidazolium pair, which have verified the presumption from experiments.

Synthesis, characterization and antibacterial properties of dihydroxy quaternary ammonium salts with long chain alkyl bromides.

Five N-methyl-N-R-N,N-bis(2-hydroxyethyl) ammonium bromides (R = -benzyl (chloride, BNQAS), -dodecyl (C12QAS), -tetradecyl (C14QAS), -hexadecyl (C16QAS), -octadecyl (C18QAS)) were prepared based on N-methyldiethanolamine (MDEA) and halohydrocarbon. Five QAS were characterized by FTIR, NMR, and MS. BNQAS, C12QAS, C14QAS, and C16QAS were confirmed by X-ray single-crystal diffraction. Their antibacterial properties indicated good antibacterial abilities against E. coli, S. aureus, B. subtilis, especially C12QAS with the best antibacterial ability (100% to E. coli, 95.65% to S. aureus, and 91.41% to B. subtilis). In addition, C12QAS also displayed the best antifungal activities than BNQAS and C18QAS against Cytospora mandshurica, Botryosphaeria ribis, Physalospora piricola, and Glomerella cingulata with the ratio of full marks. The strategy provides a facile way to design and develop new types of antibacterial drugs for application in preventing the fruit rot, especially apple.

Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production.

Analysis of lead in beverage juice using mesoporous cadmium phosphate as a solid phase adsorbent.

Toxic heavy metals in beverages can seriously harm human health. In the present work, a facile and eco-friendly biosynthesis of mesoporous cadmium phosphate (MPCP), using bovine serum albumin (BSA), has been successfully developed. BSAs were used to regulate the nucleation and growth of cadmium phosphate; MPCP has been used for lead ions removal from juice beverage solution and it has very excellent adsorption property capacity for Pb(II). Its adsorption kinetics could be modelled by the pseudo second-order rate equation, and the thermodynamic parameters ΔG, ΔH and ΔS were - 5.95 kJ mol(-1), 15.08 kJ mol(-1), and 68.09 J K(-1)mol(-1), respectively. Therefore, the present research work has provided an effective way for lead ion removal in drinks, and the results suggest that MPCP might be used as a promising adsorbent with high efficiency for heavy metal ion uptake in the beverage industry.

Synthesis of silica gel supported salicylaldehyde modified PAMAM dendrimers for the effective removal of Hg(II) from aqueous solution.

A series of silica gel supported salicylaldehyde modified PAMAM dendrimers (SiO2-G0-SA ∼ SiO2-G2.0-SA) were synthesized and their structures were characterized by FTIR, XRD, SEM, TGA, and porous structure analysis. The feasibility of these adsorbents for the removal of Hg(II) from aqueous solution was first described and the adsorption mechanism was proposed. The adsorption was found to depend on solution pH, the generation number of salicylaldehyde modified PAMAM dendrimers, contact time, temperature, and initial concentration. Results showed that the optimal pH was about 6 and the adsorption capacity increased with the increasing of generation number. Density functional theory (DFT) method was used to investigate the coordination geometries and the chelating mechanism. Adsorption kinetics was found to follow the pseudo-second-order model with film diffusion process as rate controlling step. Adsorption isotherms revealed that adsorption capacities increased with the increasing of temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were employed to analyze the equilibrium data. The adsorption can be well described by Langmuir isotherm model and took place by chemical mechanism. The thermodynamics properties indicated the adsorption processes were spontaneous and endothermic nature. The maximum adsorption capacity of SiO2-G0-SA, SiO2-G1.0-SA, and SiO2-G2.0-SA were 0.91, 1.52, and 1.81 mmol g(-1), respectively. The considerable higher adsorption capacity compared with other adsorbents indicates SiO2-G0-SA ∼ SiO2-G2.0-SA are favorable and useful for the uptake of Hg (II), and can be potentially used as promising adsorbents for the effective removal of Hg(II) from aqueous solution.

Adsorption kinetics, thermodynamics and isotherm of Hg(II) from aqueous solutions using buckwheat hulls from Jiaodong of China.

The adsorption kinetics and adsorption isotherms of buckwheat hulls in the region of Jiaodong, China (BHJC) for Hg(II) were investigated. Results revealed that the adsorption kinetics of BHJC for Hg(II) were well described by a pseudo second-order reaction model, and the adsorption thermodynamic parameters ΔG, ΔH and ΔS were -5.83 kJ mol(-1)(35°C), 73.1, and 256 JK(-1) mol(-1), respectively. Moreover, Langmuir, Freundlich and Redlich-Peterson isotherm models were applied to analyse the experimental data and to predict the relevant isotherm parameters. The best interpretation for the experimental data was given by the Langmuir isotherm equation, and the maximum adsorption capacity for Hg(II) is 243.90 mg/g at 35°C. Furthermore, investigation of the adsorption selectivity showed that BHJC displayed strong affinity for mercury in the aqueous solutions and exhibited 100% selectivity for mercury in the presence of Zn(II) and Cd(II).

Uptake of gold (III) from waste gold solution onto biomass-based adsorbents organophosphonic acid functionalized spent buckwheat hulls.

Novel biomass-based adsorbents organophosphonic acid functionalized spent buckwheat hulls (OPA-BH) with 60 mesh were successfully employed to adsorb Au(III) ions from simulated wastewater. The adsorption kinetics and isotherms both in unary ion system and in ternary ions system were investigated, and the applicability of the Langmuir, Freundlich and extended Langmuir isotherm models has been tested for the equilibrium. The process optimization was also conducted by using response surface methodology (RSM), and the maximum adsorption capacities reached 2.84 ± 0.01 mmol/g under the optimum process conditions. Furthermore, the regeneration capacities of OPA-BH were investigated by using the eluent solutions of 0.0-5.0% thiourea in 0.1 mmol/L HCl, and the results showed that the adsorption capabilities for OPA-BH were ranged between 0.77 mmol/g and 0.85 mmol/g after three cycles of adsorption-desorption processes. The research results showed that OPA-BH was favorable and useful for gold adsorption, and the high adsorption capacity and good reproducibility make it a good promising material for the precious metal uptake.