Poly-L-Histidine Attached Poly(glycidyl methacrylate) Cryogels for Heavy Metal Removal

Poly-L-histidine immobilized poly(glycidyl methacrylate) (PGMA) cryogel discs were used for the removal of heavy metal ions [Pb(II), Cd(II), Zn(II) and Cu(II)] from aqueous solutions. In the first step, PGMA cryogel discs were synthesized using glycidyl methacrylate (GMA) as a basic monomer and methylene bisacrylamide (MBAAm) as a cross linker in order to introduce active epoxy groups through the polymeric backbone. Then, the metal chelating groups are incorporated to cryogel discs by immobilizing poly-L-histidine (mol wt ≥ 5000) having poly-imidazole ring. The swelling test, fourier transform infrared spectroscopy and scanning electron microscopy were performed to characterize both the PGMA and poly-L-histidine immobilized PGMA [P-His@PGMA] cryogel discs. The effects of the metal ion concentration and pH on the adsorption capacity were studied. These parameters were varied between 3.0–6.0 and 10–800 mg/L for pH and metal ion concentration, respectively. The maximum adsorption capacity of heavy metal ions of P-His@PGMA cryogel discs were 6.9 mg/g for Pb(II), 6.4 mg/g for Cd(II), 5.6 mg/g for Cu(II) and 4.3 mg/g for > Zn(II). Desorption of heavy metal ions was studied with 0.1 M HNO₃ solution. It was observed that cryogel discs could be recurrently used without important loss in the adsorption amount after five repetitive adsorption/desorption processes. Adsorption isotherms were fitted to Langmuir model and adsorption kinetics were suited to pseudo-second order model. Thermodynamic parameters (i.e. ΔH° ΔS°, ΔG°) were also calculated at different temperatures.     

Water-insoluble cyclodextrin polymer crosslinked with citric acid for paraquat removal from water

The anionic water-insoluble cyclodextrin polymer (polyCTR-β-CD) was crosslinked between β-cyclodextrin (β-CD) and citric acid (CTR) at 180?°C during 30?minutes to eliminate paraquat (PQ) from water. The reaction yield was equal to 70.2%, the ionic exchange capacity corresponded to 3.29?mmol·g^?1 and the β-CD content was 0.29?mmol·g^?1. Then, samples were characterized by SEM, ATR-FTIR, TGA, BET and stereoscopic microscope. Adsorption experiments were investigated with different factors such as pH of the solution, contact time, initial concentration of paraquat and adsorption temperature. The relevant pH was equal to 6.5 and the optimal contact time was 120?minutes to attain adsorption equilibrium. At 30?°C, the adsorption capacity was increased (9.4, 17.4 and 20.8?mg·g^?1) when the initial concentration of paraquat was raised (25, 50 and 200?mg·L^?1 respectively). Adsorption kinetics was appropriated to the pseudo-second-order model and adsorption isotherm was fitted to the Langmuir model. For thermochemistry parameters at different temperatures, the negative ΔG° showed a spontaneous adsorption process, the negative ΔH° indicated an exothermic process and the positive ΔS° exhibited an increase disorder. Finally, the reusability of the insoluble polymer was reached 78.3% after four regeneration cycles in methanol.     

Adsorption calorimetry

The efficiency of activated carbons prepared from corncob, to remove asphaltenes from toluene modeled solutions, has been studied in this work. The activating agent effect over carbonaceous solid preparation , and also temperature effect on the asphaltenes adsorption on the prepared activated carbons, was studied. The asphaltene adsorption isotherms were determined, and the experimental data were analyzed applying the Langmuir, Freundlich, Redlich–Peterson, Toth and Radke–Prausnitz and Sips models. Redlich–Peterson model described the asphaltenes isotherm on the activated carbons better. The asphaltenes adsorption capacities at 25° for activated carbons were: 1305 mg g^?1, 1654 mg g^?1 and 559.1 mg g^?1 for GACKOH, GACKP and GACH₃PO₄, respectively. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were also evaluated from the adsorption isotherms in asphaltene solutions from toluene solutions, and it was found that the adsorption process was spontaneous and exothermic in nature. Kinetic parameters, reaction rate constant and equilibrium adsorption capacities were evaluated and correlated for each kinetic model. The results show that asphaltene adsorption is described by pseudo-second-order kinetics, suggesting that the adsorption process is chemisorption. The adsorption calorimetry was used to analyze the type of interaction between the asphaltenes and the activated carbons prepared in this work, and their values were compared with the enthalpic values obtained from the Clausius–Clapeyron equation.

     

Equilibrium and fractal-like kinetic studies of the sorption of acid and basic dyes onto watermelon shell (<Emphasis Type="Italic">Citrullus vulgaris</Emphasis>)

In the present study, batch experiments were used to determine adsorption characteristics of Watermelon Shell Biosorbent (WSB) for the uptake of anionic and cationic dyes from aqueous solution. Various factors such as initial dye concentration, adsorbent dosage, pH, contact time and temperature were systematically investigated and discussed. WSB was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and Fourier Transform Infrared Spectroscopy. The adsorption kinetics was best described by Elovich and Diffusion-Chemosorption models for Basic red 2 (BR2) (cationic dye) and Orange G (OG) (anionic dye) respectively. However, the fractional time index “α” and non-integer “n” order by Fractal-like pseudo-first order kinetic affirmed that the mechanism of interaction of both dyes with WSB was by chemical reaction. The applicability of four adsorption isotherm models for the present system was tested. The equilibrium data were found to be well represented by the Extended Langmuir isotherm equation. The monolayer adsorption capacity of WSB for BR2 and OG adsorption was found to be 125 and 27 mg/g, respectively. The effect of temperature on the adsorption process was also investigated and the values of thermodynamic parameters ΔG°, ΔH° and ΔS° revealed that the adsorption system was spontaneous.     

Application of response surface methodology to optimize the process variables for fluoride ion removal using maghemite nanoparticles

Adsorption of fluoride ion was done from its aqueous solution by using maghemite (γ-Fe₂O₃) nanoparticles. Effects of the major independent variables (temperature, adsorbent dose and pH) and their interactions during fluoride ion adsorption were determined by response surface methodology (RSM) based on three-level three-factorial Box–Behnken design (BBD). Optimized values of temperature, maghemite nanoparticle dose and pH for fluoride sorption were found as 313 K, 0.5 g/L, and 4, respectively. In order to investigate the mechanism of fluoride removal, various adsorption isotherms such as Langmuir, Freundlich, Temkin and Florry–Huggins were fitted. The experimental data revealed that the Langmuir isotherm gave a more satisfactory fit for fluoride removal. The adsorption process was rapid and obeyed pseudo-second-order kinetics. The values of thermodynamic parameters ΔG°, ΔH° and ΔS° indicated that adsorption was spontaneous and endothermic in nature.     

Surface-active properties of new cationic gemini surfactants with cyclic spacer

Three cationic gemini surface active compounds of the type (1r,4r)-1,4-dialkyl-1,4-dimethy-l-piperazine-1,4-diium bromide (Ia, Ib, and Ic), were synthesized. They were characterized using elemental analysis and ¹H-NMR spectra. Their surface-active properties were measured in aqueous solutions with different concentrations at different temperatures (25, 40, and 55°C). Various surface measurements of these gemini surfactants, (compared to the conventional one, 1-Dodecyl-1-methylpiperidinium bromide (a)) were estimated, specifically critical micelle concentration (CMC), effectiveness (π_CMC), efficiency (P_C20) as well as maximum surface excess (Γ_max) and minimum surface area (A_min). The measurements of the gemini compounds gave low CMC, high efficiency in reducing the surface tension, and intense adsorption at air/water interface. These surfactants have lower Krafft points and thus better solubility. Thermodynamic data, free energy, entropy, and enthalpy changes (ΔG°, ΔS°, and ΔH°) for micellization at the air/water interface and also for adsorption in the bulk of surface-active solutions were calculated.     

A kinetics,isotherms, and thermodynamic study of diclofenac adsorption using activated carbon prepared from olive stones

The objective of this work was to study the efficiency of activated carbon prepared from agricultural waste (olive stones; OS) on diclofenac (DCF) adsorption in aqueous solutions. The prepared charcoals were characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM)/Energy Dispersive X-Ray Analyser (EDX), and Brunauer–Emmett–Teller (BET) analysis techniques. The results show that DCF adsorption is favorable in acid medium and low temperature. The adsorption kinetics follows a pseudo-second-order kinetic model. The adsorption was found to be spontaneous (ΔG°?相似文献   

Brilliant Blue R Adsorption from Aqueous Solution on Activated Carbon Produced from Corncob Waste

Brilliant blue R adsorption from aqueous solution on activated carbon produced from corncob waste was investigated. The carbon samples were characterized by XRD, SEM, EDS and FTIR methods. The surface functional groups (carboxyl, lactone or phenol, ether, hydroxyl) disappeared at high activation temperature, resulting in a high amount of carbon with respect to oxygen. The kinetic studies of the adsorption of brilliant blue R on carbon at 10 and 45 °C showed that the first order and intraparticle diffusion models apply to the data. The reaction rate increased with the increase in temperature of adsorption/activation. Thermodynamic parameters like ΔE^#, ΔH^# and ΔS^# for adsorption were calculated from the kinetic data. The positive value of ΔH^# shows the endothermic nature of adsorption which decreased with the increase in adsorption/activation temperature. The negative values of ΔS^# reflect a decrease in the disorder of the system at the solid‐solution interface during adsorption. Equilibrium studies showed that the data fits the Langmuir model.     

Kinetics of Acid Blue 1 Adsorption from Aqueous Solution by Carbonaceous Substrate Produced from Biotic Precursor

Adsorption of acid blue 1 from aqueous solution onto carbonaceous substrate produced from the wood of Paulownia tomentosa was investigated. The samples characterized by FTIR, SEM, EDS and XRD techniques, indicated that the surface functional groups like carboxyl, lactones or phenols and ethers have disappeared at high activation temperature （800 ℃） and as a result porous structure was developed that has a positive effect on the adsorption capacity. Bangham and parabolic diffusion models were applied to the kinetic adsorption data, which show that the adsorption of acid blue 1 was a diffusion controlled process. The reaction rate increased with the increase in temperatures of both the adsorption and activation. Thermodynamic parameters like △E^≠, △H^≠, △S^≠ and △G^≠ were calculated from the kinetic data. The negative values of △S^≠ reflected the decrease in the disorder of the system at the solid-solution interface during adsorption. Gibbs free energy （△G^≠）, representing the driving force for the affinity of dye for the carbon surface, increased with the increase in sample activation and the adsorption temperatures.     

Ammonium salt of the cross-linked maleic acid–allylpropionate–styrene terpolymer as effective sorbent for removal of Cu2+ ions from water solutions (sorption of the copper ions)

The capability of the ammonium salt of the cross-linked maleic acid–allylpropionate–styrene terpolymer for the adsorption of Cu²⁺ from aqueous solutions was examined. Effect of the various experimental parameters on removal degree of the copper ions was investigated. Equilibrium data were fitted to the Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models. Kinetics studies suggested that the adsorption allowed pseudo-second-order reaction. The negative values of ΔG° and the positive value of ΔH° indicate that the sorption process is spontaneous and endothermic in nature. The positive value of ΔS° shows the increasing randomness during adsorption process. Considering the FTIR and UV–vis spectra of the sorbent after sorption, it is concluded that Cu²⁺ enters a complex with carboxylate and ester groups of the sorbent.     

Equilibrium,kinetic, and thermodynamic studies of lead ion adsorption from mine wastewater onto MoS2-clinoptilolite composite

This work explored the potential of clinoptilolite, molybdenum sulphide (MoS₂), and MoS₂-clinoptilolite composite in lead (Pb) removal from aqueous medium and industrial mining wastewater. MoS₂-clinoptilolite composite was successfully prepared by a hydrothermal method. The surface properties, structure, and composition of the synthesized composite and the parent compounds were analyzed by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. The removal efficiency of lead from aqueous solution was studied in batch-mode experiments. The MoS₂-clinoptilolite was used for the removal of Pb ions (50 mg/L) from an aqueous solution: ~100% of the Pb was removed with a MoS₂-clinoptilolite dose of 0.075 g, pH 6 at 328K within 90 min. The adsorption capacities of Pb onto MoS₂-clinoptilolite were found to be higher than those onto clinoptilolite. Metal ion adsorption behavior was well explained by the Freundlich model, that is, multilayer adsorption of Pb molecules occurred on the heterogeneous surface of adsorbents in case of clinoptilolite, while in the case of MoS₂-clinoptilolite, the Langmuir model was suitable, that is, the adsorption occurred on a monolayer surface. The rate of Pb adsorption was explained by pseudo-second-order model suggesting that the adsorption process is presumably chemisorption. Thermodynamic parameters such as ΔH°, ΔS°, and ΔG° were calculated, which indicated that the adsorption was spontaneous and exothermic in nature. The selectivity of each adsorbent for Pb was also tested by adding the adsorbents to real gold mine water which contains competitive metal ions.     

蛋白质在疏水色谱中的变性热力学

研究21-80℃温度范围内一些蛋白质和小分子在疏水相互作用色谱中的热行为。利用Van't Hoff作图(lnk'-1/T)测定蛋白质分子的热力学参数(ΔH°, ΔS°和ΔG°), 根据标准熵变(ΔS°)和标准自由能变(ΔG°)判断蛋白质在色谱过程中的构象变化, 通过ΔH°-ΔS°的线性关系估计蛋白质变性时的"补偿温度"(β), 鉴定蛋白质在疏水相互作用色谱中保留机理的同一性。     

WO3 thermodynamic properties at 80–1256 K revisited

Journal of Thermal Analysis and Calorimetry - Thermodynamic properties (heat capacity Cp, entropy S°, enthalpy change ΔH° and reduced Gibbs energy ΔΦ°) of crystalline...     

Study on the Interaction between Theasinesin and Bovine Serum Albumin by Fluorescence Method

Theasinesin (TS), a polymer of epigallocatechin gallate, is the main active component of tea polyphenols. Several studies indicate that tea polyphenols have extensive pharmacology activity. However, there is little research about the transportation and metabolism of tea polyphenols in vivo. Serum albumin is a most important protein serving as a depot protein and as a transport protein for many drugs and other bioactive small molecules. This study observed the interaction between TS and bovine serum albumin (BSA) by fluorescence and absorption spectroscopy. The results showed that both static and dynamic quenching occurred in the fluorescence quenching of BSA by TS. The binding sites number is 1.1845 and the binding sites may close to the tyrosine residues. The thermodynamic parameters ΔH°, ΔG°, ΔS° at temperatures 310 K were calculated 1.7 KJ, ?35.4 KJ, and 0.12 KJ. The negative sign of free energy (ΔG°) means that the interaction process is spontaneous. The positive enthalpy (ΔH°) and entropy (ΔS°) values of the interaction of TS and BSA indicate that the binding is mainly entropy-driven and the enthalpy is unfavorable for it, the hydrophobic forces playing a major role in the reaction. A distance of 4.037 nm was found between donor (BSA) and acceptor (TS), obtained according to the F?rster theory of non-radiation energy transfer, which indicates that the energy transfer from BSA to TS occurs with high probability. The results of synchronous fluorescence spectra and UV–vis absorption spectra showed that the peptide strands of BSA molecules extended more and the hydrophobicity decreased with the addition of TS.     

Conversion of teak wood waste into microwave-irradiated activated carbon for cationic methylene blue dye removal: Optimization and batch studies

The objective of this study is to find optimum preparation conditions in converting teak wood waste into activated carbon (TWAC) and to evaluate its performance in adsorbing cationic dye of methylene blue (MB). TWAC was produced via physiochemical activation (potassium hydroxide, KOH chemical treatment, and carbon dioxide, CO₂ gasification) and heated through microwave irradiation technique. With the aid of response surface methodology (RSM), optimized TWAC was successfully synthesized at radiation power, radiation time, and impregnation ratio (IR) of 366 W, 5.30 min, and 1.15 g/g, respectively. These preparation conditions produced TWAC with MB adsorption uptakes of 66.69 mg/g and a yield of 38.23%. Characteristics of TWAC in terms of BET surface area, mesopores surface area, total pore volume, and average pore diameter were determined to be 1345.25 m²/g, 878.63 m²/g, 0.6140 cm³/g, and 2.85 nm, respectively. Isotherm studies divulged that the MB-TWAC adsorption system followed the Langmuir model with a maximum monolayer adsorption capacity of 567.52 mg/g. In terms of kinetic studies, this adsorption system fit pseudo-second order model the best whereas Boyd plot confirmed that the adsorption process was controlled by the film diffusion mechanism. Thermodynamic parameters of enthalpy change, ΔH°, entropy change, ΔS°, Gibbs free energy, ΔG° and Arrhenius activation energy, E_a were calculated to be ?4.06 kJ/mol, 0.06 kJ/mol.K, –22.69 kJ/mol and 16.03 kJ/mol, respectively. The activation and microwave heating methods employed succeeded to produce TWAC with excellent adsorption performance in removing MB dye. TWAC was also successfully regenerated for 5 cycles via microwave heating technique.     

A thermodynamic study of α-, β-, and γ-cyclodextrin-complexed m-methyl red in alkaline solutions

The UV/Visible spectra of m-methyl red (m-MR) ({3-[4-(dimethyl-amino) phenylazo] benzoic acid}) were examined in basic, acidic and strongly acidic aqueous solutions. The observed spectra of m-MR were analyzed and compared with the tautomeric and resonance structures that suggested theoretically. Three isosbestic points in the spectra were observed around 508, 464 and 443 nm representing three different equilibriums between four different species of m-MR. The inclusion constant (K_f) for the inclusion of basic form of m-MR with alpha-, Beta-, and gamma-Cyclodextrin (α-, β- and γ-CD) was evaluated at different temperatures using Benesi-Hildebrand method. The values of K_f at 25 °C were found to be 8.70 × 10³, 4.93 × 10³ mol^?1 dm³ and 2.95 × 10⁷ mol^?2 dm⁶ basis on the inclusion complex ratios (m-MR:CD) of 1:1, 1:1, and 2:1 respectively. The values of the thermodynamic quantities ΔH°, ΔS°, ΔG° for the different inclusion processes were calculated by using Van’t Hoff plot. For all cases of the studied inclusion processes, these inclusions were favored through entropy and enthalpy changes.     

Laterite clay-based geopolymer as a potential adsorbent for the heavy metals removal from aqueous solutions

This study is focused on the investigation of low iron lateritic clay-based geopolymer as a potential adsorbent for the higher uptake of Ni(II) and Co(II) ions from aqueous solutions. BET analysis revealed that the sieved geopolymer sample (SGS) was characterized by 17.441 m²/g of surface area, 0.005 cm³/g of pore volume, and 13.549 Å of pore diameter. SEM investigation confirmed the presence of pores and cavities onto the surface of SGS. XRD analysis showed that the geopolymer is semi-crystalline in nature. It was found that the adsorption ability of SGS remained 520 mg/g for Ni(II) ions and 500 mg/g for Co(II) ions when 0.5 M solutions were stirred with SGS for 60 min. The temperature and pH of the solution were maintained at 60 °C and 7.0, respectively. The adsorption data of both heavy metal (HM) ions fitted best in the pseudo-second-order kinetic model. The low activation energy value i.e. 2.507 kJ/mol for Ni(II) ions and 2.286 kJ/mol for Co(II) ions confirmed adsorption is physisorption. Adsorption data were tested with Langmuir and Freundlich models, the data showed comparatively better fitting in the Freundlich model. The greater value of monolayer adsorption capacity (Xm) for Ni(II) ions was found 1.77 × 10⁻² mol/g while for Co(II) ions it remained 1.69 × 10⁻² mol/g confirming the better interaction of metal ions with the adsorbent surface. Negative values of ΔG° confirmed the spontaneity of the process while the positive value of ΔS° showed the randomness of adsorbate particles. The positive value of ΔH° showed that the adsorption process remained endothermic for both HM ions. The experimental results confirmed the ability of laterite clay-based geopolymer for better removal of HM ions and hence can be employed for the wastewater treatment processes at low-cost adsorbent.     

An endor and ESR study of the radical cation of N,N′-bis-(4-fluorophenyl)-4,4′-bipyridylium dichloride

The ESR and ENDOR spectra of the radical cation of N,N′-bis-(4-fluoro-phenyl)-4-4′-bipyridylium dichloride (fluorophenylquat FPQ) in methanol was studied over a temperature range from +_40° to ?90°. The ENDOR technique was used to obtain accurately the splitting constans for a highly complicated ESR spectrum and computer simulation showed excellent agreement. Fluorine ENDOR resonance was clearly observed with a line width similar to that of the protons. On decreasing the temperature the concentration of the radical cation decreases until at ?90° the ESR intensity was very small. This process is reversible and concentration studies indicate that the radical cation is in equilibrium with a diamagnetic dimer species. The thermodynamic parameters ΔH°, ΔG° and ΔS° for the process are reported.     

Adsorption of U(VI) from aqueous solution by cross-linked rice straw

Adsorption of U(VI) from aqueous solution by cross-linked rice straw(CRS) was studied with batch experiments. The adsorbent was characterized by Fourier transform infrared spectroscopy (FT-IR). The effect of contact time, initial pH, temperature, adsorbent amount and initial U(VI) concentration was investigated. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) adsorption isotherms and two kinetic models of pseudo-first-order and pseudo-second-order were used to describe the adsorption process. The result showed that the adsorption process was highly pH dependent and the favorable initial pH was 5.0. The adsorption process was rapid within first 60 min and equilibrium reached at 100 min. The adsorption process could be well defined by the Langmuir isotherm and pseudo-second-order equation, which indicated that the chemical adsorption was the rate-limiting step. The thermodynamic parameters (?H°, ?S°, ?G°) of the adsorption system were also calculated. The negative value of ?H° and ?G° indicated that the reaction was endothermic and spontaneous in nature. All the above suggested that CRS has considerable potential for the removal of U(VI) from aqueous solution.     

Fe3O4-CuO-activated carbon composite as an efficient adsorbent for bromophenol blue dye removal from aqueous solutions

Dye wastewater from industries is posing tremendous health hazards. The lethal dyes can be eliminated using nanomaterials and scientific approach like adsorption which is facile, cheap, safe as well as ecofriendly. Fe₃O₄-CuO-AC composite was prepared by a hydrothermal method and used for the removal of dyes in wastewater. The composite material was characterized by various techniques such as XRD, SEM, EDS, TEM and FT-IR. The Fe₃O₄-CuO-AC composite was used to treat five types of dyes in water. Fe₃O₄-CuO-AC composite showed the highest adsorption capability for bromophenol blue (BPB) dye. The effects of initial concentration, pH, the amount of adsorbent and temperature were also studied. The optimum conditions were found to be 20 ppm dye concentration, pH 9, an adsorbent dose of 0.06 gL^─1 at 65 °C. A removal efficiency of 97% was obtained for BPB dye during 120 min of adsorption. Kinetic studies indicated that a pseudo-second order is the most suitable model for the adsorption process. The Fe₃O₄-CuO-AC composite showed better adsorption capacity as compare to Fe₃O₄-AC except for the Methyl green dye. The maximum adsorption capacity was found to be 88.60 mg/g for BPB. Additionally, the thermodynamic parameters (ΔS°, ΔH° and ΔG°) showed that the process was spontaneous and exothermic. All the above results revealed that the Fe₃O₄-CuO-AC compositecan be an effective adsorbent for removing dyes from wastewater.