Science.gov

Sample records for adsorption capacity qm

  1. Simulation of Adsorption Processes at Metallic Interfaces: An Image Charge Augmented QM/MM Approach.

    PubMed

    Golze, Dorothea; Iannuzzi, Marcella; Nguyen, Manh-Thuong; Passerone, Daniele; Hutter, Jürg

    2013-11-12

    A novel method for including polarization effects within hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of adsorbate-metal systems is presented. The interactions between adsorbate (QM) and metallic substrate (MM) are described at the MM level of theory. Induction effects are additionally accounted for by applying the image charge formulation. The charge distribution induced within the metallic substrate is modeled by a set of Gaussian charges (image charges) centered at the metal atoms. The image charges and the electrostatic response of the QM potential are determined self-consistently by imposing the constant-potential condition within the metal. The implementation is embedded in a highly efficient Gaussian and plane wave framework and is naturally suited for periodic systems. Even though the electronic properties of the metallic substrate are not taken into account explicitly, the augmented QM/MM scheme can reproduce characteristic polarization effects of the adsorbate. The method is assessed through the investigation of structural and electronic properties of benzene, nitrobenzene, thymine, and guanine on Au(111). The study of small water clusters adsorbed on Pt(111) is also reported in order to demonstrate that the approach provides a sizable correction of the MM-based interactions between adsorbate and substrate. Large-scale molecular dynamics (MD) simulations of a water film in contact with a Pt(111) surface show that the method is suitable for simulations of liquid/metal interfaces at reduced computational cost.

  2. Simulation of Adsorption Processes at Metallic Interfaces: An Image Charge Augmented QM/MM Approach.

    PubMed

    Golze, Dorothea; Iannuzzi, Marcella; Nguyen, Manh-Thuong; Passerone, Daniele; Hutter, Jürg

    2013-11-12

    A novel method for including polarization effects within hybrid quantum mechanics/molecular mechanics (QM/MM) simulations of adsorbate-metal systems is presented. The interactions between adsorbate (QM) and metallic substrate (MM) are described at the MM level of theory. Induction effects are additionally accounted for by applying the image charge formulation. The charge distribution induced within the metallic substrate is modeled by a set of Gaussian charges (image charges) centered at the metal atoms. The image charges and the electrostatic response of the QM potential are determined self-consistently by imposing the constant-potential condition within the metal. The implementation is embedded in a highly efficient Gaussian and plane wave framework and is naturally suited for periodic systems. Even though the electronic properties of the metallic substrate are not taken into account explicitly, the augmented QM/MM scheme can reproduce characteristic polarization effects of the adsorbate. The method is assessed through the investigation of structural and electronic properties of benzene, nitrobenzene, thymine, and guanine on Au(111). The study of small water clusters adsorbed on Pt(111) is also reported in order to demonstrate that the approach provides a sizable correction of the MM-based interactions between adsorbate and substrate. Large-scale molecular dynamics (MD) simulations of a water film in contact with a Pt(111) surface show that the method is suitable for simulations of liquid/metal interfaces at reduced computational cost. PMID:26583423

  3. Gas adsorption capacity of wood pellets

    DOE PAGES

    Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim; Lau, A.; Bi, X. T.

    2016-02-03

    In this paper, temperature-programmed desorption (TPD) analysis was used to measure and analyze the adsorption of off-gases and oxygen by wood pellets during storage. Such information on how these gases interact with the material helps in the understanding of the purging/stripping behavior of off-gases to develop effective ventilation strategies for wood pellets. Steam-exploded pellets showed the lowest carbon dioxide (CO2) uptake compared to the regular and torrefied pellets. The high CO2 adsorption capacity of the torrefied pellets could be attributed to their porous structure and therefore greater available surface area. Quantifying the uptake of carbon monoxide by pellets was challengingmore » due to chemical adsorption, which formed a strong bond between the material and carbon monoxide. The estimated energy of desorption for CO (97.8 kJ/mol) was very high relative to that for CO2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO2, respectively. As for oxygen, the strong bonds that formed between the material and oxygen verified the existence of chemical adsorption and formation of an intermediate material.« less

  4. Protein adsorption to poly(ethylenimine)-modified Sepharose FF: I. a critical ionic capacity for drastically enhanced capacity and uptake kinetics.

    PubMed

    Yu, Lin-Ling; Tao, Shi-Peng; Dong, Xiao-Yan; Sun, Yan

    2013-08-30

    To explore the details of protein uptake to polymer-grafted ion exchangers, Sepharose FF was modified with poly(ethylenimine) (PEI) to prepare anion exchanger of 10 different ionic capacities (ICs, 100-1220mmol/L). Adsorption equilibria and kinetics of bovine serum albumin (BSA) were then studied. It is found that ionic capacity, i.e., the coupling density of PEI, had significant effect on both adsorption capacity (qm) and effective protein diffusivity (De). With increasing ionic capacity, the qm value increased rapidly at IC<260mmol/L and then increased slowly till reaching a plateau at IC=600mmol/L. In the IC range of 100-600mmol/L, however, the De values kept at a low level (De/D0<0.07); it first decreased from 0.05±0.01 at IC=100mmol/L to 0.01±0.01 at IC=260mmol/L and then increased to 0.06±0.01 at IC=600mmol/L. Thereafter, sharp increases of the qm and De values [36% (from 201 to 273mg/mL) and 670% (from 0.06±0.01 to 0.49±0.04), respectively] were observed in the narrow range of IC from 600 to 740mmol/L. Finally, at IC>740mmol/L, the qm value decreased significantly while the De value increased moderately with increasing the IC. The results indicate that PEI chains played an important role in protein adsorption and transport. In brief, there was a critical IC (cIC) or PEI chain density, above which protein adsorption and transport behaviors changed drastically. The cIC was identified to be about 600mmol/L. Estimation of PEI grafting-layer thickness suggests that PEI chains formed an extended three-dimensional grafting-layer at IC>cIC, which provided high flexibility as well as accessibility of the chains for protein binding. Therefore, at IC>cIC, the adjacent PEI chains became close and flexible enough, leading to facilitated transport of adsorbed protein molecules by the interactions of neighboring chains mediated by the bound molecules. It is regarded as "chain delivery" effect. At the same time, improved accessibility of binding sites led the

  5. Effect of carboxyethylation degree on the adsorption capacity of Cu(II) by N-(2-carboxyethyl)chitosan from squid pens.

    PubMed

    Huang, Jun; Xie, Haihua; Ye, Hui; Xie, Tian; Lin, Yuecheng; Gong, Jinyan; Jiang, Chengjun; Wu, Yuanfeng; Liu, Shiwang; Cui, Yanli; Mao, Jianwei; Mei, Lehe

    2016-03-15

    Chitosan was prepared by N-deacetylation of squid pens β-chitin, and N-carboxyethylated chitosan (N-CECS) with different degrees of substitution (DS) were synthesized. DS values of N-CECS derivatives calculated by (1)H nuclear magnetic resonance (NMR) spectroscopy were 0.60, 1.02 and 1.46, respectively. The adsorption capacity of Cu(II) by N-CECS correlated well with the DS and pH ranging from 3.2 to 5.8. The maximum Cu(II) adsorption capacity (qm) of all three N-CECS at pH 5.4 was 207.5mg g(-1), which was 1.4-fold higher than that of chitosan. The adsorption equilibrium process was better described by the Langmuir than Freundlich isotherm model. Adsorption of Cu(II) ion onto N-CECS followed a pseudo-second order mechanism with chemisorption as the rate-limiting step. In a ternary adsorption system, the adsorption capacity of Cu(II) by N-CECS also presented high values, and qm for Cu(II), Cd(II), and Pb(II) were 150.2, 28.8, and 187.9mg g(-1), respectively.

  6. Evaluation of the potassium adsorption capacity of a potassium adsorption filter during rapid blood transfusion.

    PubMed

    Matsuura, H; Akatsuka, Y; Muramatsu, C; Isogai, S; Sugiura, Y; Arakawa, S; Murayama, M; Kurahashi, M; Takasuga, H; Oshige, T; Yuba, T; Mizuta, S; Emi, N

    2015-05-01

    The concentration of extracellular potassium in red blood cell concentrates (RCCs) increases during storage, leading to risk of hyperkalemia. A potassium adsorption filter (PAF) can eliminate the potassium at normal blood transfusion. This study aimed to investigate the potassium adsorption capacity of a PAF during rapid blood transfusion. We tested several different potassium concentrations under a rapid transfusion condition using a pressure bag. The adsorption rates of the 70-mEq/l model were 76·8%. The PAF showed good potassium adsorption capacity, suggesting that this filter may provide a convenient method to prevent hyperkalemia during rapid blood transfusion.

  7. Evaluating the Adsorptive Capacities of Chemsorb 1000 and Chemsorb 1425

    NASA Technical Reports Server (NTRS)

    Monje, Oscar Alberto Monje; Surma, Jan M.; Johnsey, Marissa N.; Melendez, Orlando

    2014-01-01

    The Air Revitalization Lab at KSC tested Chemsorb 1000 and 1425, two candidate sorbents for use in future air revitalization technologies being evaluated by the ARREM project. Chemsorb 1000 and 1425 are granular coconut-shell activated carbon sorbents produced by Molecular Products, Inc. that may be used in the TCCS. Chemsorb 1000 is a high grade activated carbon for organic vapor adsorption. In contrast, Chemsorb 1425 is a high-grade impregnated activated carbon for adsorption of airborne ammonia and amines. Chemsorb 1000 was challenged with simulated spacecraft gas streams in order to determine its adsorptive capacities for mixtures of volatile organics compounds. Chemsorb 1425 was challenged with various NH3 concentrations to determine its adsorptive capacity.

  8. High capacity adsorption media and method of producing

    DOEpatents

    Tranter, Troy J.; Mann, Nicholas R.; Todd, Terry A.; Herbst, Ronald S.

    2010-10-05

    A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving and/or suspending at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

  9. High capacity adsorption media and method of producing

    DOEpatents

    Tranter, Troy J.; Herbst, R. Scott; Mann, Nicholas R.; Todd, Terry A.

    2008-05-06

    A method of producing an adsorption medium to remove at least one constituent from a feed stream. The method comprises dissolving at least one metal compound in a solvent to form a metal solution, dissolving polyacrylonitrile into the metal solution to form a PAN-metal solution, and depositing the PAN-metal solution into a quenching bath to produce the adsorption medium. The at least one constituent, such as arsenic, selenium, or antimony, is removed from the feed stream by passing the feed stream through the adsorption medium. An adsorption medium having an increased metal loading and increased capacity for arresting the at least one constituent to be removed is also disclosed. The adsorption medium includes a polyacrylonitrile matrix and at least one metal hydroxide incorporated into the polyacrylonitrile matrix.

  10. Evaluation of the adsorption capacity of alkali-treated waste materials for the adsorption of sulphamethoxazole.

    PubMed

    Kurup, Lisha

    2012-01-01

    The present work is to develop potential adsorbents from waste material and employ them for the removal of a hazardous antibacterial, sulphamethoxazole, from the wastewater by the Adsorption technique. The Adsorption technique was used to impound the dangerous antibiotics from wastewater using Deoiled Soya (DOS), an agricultural waste, and Water Hyacinth (WH), a prolific colonizer. The adsorption capacity of these adsorbents was further enhanced by treating them with sodium hydroxide solution and it was seen that the adsorption capacity increases by 10 to 25%. Hence a comparative account of the adsorption studies of all the four adsorbents, i.e. DOS, Alkali-treated DOS, WH and Alkali-treated Water Hyacinth has been discussed in this paper. Different isotherms like Freundlich, Langmuir and Dubinin-Radushkevich were also deduced from the adsorption data. Isotherm studies were in turn used in estimating the thermodynamic parameters. DOS showed sorption capacity of 0.0007 mol g(-1) while Alkali-treated Deoiled Soya exhibited 0.0011 mol g(-1) of sorption capacity, which reveals that the adsorption is higher in case of alkali-treated adsorbent. The mean sorption energy (E) was obtained between 9 and 12 kJ mol, which shows that the reaction proceeds by ion exchange reaction. Kinetic study reveals that the reaction follows pseudo-second-order rate equation. Moreover, mass transfer studies performed for the ongoing processes show that the mass transfer coefficient obtained for alkali-treated moieties was higher than the parent moieties. The breakthrough curves plotted from the column studies show percentage saturation of 90-98%. About 87-97% of sulphamethoxazole was recovered from column by desorption. PMID:22508113

  11. Effect of calcium on adsorption capacity of powdered activated carbon.

    PubMed

    Li, Gang; Shang, Junteng; Wang, Ying; Li, Yansheng; Gao, Hong

    2013-12-01

    We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca(2+), were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca(2+) was doped into HA. Also, HA and Ca(2+) taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca(2+) concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca(2+), pH had a small rise, but the extent of pH of later solution was bigger. PMID:25078809

  12. Adsorption of Pb(II) on mesoporous activated carbons fabricated from water hyacinth using H3PO4 activation: Adsorption capacity, kinetic and isotherm studies

    NASA Astrophysics Data System (ADS)

    Huang, Yang; Li, Shunxing; Chen, Jianhua; Zhang, Xueliang; Chen, Yiping

    2014-02-01

    Activated carbons with high mesoporosity and abundant oxygen-containing functional groups were prepared from water hyacinth using H3PO4 activation (WHAC) to eliminate Pb(II) in water. Characterizations of the WHAC were performed using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The BET analysis showed that WHAC possesses a high mesoporosity (93.9%) with a BET surface area of 423.6 m2/g. The presence of oxygen-containing functional groups including hydroxyl, carbonyl, carboxyl and phosphate groups renders the WHAC a favorable adsorbent for Pb(II) with the maximum monolayer capacity (qm) 118.8 mg/g. The adsorption behavior follows pseudo-first order kinetic and Langmuir isotherm. The desorption study demonstrated that the WHAC could be readily regenerated using 0.1 M HCl (pH = 1.0). The desorbed WHAC could be reused at least six times without significant adsorption capacity reduction. The adsorption process was spontaneous and endothermic with ΔG (-0.27, -1.13, -3.02, -3.62, -5.54, and -9.31 kJ/mol) and ΔH (38.72 kJ/mol). Under the optimized conditions, a small amount of the adsorbent (1.0 g/L) could remove as much as 90.1% of Pb(II) (50 mg/L) in 20 min at pH 6.0 and temperature of 298 K. Therefore, the WHAC has a great potential to be an economical and efficient adsorbent in the treatment of lead-contaminated water.

  13. High-capacity adsorption of aniline using surface modification of lignocellulose-biomass jute fibers.

    PubMed

    Gao, Da-Wen; Hu, Qi; Pan, Hongyu; Jiang, Jiping; Wang, Peng

    2015-10-01

    Pyromellitic dianhydride (PMDA) modified jute fiber (MJF) were prepared with microwave treatment to generate a biosorbent for aniline removal. The characterization of the biosorbent was investigated by SEM, BET and FT-IR analysis to discuss the adsorption mechanism. The studies of various factors influencing the adsorption behavior indicated that the optimum dosage for aniline adsorption was 3g/L, the maximum adsorption capacity was observed at pH 7.0 and the adsorption process is spontaneous and endothermic. The aniline adsorption follows the pseudo second order kinetic model and Langmuir isotherm model. Moreover, the biosorbent could be regenerated through the desorption of aniline by using 0.5M HCl solution, and the adsorption capacity after regeneration is even higher than that of virgin MJF. All these results prove MJF is a promising adsorbent for aniline removal in wastewater.

  14. High-capacity adsorption of aniline using surface modification of lignocellulose-biomass jute fibers.

    PubMed

    Gao, Da-Wen; Hu, Qi; Pan, Hongyu; Jiang, Jiping; Wang, Peng

    2015-10-01

    Pyromellitic dianhydride (PMDA) modified jute fiber (MJF) were prepared with microwave treatment to generate a biosorbent for aniline removal. The characterization of the biosorbent was investigated by SEM, BET and FT-IR analysis to discuss the adsorption mechanism. The studies of various factors influencing the adsorption behavior indicated that the optimum dosage for aniline adsorption was 3g/L, the maximum adsorption capacity was observed at pH 7.0 and the adsorption process is spontaneous and endothermic. The aniline adsorption follows the pseudo second order kinetic model and Langmuir isotherm model. Moreover, the biosorbent could be regenerated through the desorption of aniline by using 0.5M HCl solution, and the adsorption capacity after regeneration is even higher than that of virgin MJF. All these results prove MJF is a promising adsorbent for aniline removal in wastewater. PMID:26172392

  15. Predicting the adsorption capacity and isotherm curvature of organic compounds onto activated carbons in natural waters.

    PubMed

    Hung, H W; Lin, T F

    2006-03-01

    A simple approach to predict the adsorption capacity and isotherm curvature of organic compounds onto activated carbon in natural water was investigated. A combination of the well-known equivalent background compound (EBC), and the simplified competitive adsorption model (SCAM) was employed to delineate the equilibrium capacity. This SCAM-EBC approach may reduce the numerical and experimental effort to obtain the parameters required to predict the adsorption capacity for a specific adsorption system. Several sets of experimental data, including weakly adsorbing (MTBE), strongly adsorbing compounds (TCP, atrazine, and chloroform), and two taste and odor causing compounds (MIB and geosmin) onto different activated carbons in three natural waters and a synthetic groundwater, were tested to verify the SCAM-EBC approach. Based on the approach, a parameter, called relative adsorptivity, describing the adsorption preference of the adsorbent between EBC and the target compound was employed to simulate the isotherm curvature in natural water. The relative adsorptivity of the SCAM-EBC approach is constant and can be directly obtained from the SCAM-EBC parameters in a specific adsorption system. The potential and extent of isotherm curvature can be simulated by only changing the parameter of relative adsorptivity. The marked isotherm curvature was found while the relative adsorptivity is larger than 2.0 to 4.0 for all the systems tested.

  16. Modeling high adsorption capacity and kinetics of organic macromolecules on super-powdered activated carbon.

    PubMed

    Matsui, Yoshihiko; Ando, Naoya; Yoshida, Tomoaki; Kurotobi, Ryuji; Matsushita, Taku; Ohno, Koichi

    2011-02-01

    The capacity to adsorb natural organic matter (NOM) and polystyrene sulfonates (PSSs) on small particle-size activated carbon (super-powdered activated carbon, SPAC) is higher than that on larger particle-size activated carbon (powdered-activated carbon, PAC). Increased adsorption capacity is likely attributable to the larger external surface area because the NOM and PSS molecules do not completely penetrate the adsorbent particle; they preferentially adsorb near the outer surface of the particle. In this study, we propose a new isotherm equation, the Shell Adsorption Model (SAM), to explain the higher adsorption capacity on smaller adsorbent particles and to describe quantitatively adsorption isotherms of activated carbons of different particle sizes: PAC and SPAC. The SAM was verified with the experimental data of PSS adsorption kinetics as well as equilibrium. SAM successfully characterized PSS adsorption isotherm data for SPACs and PAC simultaneously with the same model parameters. When SAM was incorporated into an adsorption kinetic model, kinetic decay curves for PSSs adsorbing onto activated carbons of different particle sizes could be simultaneously described with a single kinetics parameter value. On the other hand, when SAM was not incorporated into such an adsorption kinetic model and instead isotherms were described by the Freundlich model, the kinetic decay curves were not well described. The success of the SAM further supports the adsorption mechanism of PSSs preferentially adsorbing near the outer surface of activated carbon particles. PMID:21172719

  17. Structural properties and adsorption capacity of holocellulose aerogels synthesized from an alkali hydroxide-urea solution

    NASA Astrophysics Data System (ADS)

    Kwon, Gu-Joong; Kim, Dae-Young; Hwang, Jae-Hyun; Kang, Joo-Hyon

    2014-05-01

    A tulip tree was used to synthesize a holocellulose aerogel from an aqueous alkali hydroxide-urea solution with the substitution of an organic solvent followed by freeze-drying. For comparison, the synthesized holocellulose aerogels were divided into two groups according to the source of the hydrogel, an upper suspended layer and a bottom concentrated layer of the centrifuged solution of cellulose and NaOH/urea solvents. We investigated the effects of the temperature of the pre-cooled NaOH/urea solution ( i.e., dissolution temperature) on the pore structure and the adsorption capacity of the holocellulose aerogel. A nano-fibrillar network structure of the holocellulose aerogel was observed, with little morphological difference in pore structure for different dissolution temperatures. Both micropores and mesopores were observed in the holocellulose aerogel. The specific surface area of the holocellulose aerogel was generally greater at lower dissolution temperatures. In a series of adsorption tests using methylene blue, the holocellulose aerogel showed the greatest adsorption capacity at the lowest dissolution temperature tested (-2°C). However, the dissolution temperature generally had little effect on the adsorption capacity. The holocellulose aerogel produced from the upper suspended layer of the centrifuged hydrogel solution showed a greater porosity and adsorption capacity than the one produced from the bottom concentrated layer. Overall, the aerogel made by utilizing a delignified tulip tree display a high surface area and a high adsorption property, indicating its possible application in eco-friendly adsorption materials.

  18. QM02 Strength Measurement

    SciTech Connect

    Welch, J; Wu, J.; /SLAC

    2010-11-24

    In late April, Paul Emma reported that his orbit fitting program could find a reasonably good fit only if the strength of QM02 was changed from design value of -5.83 kG to -6.25 kG - a strength change of 7.3%. In late May, we made a focal length measurement of QM02 by turning off all focusing optics between YC07 and BPMS1 (in the spectrometer line) except for QM02 and adjusted the strength of QM02 so that vertical kicks by YC07 did not produce any displacements at BPMS1 (see Figure 1). The result was quoted in the LCLS elog was that QM02 appeared to 6% too weak, and approximately agreed with Paul's observation. The analysis used for the entry in the log book was based on the thin lens approximation and used the following numbers: Distance YC07 to QM02 - 5.128 m; Distance QM02 to BPMS1 - 1.778 m; and Energy - 135 MeV. These distances were computed from the X,Z coordinates given the on the large plot of the Injector on the wall of the control room. On review of the MAD output file coordinates, it seems that the distance used for QM02 to BPMS1 is not 1.778 m. The correct value is Distance, center of QM02 to BPMS1 - 1.845 m. There may be a typo on the wall chart values for the coordinates of BPMS1, or perhaps there was a misinterpretation of edge versus center of QM02. In any case, the effect of this change is that the thin lens estimate changes from 6% too weak to 9% too weak. At John Galayda's suggestion, we looked into the thin lens versus thick lens approximation. A Mathematica program was written to solve for the K value of the QM02, in the thick lens approximation, that provides point to point focusing from YC07 to BPMS1, and to compare this number with the value obtained using the thin lens approximation. The length of QM02 used in the thick lens calculation is the effective length determined by magnetic measurements of 0.108 m. The result of the Mathematica calculation is that the thin lens approximation predicts less magnet strength is required to produce the

  19. Enhancement of the anionic dye adsorption capacity of clinoptilolite by Fe(3+)-grafting.

    PubMed

    Akgül, Murat

    2014-02-28

    In this paper, a batch system was applied to study the adsorption behavior of congo red (CR) on raw and modified clinoptilolites. Raw clinoptilolite (Raw-CL) was treated with Fe(NO3)3 in ethanol to obtain its iron-grafted form (Fe-CL). Adsorbents were characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR), energy dispersive X-ray spectroscopy (EDX), thermogravimetric/differential thermal analysis (TG/DTA), zeta-potential measurement and N2 gas adsorption-desorption techniques. Effects of the experimental parameters (initial pH, dye concentration, temperature and adsorption time) were investigated to find optimum conditions that result in highest adsorption capacity for CR removal. The obtained results suggest that the solution pH appears to be a key factor of the CR adsorption process. The maximum dye adsorption was achieved with Fe-CL adsorbent at pH ∼6.3 and the corresponding adsorption capacity was found to be 36.7mg/g, which is higher than that of its raw counterpart (16.9mg/g). A significant decrease in CR removal was given by Fe-CL between pH 7 and 11 opposite to Raw-CL which has nearly constant qe in the same pH range. The Fe(3+)-grafting increased the zeta potential of raw clinoptilolite, leading to a higher adsorption capacity compared to that of unfunctionalized adsorbent. Also, temperature change was found to have a significant effect on the adsorption process. PMID:24413045

  20. Ultrahigh CO2 adsorption capacity on carbon molecular sieves at room temperature.

    PubMed

    Silvestre-Albero, Joaquín; Wahby, Anass; Sepúlveda-Escribano, Antonio; Martínez-Escandell, Manuel; Kaneko, Katsumi; Rodríguez-Reinoso, Francisco

    2011-06-28

    Although metal-organic framework (MOF) materials have been postulated as superior to any other sorbent for CO(2) adsorption at room temperature, here we prove that the appropriate selection of the raw material and the synthesis conditions allows the preparation of carbon molecular sieves (CMSs) with adsorption capacity, on a volumetric basis, highly exceeding those reported in the literature for MOFs. Furthermore, the excellent sorption properties of CMSs over the whole pressure range (up to 50 bar) are fully reversible after different adsorption/desorption cycles.

  1. Correlation and prediction of adsorption capacity and affinity of aromatic compounds on carbon nanotubes.

    PubMed

    Wu, Wenhao; Yang, Kun; Chen, Wei; Wang, Wendi; Zhang, Jie; Lin, Daohui; Xing, Baoshan

    2016-01-01

    Adsorption of 22 nonpolar and polar aromatic compounds on 10 carbon nanotubes (CNTs) with various diameters, lengths and surface oxygen-containing group contents was investigated to develop predictive correlations for adsorption, using the isotherm fitting of Polanyi theory-based Dubinin-Ashtakhov (DA) model. Adsorption capacity of aromatic compounds on CNTs is negatively correlated with melting points of aromatic compounds, and surface oxygen-containing group contents and surface area ratios of mesopores to total pores of CNTs, but positively correlated with total surface area of CNTs. Adsorption affinity is positively correlated with solvatochromic parameters of aromatic compounds, independent of tube lengths and surface oxygen-containing group contents of CNTs, but negatively correlated with surface area ratios of mesopores to total pores of CNTs. The correlations of adsorption capacity and adsorption affinity with properties of both aromatic compounds and CNTs clearly have physical significance, can be used successfully with DA model to predict adsorption of aromatic compounds on CNTs from the well-known physiochemical properties of aromatic compounds (i.e., solvatochromic parameters, melting points) and CNTs (i.e., surface area and total acidic group contents), and thus can facilitate the environmental application of CNTs as sorbents and environmental risk assessment of both aromatic contaminants and CNTs.

  2. Carbon nanotube membranes with ultrahigh specific adsorption capacity for water desalination and purification.

    PubMed

    Yang, Hui Ying; Han, Zhao Jun; Yu, Siu Fung; Pey, Kin Leong; Ostrikov, Kostya; Karnik, Rohit

    2013-01-01

    Development of technologies for water desalination and purification is critical to meet the global challenges of insufficient water supply and inadequate sanitation, especially for point-of-use applications. Conventional desalination methods are energy and operationally intensive, whereas adsorption-based techniques are simple and easy to use for point-of-use water purification, yet their capacity to remove salts is limited. Here we report that plasma-modified ultralong carbon nanotubes exhibit ultrahigh specific adsorption capacity for salt (exceeding 400% by weight) that is two orders of magnitude higher than that found in the current state-of-the-art activated carbon-based water treatment systems. We exploit this adsorption capacity in ultralong carbon nanotube-based membranes that can remove salt, as well as organic and metal contaminants. These ultralong carbon nanotube-based membranes may lead to next-generation rechargeable, point-of-use potable water purification appliances with superior desalination, disinfection and filtration properties. PMID:23941894

  3. Carbon nanotube membranes with ultrahigh specific adsorption capacity for water desalination and purification.

    PubMed

    Yang, Hui Ying; Han, Zhao Jun; Yu, Siu Fung; Pey, Kin Leong; Ostrikov, Kostya; Karnik, Rohit

    2013-01-01

    Development of technologies for water desalination and purification is critical to meet the global challenges of insufficient water supply and inadequate sanitation, especially for point-of-use applications. Conventional desalination methods are energy and operationally intensive, whereas adsorption-based techniques are simple and easy to use for point-of-use water purification, yet their capacity to remove salts is limited. Here we report that plasma-modified ultralong carbon nanotubes exhibit ultrahigh specific adsorption capacity for salt (exceeding 400% by weight) that is two orders of magnitude higher than that found in the current state-of-the-art activated carbon-based water treatment systems. We exploit this adsorption capacity in ultralong carbon nanotube-based membranes that can remove salt, as well as organic and metal contaminants. These ultralong carbon nanotube-based membranes may lead to next-generation rechargeable, point-of-use potable water purification appliances with superior desalination, disinfection and filtration properties.

  4. Investigation of Morphology and Hydrogen Adsorption Capacity of Disordered Carbons

    NASA Astrophysics Data System (ADS)

    He, Lilin; Melnichenko, Yuri; Gallego, Nidia; Contescu, Cristian

    2014-03-01

    We have applied small angle neutron scattering (SANS) technique to study the morphologies and hydrogen adsorption capabilities of wood-based ultramicroporous carbon and poly(furfuryl alcohol) derived carbon. The Polydispersed Spherical model and chord length analysis of the scattering profiles were performed to obtain morphological parameters such as average pore size and pore size distribution of the dry carbons, which agreed reasonably well with the independent gas sorption measurements. The hydrogen physisorbed in these two carbons at room temperature and moderate pressures was investigated by In-situ SANS measurements. The experimental data analyzed using a modified Kalliat model for decoupling scattering contributions from pores with different sizes indicates that the molecular hydrogen condenses preferentially in narrow micropores at all measured pressures, which supports the theoretical prediction by quantum mechanical and thermodynamical models.

  5. Adsorption of selected pharmaceuticals and an endocrine disrupting compound by granular activated carbon. 1. Adsorption capacity and kinetics

    SciTech Connect

    Yu, Z.; Peldszus, S.; Huck, P.M.

    2009-03-01

    The adsorption of two representative PhACs (naproxen and carbamazepine) and one EDC (nonylphenol) were evaluated on two granular activated carbons (GAC) namely coal-based Calgon Filtrasorb 400 and coconut shell-based PICA CTIF TE. The primary objective was to investigate preloading effects by natural organic matter (NOM) on adsorption capacity and kinetics under conditions and concentrations (i.e., ng/L) relevant for drinking water treatment. Isotherms demonstrated that all compounds were significantly negatively impacted by NOM fouling. Adsorption capacity reduction was most severe for the acidic naproxen, followed by the neutral carbamazepine and then the more hydrophobic nonylphenol. The GAC with the wider pore size distribution had considerably greater NOM loading, resulting in lower adsorption capacity. Different patterns for the change in Freundlich KF and 1/n with time revealed different competitive mechanisms for the different compounds. Mass transport coefficients determined by short fixed-bed (SFB) tests with virgin and preloaded GAC demonstrated that film diffusion primarily controls mass transfer on virgin and preloaded carbon. Naproxen suffered the greatest deteriorative effect on kinetic parameters due to preloading, followed by carbamazepine, and then nonylphenol. A type of surface NOM/biofilm, which appeared to add an additional mass transfer resistance layer and thus reduce film diffusion, was observed. In addition, electrostatic interactions between NOM/biofilm and the investigated compounds are proposed to contribute to the reduction of film diffusion. A companion paper building on this work describes treatability studies in pilot-scale GAC adsorbers and the effectiveness of a selected fixed-bed model. 32 refs., 3 figs., 2 tabs.

  6. Influence of in situ biofilm coverage on the radionuclide adsorption capacity of subsurface granite.

    PubMed

    Anderson, Craig; Jakobsson, Anna-Maria; Pedersen, Karsten

    2007-02-01

    Any migration of radionuclides from nuclear waste repositories is expected to be mitigated by adsorption to the host rocks surrounding hydraulically conductive fractures. Fluid rock interfaces are considered to be important barriers for nuclear waste disposal schemes but their adsorptive capacity can be affected by the growth of microbial biofilms. This study indicates that biofilms growing on fracture surfaces decrease the rocks adsorption capacity for migrating radionuclides except for trivalent species. Potential suppression of adsorption by biofilms should, therefore, be accounted for in performance safety assessment models. In this study, the adsorptive capacity of in situ anaerobic biofilms grown 450 m underground on either glass or granite slides was compared to the capacity of the same surfaces without biofilms. Surfaces were exposed to the radiotracers 60Co(II), 147Pm(III), 241Am(III), 234Th(IV), and 237Np(V) for a period of 660 h in a pH neutral anaerobic synthetic groundwater. Adsorption was investigated at multiple time points over the 660 h using liquid scintillation and ICP-MS. Results indicate that these surfaces adsorb between 0 and 85% of the added tracers under the conditions of the specific experiments. After 660 h, the distribution coefficients, R (ratio between what is sorbed and what is left in the aqueous phase), approached 3 x 10(4) m for 60Co, 3 x 10(5) m for 147Pm and 241Am, 1 x 10(6)m for 234Th, and 1 x 10(3) m for 237Np. The highest rate of adsorption was during the first 200 h of the adsorption experiments and started to approach equilibrium after 500 h. Adsorption to colloids and precipitates contributed to decreases of up to 20% in the available 60Co, 147Pm, 241Am, and 237Np in the adsorption systems. In the 234Th system 95% of the aqueous 234Th was removed by adsorbing to colloids. Although the range of Rvalues for each surface tested generally overlapped, the biofilms consistently demonstrated lower R values except for the trivalant

  7. [Surface characteristics of alkali modified activated carbon and the adsorption capacity of methane].

    PubMed

    Zhang, Meng-Zhu; Li, Lin; Liu, Jun-Xin; Sun, Yong-Jun; Li, Guo-Bin

    2013-01-01

    Coconut shell based activated carbon was modified by alkali with different concentrations. The surface structures of tested carbons were observed and analyzed by SEM and BET methods. Boehm's titration and SEM/EDS methods were applied to assay the functional groups and elements on the carbon surface. The adsorption of methane on tested carbons was investigated and adsorption behavior was described by the adsorption isotherms. Results showed that surface area and pore volume of modified carbon increased and surface oxygen groups decreased as the concentration of the alkali used increased, with no obvious change in pore size. When concentration of alkali was higher than 3.3 mol x L(-1), the specific surface area and pore volume of modified carbon was larger than that of original carbon. Methane adsorption capacity of alkali modified carbon increased 24%. Enlargement of surface area and pore volume, reduction of surface oxygen groups will benefit to enhance the methane adsorption ability on activated carbon. Adsorption behavior of methane followed the Langmuir isotherm and the adsorption coefficient was 163.7 m3 x mg(-1).

  8. Effect of purity on adsorption capacities of a Mars-like clay mineral at different pressures

    NASA Technical Reports Server (NTRS)

    Jenkins, Traci; Mcdoniel, Bridgett; Bustin, Roberta; Allton, Judith H.

    1992-01-01

    There has been considerable interest in adsorption of carbon dioxide on Marslike clay minerals. Some estimates of the carbon dioxide reservoir capacity of the martian regolith were calculated from the amount of carbon dioxide adsorbed on the ironrich smectite nontronite under martian conditions. The adsorption capacity of pure nontronite could place upper limits on the regolith carbon dioxide reservoir, both at present martian atmospheric pressure and at the postulated higher pressures required to permit liquid water on the surface. Adsorption of carbon dioxide on a Clay Mineral Society standard containing nontronite was studied over a wide range of pressures in the absence of water. Similar experiments were conducted on the pure nontronite extracted from the natural sample. Heating curves were obtained to help characterize and determine the purity of the clay sample.

  9. Fugitive gas adsorption capacity of biomass and animal-manure derived biochars

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This research characterized and investigated ammonia and hydrogen sulfide gas adsorption capacities of low- and high-temperature biochars made from wood shavings and chicken litter. The biochar samples were activated with steam or phosphoric acid. The specific surface areas and pore volumes of the a...

  10. Ammonia adsorption capacity of biomass and animal-manure derived biochars

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this research was to characterize and investigate ammonia and hydrogen sulfide gas adsorption capacities of low- and high-temperature biochars made from wood shavings and chicken litter. The biochar samples were activated with steam or phosphoric acid. The specific surface areas and...

  11. Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char

    USGS Publications Warehouse

    Lizzio, A.A.; DeBarr, J.A.

    1996-01-01

    The objective of this study was to determine whether activated char produced from Illinois coal could be used effectively to remove sulfur dioxide from coal combustion flue gas. Chars were prepared from a high-volatile Illinois bituminous coal under a wide range of pyrolysis and activation conditions. A novel char preparation technique was developed to prepare chars with SO2 adsorption capacities significantly greater than that of a commercial activated carbon. In general, there was no correlation between SO2 adsorption capacity and surface area. Temperature-programmed desorption (TPD) was used to determine the nature and extent of carbon-oxygen (C-O) complexes formed on the char surface. TPD data revealed that SO2 adsorption was inversely proportional to the amount of C-O complex. The formation of a stable C-O complex during char preparation may have served only to occupy carbon sites that were otherwise reactive towards SO2 adsorption. A fleeting C(O) complex formed during SO2 adsorption is postulated to be the reaction intermediate necessary for conversion of SO2 to H2SO4. Copyright ?? 1996 Elsevier Science Ltd.

  12. Influence of the inherent properties of drinking water treatment residuals on their phosphorus adsorption capacities.

    PubMed

    Bai, Leilei; Wang, Changhui; He, Liansheng; Pei, Yuansheng

    2014-12-01

    Batch experiments were conducted to investigate the phosphorus (P) adsorption and desorption on five drinking water treatment residuals (WTRs) collected from different regions in China. The physical and chemical characteristics of the five WTRs were determined. Combined with rotated principal component analysis, multiple regression analysis was used to analyze the relationship between the inherent properties of the WTRs and their P adsorption capacities. The results showed that the maximum P adsorption capacities of the five WTRs calculated using the Langmuir isotherm ranged from 4.17 to 8.20mg/g at a pH of 7 and further increased with a decrease in pH. The statistical analysis revealed that a factor related to Al and 200 mmol/L oxalate-extractable Al (Alox) accounted for 36.5% of the variations in the P adsorption. A similar portion (28.5%) was attributed to an integrated factor related to the pH, Fe, 200 mmol/L oxalate-extractable Fe (Feox), surface area and organic matter (OM) of the WTRs. However, factors related to other properties (Ca, P and 5 mmol/L oxalate-extractable Fe and Al) were rejected. In addition, the quantity of P desorption was limited and had a significant negative correlation with the (Feox+Alox) of the WTRs (p<0.05). Overall, WTRs with high contents of Alox, Feox and OM as well as large surface areas were proposed to be the best choice for P adsorption in practical applications.

  13. Nanosheet-structured boron nitride spheres with a versatile adsorption capacity for water cleaning.

    PubMed

    Liu, Fei; Yu, Jie; Ji, Xixi; Qian, Muqi

    2015-01-28

    Here, we report the synthesis of nanosheet-structured boron nitride spheres (NSBNSs) by a catalyzing thermal evaporation method from solid B powders. The NSBNSs consist of radially oriented ultrathin nanosheets with the sheet edges oriented on the surface. Formation of this unique structure occurs only at a certain reaction temperature. The diameter from 4 μm to 700 nm and the nanosheet thickness from 9.1 to 3.1 nm of the NSBNSs can be well-controlled by appropriately changing the mass ratio of boron powders and catalyst. The NSBNSs possess versatile adsorption capacity, exhibiting excellent adsorption performance for oil, dyes, and heavy metal ions from water. The oil uptake reaches 7.8 times its own weight. The adsorption capacities for malachite green and methylene blue are 324 and 233 mg/g, while those for Cu(2+), Pb(2+), and Cd(2+) are 678.7, 536.7, and 107.0 mg/g, respectively. The adsorption capacities of the NSBNSs for Cu(2+) and Pb(2+) are higher or much higher than those of the adsorbents reported previously. These results demonstrate the great potential of NSBNSs for water treatment and cleaning. PMID:25552343

  14. Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-05-03

    A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  15. Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2015-06-02

    Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  16. Amination of activated carbon for enhancing phenol adsorption: Effect of nitrogen-containing functional groups

    NASA Astrophysics Data System (ADS)

    Yang, Guo; Chen, Honglin; Qin, Hangdao; Feng, Yujun

    2014-02-01

    To study the contribution of different nitrogen-containing functional groups to enhancement of phenol adsorption, the aminated activated carbons (AC) were characterized by N2 adsorption/desorption, XPS, Boehm titration, and pH drift method and tested for adsorption behaviors of phenol. Adsorption isotherm fitting revealed that the Langmuir model was preferred for the aminated ACs. The adsorption capacity per unit surface area (qm/SSABET) was linearly correlated with the amount of pyridinic and pyrrolic N, which suggested that these two functional groups played a critical role in phenol adsorption. The enhancement of adsorption capacity was attributed to the strengthened π-π dispersion between phenol and basal plane of AC by pyridinic, pyrrolic N. The adsorption kinetics was found to follow the pseudo-second-order kinetic model, and intraparticle diffusion was one of the rate-controlling steps in the adsorption process.

  17. Novel biosorbent with high adsorption capacity prepared by chemical modification of white pine (Pinus durangensis) sawdust. Adsorption of Pb(II) from aqueous solutions.

    PubMed

    Salazar-Rabago, J J; Leyva-Ramos, R

    2016-03-15

    The natural sawdust (NS) from white pine (Pinus durangensis) was chemically modified by a hydrothermal procedure using citric, malonic and tartaric acids. The adsorption capacity of modified sawdust (MS) towards Pb(II) was considerably enhanced due to the introduction of carboxylic groups on the surface of MS during the modification, and the adsorption capacity was almost linearly dependent on the concentration of carboxylic sites. The NS surface was acidic, and the MS surface became more acidic after the modification. At T = 25 °C and pH = 5, the maximum adsorption capacity of the optimal MS towards Pb(II) was 304 mg/g, which is exceptionally high compared to NS and other MS reported previously. The adsorption capacity of MS was considerably reduced from 304 to 154 mg/g by decreasing the solution pH from 5 to 3 due to electrostatic interactions. The adsorption of Pb(II) on MS was reversible at pH = 2, but not at pH = 5. The contribution percentage of ion exchange to the overall adsorption capacity ranged from 70 to 99% and 10-66% at the initial pH of 3 and 5, respectively. Hence, the adsorption of Pb(II) on MS was mainly due to ion exchange at pH = 3 and to both ion exchange and electrostatic attraction at pH = 5.

  18. A Porous Aromatic Framework Constructed from Benzene Rings Has a High Adsorption Capacity for Perfluorooctane Sulfonate

    PubMed Central

    Luo, Qin; Zhao, Changwei; Liu, Guixia; Ren, Hao

    2016-01-01

    A low-cost and easily constructed porous aromatic framework (PAF-45) was successfully prepared using the Scholl reaction. PAF-45 was, for the first time, used to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Systematic experiments were performed to determine the adsorption capacity of PAF-45 for PFOS and to characterize the kinetics of the adsorption process. The adsorption of PFOS onto PAF-45 reached equilibrium in 30 min, and the adsorption capacity of PAF-45 for PFOS was excellent (5847 mg g−1 at pH 3). The amount of PFOS adsorbed by PAF-45 increased significantly as the cation (Na+, Mg2+, or Fe3+) concentration increased, which probably occurred because the cations enhanced the interactions between the negatively charged PFOS molecules and the positively charged PAF-45 surface. The cations Na+, Mg2+, and Fe3+ were found to form complexes with PFOS anions in solution. Density functional theory was used to identify the interactions between PFOS and Na+, Mg2+, and Fe3+. We expect that materials of the same type as PAF-45 could be useful adsorbents for removing organic pollutants from industrial wastewater and contaminated surface water. PMID:26843015

  19. A Porous Aromatic Framework Constructed from Benzene Rings Has a High Adsorption Capacity for Perfluorooctane Sulfonate

    NASA Astrophysics Data System (ADS)

    Luo, Qin; Zhao, Changwei; Liu, Guixia; Ren, Hao

    2016-02-01

    A low-cost and easily constructed porous aromatic framework (PAF-45) was successfully prepared using the Scholl reaction. PAF-45 was, for the first time, used to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Systematic experiments were performed to determine the adsorption capacity of PAF-45 for PFOS and to characterize the kinetics of the adsorption process. The adsorption of PFOS onto PAF-45 reached equilibrium in 30 min, and the adsorption capacity of PAF-45 for PFOS was excellent (5847 mg g‑1 at pH 3). The amount of PFOS adsorbed by PAF-45 increased significantly as the cation (Na+, Mg2+, or Fe3+) concentration increased, which probably occurred because the cations enhanced the interactions between the negatively charged PFOS molecules and the positively charged PAF-45 surface. The cations Na+, Mg2+, and Fe3+ were found to form complexes with PFOS anions in solution. Density functional theory was used to identify the interactions between PFOS and Na+, Mg2+, and Fe3+. We expect that materials of the same type as PAF-45 could be useful adsorbents for removing organic pollutants from industrial wastewater and contaminated surface water.

  20. Prediction of activated carbon adsorption capacities for organic vapors using quantitative structure-activity relationship methods

    SciTech Connect

    Nirmalakhandan, N.N. ); Speece, R.E. )

    1993-08-01

    Quantitative structure-activity relationship (QSAR) methods were used to develop models to estimate and predict activated carbon adsorption capacities for organic vapors. Literature isothermal data from two sources for 22 organic contaminants on six different carbons were merged to form a training set of 75 data points. Two different QSAR approaches were evaluated: the molecular connectivity approach and the linear solvation energy relationship approach. The QSAR model developed in this study using the molecular connectivity approach was able to fit the experimental data with r = 0.96 and standard error of 0.09. The utility of the model was demonstrated by using predicted k values to calculate adsorption capacities of 12 chemicals on two different carbons and comparing them with experimentally determined values. 9 refs., 1 fig., 3 tabs.

  1. Dispersion of chitosan on perlite for enhancement of copper(II) adsorption capacity.

    PubMed

    Hasan, Shameem; Ghosh, Tushar K; Viswanath, Dabir S; Boddu, Veera M

    2008-04-01

    Chitosan coated perlite beads were prepared by drop-wise addition of slurry, made of chitosan dissolved in oxalic acid and perlite, to an alkaline bath (0.7 M NaOH). The beads that contained 32% chitosan enhanced the accessibility of OH and amine groups present in chitosan for adsorption of copper ions. The experiments using Cu(II) ions were carried out in the concentration range of 50-4100 mg/L (0.78-64.1 mmol/L). Adsorption capacity for Cu(II) was pH dependent and a maximum uptake of 104 mg/g of beads (325 mg/g of chitosan) was obtained at pH 4.5 when its equilibrium concentration in the solution was 812.5 mg/L at 298 K. The XPS and TEM data suggested that copper was mainly adsorbed as Cu(II) and was attached to amine groups. The adsorption data could be fitted to one-site Langmuir adsorption model. Anions in the solution had minimal effect on Cu(II) adsorption by chitosan coated perlite beads. EDTA was used effectively for the regeneration of the bed. The diffusion coefficient of Cu(II) onto chitosan coated beads was calculated from the breakthrough curve and was found to be 2.02 x 10(-8) cm(2)/s.

  2. High-capacity adsorption of dissolved hexavalent chromium using amine-functionalized magnetic corn stalk composites.

    PubMed

    Song, Wen; Gao, Baoyu; Zhang, Tengge; Xu, Xing; Huang, Xin; Yu, Huan; Yue, Qinyan

    2015-08-01

    Easily separable amine-functionalized magnetic corn stalk composites (AF-MCS) were employed for effective adsorption and reduction of toxic hexavalent chromium [Cr(VI)] to nontoxic Cr(III). The saturated magnetization of AF-MCS reached 6.2emu/g, and as a result, it could be separated from aqueous solution by a magnetic process for its superparamagnetism. The studies of various factors influencing the sorption behavior indicated that the optimum AF-MCS dosage for Cr(VI) adsorption was 1g/L, and the maximum adsorption capacity was observed at pH 3.0. The chromium adsorption perfectly fitted the Langmuir isotherm model and pseudo second order kinetic model. Furthermore, characterization of AF-MCS was investigated by means of XRD, SEM, TEM, FT-IR, BET, VSM and XPS analysis to discuss the uptake mechanism. Basically, these results demonstrated that AF-MCS prepared in this work has shown its merit in effective removal of Cr(VI) and rapid separation from effluents simultaneously.

  3. Determination of the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon using thermogravimetric analysis

    SciTech Connect

    Hsun-Yu Lin; Chung-Shin Yuan; Wei-Ching Chen; Chung-Hsuang Hung

    2006-11-15

    This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl{sub 2} was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl{sub 2} were 1.75, 0.688, and 0.230 mg of HgCl{sub 2} per gram of powdered activated carbon derived from carbon black at 30, 70, and 150{sup o} for 500 {mu}g/m{sup 3} of HgCl{sub 2}, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer-Emmett-eller (BET) models were used to simulate the adsorption of HgCl{sub 2}. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30{sup o}, whereas the Freundlich isotherm fit the experimental results better at 70 and 150{sup o}. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl{sub 2} by PAC-derived carbon black favored adsorption at various HgCl{sub 2} concentrations and temperatures. 35 refs., 7 figs., 3 tabs.

  4. A review on modification methods to cellulose-based adsorbents to improve adsorption capacity.

    PubMed

    Hokkanen, Sanna; Bhatnagar, Amit; Sillanpää, Mika

    2016-03-15

    In recent decades, increased domestic, agricultural and industrial activities worldwide have led to the release of various pollutants, such as toxic heavy metals, inorganic anions, organics, micropollutants and nutrients into the aquatic environment. The removal of these wide varieties of pollutants for better quality of water for various activities is an emerging issue and a robust and eco-friendly treatment technology is needed for the purpose. It is well known that cellulosic materials can be obtained from various natural sources and can be employed as cheap adsorbents. Their adsorption capacities for heavy metal ions and other aquatic pollutants can be significantly affected upon chemical treatment. In general, chemically modified cellulose exhibits higher adsorption capacities for various aquatic pollutants than their unmodified forms. Numerous chemicals have been used for cellulose modifications which include mineral and organic acids, bases, oxidizing agent, organic compounds, etc. This paper reviews the current state of research on the use of cellulose, a naturally occurring material, its modified forms and their efficacy as adsorbents for the removal of various pollutants from waste streams. In this review, an extensive list of various cellulose-based adsorbents from literature has been compiled and their adsorption capacities under various conditions for the removal of various pollutants, as available in the literature, are presented along with highlighting and discussing the key advancement on the preparation of cellulose-based adsorbents. It is evident from the literature survey presented herein that modified cellulose-based adsorbents exhibit good potential for the removal of various aquatic pollutants. However, still there is a need to find out the practical utility of these adsorbents on a commercial scale, leading to the improvement of pollution control. PMID:26789698

  5. Adsorption capacities of activated carbons for geosmin and 2-methylisoborneol vary with activated carbon particle size: Effects of adsorbent and adsorbate characteristics.

    PubMed

    Matsui, Yoshihiko; Nakao, Soichi; Sakamoto, Asuka; Taniguchi, Takuma; Pan, Long; Matsushita, Taku; Shirasaki, Nobutaka

    2015-11-15

    The adsorption capacities of nine activated carbons for geosmin and 2-methylisoborneol (MIB) were evaluated. For some carbons, adsorption capacity substantially increased when carbon particle diameter was decreased from a few tens of micrometers to a few micrometers, whereas for other carbons, the increase of adsorption capacity was small for MIB and moderate for geosmin. An increase of adsorption capacity was observed for other hydrophobic adsorbates besides geosmin and MIB, but not for hydrophilic adsorbates. The parameter values of a shell adsorption model describing the increase of adsorption capacity were negatively correlated with the oxygen content of the carbon among other characteristics. Low oxygen content indicated low hydrophilicity. The increase of adsorption capacity was related to the hydrophobic properties of both adsorbates and activated carbons. For adsorptive removal of hydrophobic micropollutants such as geosmin, it is therefore recommended that less-hydrophilic activated carbons, such as coconut-shell-based carbons, be microground to a particle diameter of a few micrometers to enhance their equilibrium adsorption capacity. In contrast, adsorption by hydrophilic carbons or adsorption of hydrophilic adsorbates occur in the inner pores, and therefore adsorption capacity is unchanged by particle size reduction. PMID:26302219

  6. Adsorption capacities of activated carbons for geosmin and 2-methylisoborneol vary with activated carbon particle size: Effects of adsorbent and adsorbate characteristics.

    PubMed

    Matsui, Yoshihiko; Nakao, Soichi; Sakamoto, Asuka; Taniguchi, Takuma; Pan, Long; Matsushita, Taku; Shirasaki, Nobutaka

    2015-11-15

    The adsorption capacities of nine activated carbons for geosmin and 2-methylisoborneol (MIB) were evaluated. For some carbons, adsorption capacity substantially increased when carbon particle diameter was decreased from a few tens of micrometers to a few micrometers, whereas for other carbons, the increase of adsorption capacity was small for MIB and moderate for geosmin. An increase of adsorption capacity was observed for other hydrophobic adsorbates besides geosmin and MIB, but not for hydrophilic adsorbates. The parameter values of a shell adsorption model describing the increase of adsorption capacity were negatively correlated with the oxygen content of the carbon among other characteristics. Low oxygen content indicated low hydrophilicity. The increase of adsorption capacity was related to the hydrophobic properties of both adsorbates and activated carbons. For adsorptive removal of hydrophobic micropollutants such as geosmin, it is therefore recommended that less-hydrophilic activated carbons, such as coconut-shell-based carbons, be microground to a particle diameter of a few micrometers to enhance their equilibrium adsorption capacity. In contrast, adsorption by hydrophilic carbons or adsorption of hydrophilic adsorbates occur in the inner pores, and therefore adsorption capacity is unchanged by particle size reduction.

  7. Adsorptive capacity and evolution of the pore structure of alumina on reaction with gaseous hydrogen fluoride.

    PubMed

    McIntosh, Grant J; Agbenyegah, Gordon E K; Hyland, Margaret M; Metson, James B

    2015-05-19

    Brunauer-Emmet-Teller (BET) specific surface areas are generally used to gauge the propensity of uptake on adsorbents, with less attention paid to kinetic considerations. We explore the importance of such parameters by modeling the pore size distributions of smelter grade aluminas following HF adsorption, an industrially important process in gas cleaning at aluminum smelters. The pore size distributions of industrially fluorinated aluminas, and those contacted with HF in controlled laboratory trials, are reconstructed from the pore structure of the untreated materials when filtered through different models of adsorption. These studies demonstrate the presence of three distinct families of pores: those with uninhibited HF uptake, kinetically limited porosity, and pores that are surface blocked after negligible scrubbing. The surface areas of the inaccessible and blocked pores will overinflate estimates of the adsorption capacity of the adsorbate. We also demonstrate, contrary to conventional understanding, that porosity changes are attributed not to monolayer uptake but more reasonably to pore length attenuation. The model assumes nothing specific regarding the Al2O3-HF system and is therefore likely general to adsorbate/adsorbent phenomena.

  8. Volumetric Interpretation of Protein Adsorption: Capacity Scaling with Adsorbate Molecular Weight and Adsorbent Surface Energy

    PubMed Central

    Parhi, Purnendu; Golas, Avantika; Barnthip, Naris; Noh, Hyeran; Vogler, Erwin A.

    2009-01-01

    Silanized-glass-particle adsorbent capacities are extracted from adsorption isotherms of human serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa) for adsorbent surface energies sampling the observable range of water wettability. Adsorbent capacity expressed as either mass-or-moles per-unit-adsorbent-area increases with protein molecular weight (MW) in a manner that is quantitatively inconsistent with the idea that proteins adsorb as a monolayer at the solution-material interface in any physically-realizable configuration or state of denaturation. Capacity decreases monotonically with increasing adsorbent hydrophilicity to the limit-of-detection (LOD) near τo = 30 dyne/cm (θ~65o) for all protein/surface combinations studied (where τo≡γlvocosθ is the water adhesion tension, γlvo is the interfacial tension of pure-buffer solution, and θ is the buffer advancing contact angle). Experimental evidence thus shows that adsorbent capacity depends on both adsorbent surface energy and adsorbate size. Comparison of theory to experiment implies that proteins do not adsorb onto a two-dimensional (2D) interfacial plane as frequently depicted in the literature but rather partition from solution into a three-dimensional (3D) interphase region that separates the physical surface from bulk solution. This interphase has a finite volume related to the dimensions of hydrated protein in the adsorbed state (defining “layer” thickness). The interphase can be comprised of a number of adsorbed-protein layers depending on the solution concentration in which adsorbent is immersed, molecular volume of the adsorbing protein (proportional to MW), and adsorbent hydrophilicity. Multilayer adsorption accounts for adsorbent capacity over-and-above monolayer and is inconsistent with the idea that protein adsorbs to surfaces primarily through protein/surface interactions because proteins within second (or higher

  9. Superior adsorption capacity of g-C₃N₄ for heavy metal ions from aqueous solutions.

    PubMed

    Shen, Congcong; Chen, Changlun; Wen, Tao; Zhao, Zhiwei; Wang, Xiangke; Xu, Anwu

    2015-10-15

    In this work, graphitic-C3N4 (g-C3N4) was synthesized by a simple and environmentally friendly salt melt method, and characterized by using field-emission scanning and transmission electron microscopy, X-ray diffraction, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and N2 adsorption-desorption analysis. The as-prepared g-C3N4 was used as an adsorbent to remove heavy metal ions from aqueous solutions. The adsorption kinetics of Pb(II) and Cu(II) followed the pseudo-second-order model. The g-C3N4 exhibited much higher adsorption capacity toward heavy metal ions (1.36 mmol/g for Pb(II), 2.09 mmol/g for Cu(II), 1.00 mmol/g for Cd(II) and 0.64 mmol/g for Ni(II)) than other adsorbents. The adsorption of Pb(II) and Cu(II) on g-C3N4 was slightly affected by ionic strength at pH<5.0 and increased with the increase of ionic strength at pH>5.0. The inner-sphere surface complexation mechanism was suitable to explain the interaction between heavy metal ions and the nitrogen- and carbon-containing functional groups of the g-C3N4. The experimental results reveal that g-C3N4 is a potential adsorbent for the removal of heavy metal ions from large volumes of aqueous solutions.

  10. Diamine-appended metal-organic frameworks: enhanced formaldehyde-vapor adsorption capacity, superior recyclability and water resistibility.

    PubMed

    Wang, Zhong; Wang, WenZhong; Jiang, Dong; Zhang, Ling; Zheng, Yali

    2016-07-28

    Capturing formaldehyde (HCHO) from indoor air with porous adsorbents still faces challenges due to their low uptake capacity, difficult regeneration, and especially, the sorption capacity reduction that is caused by the competitive adsorption of H2O when exposed to a humid atmosphere. In this work, MIL-101 is modified with ethylenediamine (ED) on its open-metal sites to substantially improve the HCHO adsorption properties. The HCHO uptake capacity of modified MIL-101 can be up to 5.49 mmol g(-1) in this study, which is among the highest-levels of various adsorbents reported thus far. Moreover, this modification both improved the material's recyclability and water resistibility, allowing for cyclic and selective tests with stable adsorption capacities, revealing the potential utility of amine-modified MOFs for indoor air purification. PMID:27338802

  11. Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water.

    PubMed

    Lin, Kun-Yi Andrew; Chang, Hsuan-Ang

    2015-11-01

    Zeolitic imidazole frameworks (ZIFs), a new class of adsorbents, are proposed to adsorb Malachite Green (MG) in water. Particularly, ZIF-67 was selected owing to its stability in water and straightforward synthesis. The as-synthesized ZIF-67 was characterized and used to adsorb MG from water. Factors affecting the adsorption capacity were investigated including mixing time, temperature, the presence of salts and pH. The kinetics, adsorption isotherm and thermodynamics of the MG adsorption to ZIF-67 were also studied. The adsorption capacity of ZIF-67 for MG could be as high as 2430mgg(-1) at 20°C, which could be improved at the higher temperatures. Such an ultra-high adsorption capacity of ZIF-67 was almost 10-times of those of conventional adsorbents, including activated carbons and biopolymers. A mechanism for the high adsorption capacity was proposed and possibly attributed to the π-π stacking interaction between MG and ZIF-67. ZIF-67 also could be conveniently regenerated by washing with ethanol and the regeneration efficiency could remain 95% up to 4 cycles of the regeneration. ZIF-67 was also able to remove MG from the aquaculture wastewater, in which MG can be typically found. These features enable ZIF-67 to be one of the most effective and promising adsorbent to remove MG from water.

  12. Ultra-high adsorption capacity of zeolitic imidazole framework-67 (ZIF-67) for removal of malachite green from water.

    PubMed

    Lin, Kun-Yi Andrew; Chang, Hsuan-Ang

    2015-11-01

    Zeolitic imidazole frameworks (ZIFs), a new class of adsorbents, are proposed to adsorb Malachite Green (MG) in water. Particularly, ZIF-67 was selected owing to its stability in water and straightforward synthesis. The as-synthesized ZIF-67 was characterized and used to adsorb MG from water. Factors affecting the adsorption capacity were investigated including mixing time, temperature, the presence of salts and pH. The kinetics, adsorption isotherm and thermodynamics of the MG adsorption to ZIF-67 were also studied. The adsorption capacity of ZIF-67 for MG could be as high as 2430mgg(-1) at 20°C, which could be improved at the higher temperatures. Such an ultra-high adsorption capacity of ZIF-67 was almost 10-times of those of conventional adsorbents, including activated carbons and biopolymers. A mechanism for the high adsorption capacity was proposed and possibly attributed to the π-π stacking interaction between MG and ZIF-67. ZIF-67 also could be conveniently regenerated by washing with ethanol and the regeneration efficiency could remain 95% up to 4 cycles of the regeneration. ZIF-67 was also able to remove MG from the aquaculture wastewater, in which MG can be typically found. These features enable ZIF-67 to be one of the most effective and promising adsorbent to remove MG from water. PMID:25697373

  13. Influence of Environmental Factors on the Adsorption Capacity and Thermal Conductivity of Silica Nano-Porous Materials.

    PubMed

    Zhang, Hu; Gu, Wei; Li, Ming-Jia; Fang, Wen-Zhen; Li, Zeng-Yao; Tao, Wen-Quan

    2015-04-01

    In this work, the influence of temperature and humidity environment on the water vapor adsorption capacity and effective thermal conductivity of silica nano-porous material is conducted within a relative humidity range from 15% to 90% at 25 °C, 40 °C and 55 °C, respectively. The experiment results show that both the temperature and relative humidity have significant influence on the adsorption capacity and effective thermal conductivity of silica nano-porous materials. The adsorption capacity and effective thermal conductivity increase with humidity because of the increases of water vapor concentration. The effective thermal conductivity increases linearly with adsorption saturation capacity at constant temperature. Because adsorption process is exothermic reaction, the increasing temperature is not conducive to the adsorption. But the effective thermal conductivity increases with the increment of temperature at the same water uptake because of the increment of water thermal conductivity with temperature Geometric models and unit cell structure are adopted to predict the effective thermal conductivity and comparisons with the experimental result are made, and for the case of moist silica nano-porous materials with high porosity no quantitative agreement is found. It is believed that the adsorbed water will fill in the nano-pores and gap and form lots of short cuts, leading to a significant reduction of the thermal resistance.

  14. Study on the Adsorption Capacities for Airborne Particulates of Landscape Plants in Different Polluted Regions in Beijing (China).

    PubMed

    Zhang, Wei-Kang; Wang, Bing; Niu, Xiang

    2015-08-14

    Urban landscape plants are an important component of the urban ecosystem, playing a significant role in the adsorption of airborne particulates and air purification. In this study, six common landscape plants in Beijing were chosen as research subjects, and the adsorption capacities for each different plant leaf and the effects of the leaf structures for the adsorption capacities for particulates were determined. Preliminary results show that needle-leaved tree species adsorbed more airborne particulates than broad-leaved tree species for the same leaf area. Pinus tabuliformis exhibits the highest adsorption capacity, at 3.89 ± 0.026 μg·cm(-2), almost two times as much as that of Populus tomentosa (2.00 ± 0.118 μg·cm(-2)). The adsorption capacities for PM10 of the same tree species leaves, in different polluted regions had significant differences, and the adsorption capacities for PM10 of the tree species leaf beside the Fifth Ring Road were higher than those of the tree species leaves in the Botanical Garden, although the adsorption capacities for PM2.5 of the same tree species in different polluted regions had no significant differences. By determining the soluble ion concentrations of the airborne particulates in two regions, it is suggested that the soluble ion concentrations of PM10 in the atmosphere in the Botanical Garden and beside the Fifth Ring Road have significant differences, while those of PM2.5 in the atmosphere had no significant differences. In different polluted regions there are significant adaptive changes to the leaf structures, and when compared with slightly polluted region, in the seriously polluted region the epidermis cells of the plant leaves shrinked, the surface textures of the leaves became rougher, and the stomas' frequency and the pubescence length increased. Even though the plant leaves exposed to the seriously polluted region changed significantly, these plants can still grow normally and healthily.

  15. Study on the Adsorption Capacities for Airborne Particulates of Landscape Plants in Different Polluted Regions in Beijing (China)

    PubMed Central

    Zhang, Wei-Kang; Wang, Bing; Niu, Xiang

    2015-01-01

    Urban landscape plants are an important component of the urban ecosystem, playing a significant role in the adsorption of airborne particulates and air purification. In this study, six common landscape plants in Beijing were chosen as research subjects, and the adsorption capacities for each different plant leaf and the effects of the leaf structures for the adsorption capacities for particulates were determined. Preliminary results show that needle-leaved tree species adsorbed more airborne particulates than broad-leaved tree species for the same leaf area. Pinus tabuliformis exhibits the highest adsorption capacity, at 3.89 ± 0.026 μg·cm−2, almost two times as much as that of Populus tomentosa (2.00 ± 0.118 μg·cm−2). The adsorption capacities for PM10 of the same tree species leaves, in different polluted regions had significant differences, and the adsorption capacities for PM10 of the tree species leaf beside the Fifth Ring Road were higher than those of the tree species leaves in the Botanical Garden, although the adsorption capacities for PM2.5 of the same tree species in different polluted regions had no significant differences. By determining the soluble ion concentrations of the airborne particulates in two regions, it is suggested that the soluble ion concentrations of PM10 in the atmosphere in the Botanical Garden and beside the Fifth Ring Road have significant differences, while those of PM2.5 in the atmosphere had no significant differences. In different polluted regions there are significant adaptive changes to the leaf structures, and when compared with slightly polluted region, in the seriously polluted region the epidermis cells of the plant leaves shrinked, the surface textures of the leaves became rougher, and the stomas’ frequency and the pubescence length increased. Even though the plant leaves exposed to the seriously polluted region changed significantly, these plants can still grow normally and healthily. PMID:26287227

  16. Suitability of adsorption isotherms for predicting the retention capacity of active slag filters removing phosphorus from wastewater.

    PubMed

    Pratt, C; Shilton, A

    2009-01-01

    Active slag filters are an emerging technology for removing phosphorus (P) from wastewater. A number of researchers have suggested that adsorption isotherms are a useful tool for predicting P retention capacity. However, to date the appropriateness of using isotherms for slag filter design remains unverified due to the absence of benchmark data from a full-scale, field filter operated to exhaustion. This investigation compared the isotherm-predicted P retention capacity of a melter slag with the P adsorption capacity determined from a full-scale, melter slag filter which had reached exhaustion after five years of successfully removing P from waste stabilization pond effluent. Results from the standard laboratory batch test showed that P adsorption correlated more strongly with the Freundlich Isotherm (R(2)=0.97, P<0.01) than the Langmuir Isotherm, a similar finding to previous studies. However, at a P concentration of 10 mg/L, typical of domestic effluent, the Freundlich equation predicted a retention capacity of 0.014 gP/kg slag; markedly lower than the 1.23 gP/kg slag adsorbed by the field filter. Clearly, the result generated by the isotherm bears no resemblance to actual field capacity. Scanning electron microscopy analysis revealed porous, reactive secondary minerals on the slag granule surfaces from the field filter which were likely created by weathering. This slow weathering effect, which generates substantial new adsorption sites, is not accounted for by adsorption isotherms rendering them ineffective in slag filter design. PMID:19403982

  17. Reservoir capacity estimates in shale plays based on experimental adsorption data

    NASA Astrophysics Data System (ADS)

    Ngo, Tan

    from different measurement techniques using representative fluids (such as CH4 and CO2) at elevated pressures, and the adsorbed density can range anywhere between the liquid and the solid state of the adsorbate. Whether these discrepancies are associated with the inherent heterogeneity of mudrocks and/or with poor data quality requires more experiments under well-controlled conditions. Nevertheless, it has been found in this study that methane GIP estimates can vary between 10-45% and 10-30%, respectively, depending on whether the free or the total amount of gas is considered. Accordingly, CO2 storage estimates range between 30-90% and 15-50%, due to the larger adsorption capacity and gas density at similar pressure and temperature conditions. A manometric system has been designed and built that allows measuring the adsorption of supercritical fluids in microporous materials. Preliminary adsorption tests have been performed using a microporous 13X zeolite and CO 2 as an adsorbing gas at a temperature of 25oC and 35oC and at pressures up to 500 psi. Under these conditions, adsorption is quantified with a precision of +/- 3%. However, relative differences up to 15-20% have been observed with respect to data published in the literature on the same adsorbent and at similar experimental conditions. While it cannot be fully explained with uncertainty analysis, this discrepancy can be reduced by improving experiment practice, thus including the application of a higher adsorbent's regeneration temperature, of longer equilibrium times and of a careful flushing of the system between the various experimental steps. Based on the results on 13X zeolite, virtual tests have been conducted to predict the performance of the manometric system to measure adsorption on less adsorbing materials, such as mudrocks. The results show that uncertainties in the estimated adsorbed amount are much more significant in shale material and they increase with increasing pressure. In fact, relative

  18. The adsorptive capacity of vapor-phase mercury chloride onto powdered activated carbon derived from waste tires

    SciTech Connect

    Hsun-Yu Lin; Chung-Shin Yuan; Chun-Hsin Wu; Chung-Hsuang Hung

    2006-11-15

    Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl{sub 2}) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150{sup o}C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer Emmett Teller (BET) surface area could adsorb more HgCl{sub 2} at room temperature. The equilibrium adsorptive capacity of HgCl{sub 2} for WPAC measured in this study was 1.49 x 10{sup -1} mg HgCl{sub 2}/g PAC at 25{sup o}C with an initial HgCl{sub 2} concentration of 25 {mu}g/m{sup 3}. With the increase of adsorption temperature {le} 150{sup o}C, the equilibrium adsorptive capacity of HgCl{sub 2} for WPAC was decreased to 1.34 x 10{sup -1} mg HgCl{sub 2}/g PAC. Furthermore, WPAC with higher sulfur contents could adsorb even more HgCl{sub 2}. It was demonstrated that the mechanisms for adsorbing HgCl{sub 2} onto WPAC were physical adsorption and chemisorption at 25 and 150{sup o}C, respectively. 35 refs., 4 figs., 4 tabs.

  19. Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area.

    PubMed Central

    Lipson, S M; Stotzky, G

    1983-01-01

    The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the

  20. Reservoir capacity estimates in shale plays based on experimental adsorption data

    NASA Astrophysics Data System (ADS)

    Ngo, Tan

    from different measurement techniques using representative fluids (such as CH4 and CO2) at elevated pressures, and the adsorbed density can range anywhere between the liquid and the solid state of the adsorbate. Whether these discrepancies are associated with the inherent heterogeneity of mudrocks and/or with poor data quality requires more experiments under well-controlled conditions. Nevertheless, it has been found in this study that methane GIP estimates can vary between 10-45% and 10-30%, respectively, depending on whether the free or the total amount of gas is considered. Accordingly, CO2 storage estimates range between 30-90% and 15-50%, due to the larger adsorption capacity and gas density at similar pressure and temperature conditions. A manometric system has been designed and built that allows measuring the adsorption of supercritical fluids in microporous materials. Preliminary adsorption tests have been performed using a microporous 13X zeolite and CO 2 as an adsorbing gas at a temperature of 25oC and 35oC and at pressures up to 500 psi. Under these conditions, adsorption is quantified with a precision of +/- 3%. However, relative differences up to 15-20% have been observed with respect to data published in the literature on the same adsorbent and at similar experimental conditions. While it cannot be fully explained with uncertainty analysis, this discrepancy can be reduced by improving experiment practice, thus including the application of a higher adsorbent's regeneration temperature, of longer equilibrium times and of a careful flushing of the system between the various experimental steps. Based on the results on 13X zeolite, virtual tests have been conducted to predict the performance of the manometric system to measure adsorption on less adsorbing materials, such as mudrocks. The results show that uncertainties in the estimated adsorbed amount are much more significant in shale material and they increase with increasing pressure. In fact, relative

  1. Evaluation of Adsorption Capacity of Montmorillonite and Aluminium-pillared Clay for Pb2+, Cu2+ and Zn2.

    PubMed

    Humelnicu, Doina; Ignat, Maria; Suchea, Mirela

    2015-01-01

    Adsorption capacity of the two adsorbents was investigated as a function of contact time between adsorbent and heavy metal ions solutions, the initial heavy metals concentration of the synthetic wastewater, pH value, temperature and adsorbent mass. Preliminary experiments at different pH values between 2.0 and 7.0 were performed, and were observed that maximum adsorption occurs at pH 5 for copper (q(max) = 92.59 mg · g(–1)), 6.0 for lead (qmax = 97.08 mg · g(–1)) and 6.5 for zinc ions (q(max) = 73.52 mg · g(–1)), respectively. The sorption capacity of studied adsorbents for Pb(2+), Cu(2+) and Zn(2+) was calculated using Langmuir and Freundlich models. Thermodynamic parameters – enthalpy change (ΔH(0)), entropychange (ΔS(0)) and free energy (ΔG(0)) – were calculated for predicting the nature of adsorption. Scanning electron micrograph(SEM) revealed changes in the surface morphology of the adsorbent as a result of heavy metal ions adsorption.EDS characterization confirmed qualitatively the presence of adsorbed species in the samples. On the basis of the obtained results the adsorption it was proposed an ordered adsorption: Pb(2+), Cu(2+) and Zn(2+), on the sorbents we investigated. PMID:26680724

  2. Preparation of mesoporous poly (acrylic acid)/SiO2 composite nanofiber membranes having adsorption capacity for indigo carmine dye

    NASA Astrophysics Data System (ADS)

    Xu, Ran; Jia, Min; Li, Fengting; Wang, Hongtao; Zhang, Bingru; Qiao, Junlian

    2012-03-01

    Mesoporous poly (acrylic acid)/SiO2 (PAA/SiO2) composite nanofiber membranes functionalized with mercapto groups were fabricated by a sol-gel electrospinning method, and their adsorption capacity for indigo carmine was investigated. The membranes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, x-ray powder diffraction (XRD), and nitrogen adsorption-desorption measurement. SEM and TEM observation results showed that the PAA/SiO2 fibers had diameters between 400-800 nm and mesopores with an average pore size of 3.88 nm. The specific surface area of the mesoporous nanofiber membranes was 514.89 m2/g. The characteristic peaks for mercapto group vibration in FTIR and Raman spectra demonstrated that the mercapto groups have been incorporated into the silica skeleton. The adsorption isotherm data of indigo carmine on the membranes fit well with Redlich-Peterson model, and the maximum adsorption capacity calculated was 523.11 mg/g. It was found that the removal rate of indigo carmine by the membranes reached a maximum of 98% in 90 min and the adsorption kinetics followed a pseudo-second-order model. The high adsorption capacity of PAA/SiO2 nanofiber membrane makes it a promising adsorbent for indigo carmine removal from the wastewater.

  3. Enhancing adsorption capacity of toxic malachite green dye through chemically modified breadnut peel: equilibrium, thermodynamics, kinetics and regeneration studies.

    PubMed

    Chieng, Hei Ing; Lim, Linda B L; Priyantha, Namal

    2015-01-01

    Breadnut skin, in both its unmodified (KS) and base-modified (BM-KS) forms, was investigated for its potential use as a low-cost adsorbent for the removal of toxic dye, malachite green (MG). Characterization of the adsorbents was carried out using scanning electron microscope, X-ray fluorescence and Fourier transform infra-red spectroscopy. Batch adsorption experiments, carried out under optimized conditions, for the adsorption of MG were fitted using five isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Sips) and six error functions to determine the best-fit model. The adsorption capacity was greatly enhanced when breadnut skin was chemically modified with NaOH, leading to an adsorption capacity of 353.0 mg g(-1), that was far superior to most reported adsorbents for the removal of MG. Thermodynamics studies indicated that the adsorption of MG was spontaneous on KS and BM-KS, and the reactions were endothermic and exothermic, respectively. Kinetics studies showed that both followed the pseudo-second order. Regeneration experiments on BM-KS indicated that its adsorption capacity was still maintained at>90% even after five cycles. It can be concluded that NaOH-modified breadfruit skin has great potential to be utilized in real-life application as a low-cost adsorbent for the removal of MG in wastewater treatment.

  4. Enhancing adsorption capacity of toxic malachite green dye through chemically modified breadnut peel: equilibrium, thermodynamics, kinetics and regeneration studies.

    PubMed

    Chieng, Hei Ing; Lim, Linda B L; Priyantha, Namal

    2015-01-01

    Breadnut skin, in both its unmodified (KS) and base-modified (BM-KS) forms, was investigated for its potential use as a low-cost adsorbent for the removal of toxic dye, malachite green (MG). Characterization of the adsorbents was carried out using scanning electron microscope, X-ray fluorescence and Fourier transform infra-red spectroscopy. Batch adsorption experiments, carried out under optimized conditions, for the adsorption of MG were fitted using five isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Sips) and six error functions to determine the best-fit model. The adsorption capacity was greatly enhanced when breadnut skin was chemically modified with NaOH, leading to an adsorption capacity of 353.0 mg g(-1), that was far superior to most reported adsorbents for the removal of MG. Thermodynamics studies indicated that the adsorption of MG was spontaneous on KS and BM-KS, and the reactions were endothermic and exothermic, respectively. Kinetics studies showed that both followed the pseudo-second order. Regeneration experiments on BM-KS indicated that its adsorption capacity was still maintained at>90% even after five cycles. It can be concluded that NaOH-modified breadfruit skin has great potential to be utilized in real-life application as a low-cost adsorbent for the removal of MG in wastewater treatment. PMID:25409587

  5. Preparation of a porous clay heterostructure and study of its adsorption capacity of phenol and chlorinated phenols from aqueous solutions.

    PubMed

    Arellano-Cárdenas, Sofía; Gallardo-Velázquez, Tzayhrí; Osorio-Revilla, Guillermo; López-Cortez, Ma del Socorro

    2008-01-01

    A porous clay heterostructure (PCH) from a Mexican clay was prepared and characterized, and its aqueous phenol and dichlorophenols (DCPs) adsorption capacities were studied using a batch equilibrium technique. The PCH displayed a surface area of 305.5 m2/g, 37.2 A average porous diameter, and a basal space of 23.2 A. The adsorption capacity shown by the PCH for both phenol and DCPs from water (14.5 mg/g for phenol; 48.7 mg/g for 3,4-DCP; and 45.5 mg/g for 2,5-DCP) suggests that the PCH has both hydrophobic and hydrophilic characteristics, as a result of the presence of silanol and siloxane groups formed during the pillaring and calcination of the PCH. The values of maximal adsorption capacity for dichlorophenols were higher than those reported for aluminum pillared clays and some inorgano-organo clays and comparable with some ionic exchange resins.

  6. Metal and proton adsorption capacities of natural and cloned Sphagnum mosses.

    PubMed

    Gonzalez, Aridane G; Pokrovsky, Oleg S; Beike, Anna K; Reski, Ralf; Di Palma, Anna; Adamo, Paola; Giordano, Simonetta; Fernandez, J Angel

    2016-01-01

    Terrestrial mosses are commonly used as bioindicators of atmospheric pollution. However, there is a lack of standardization of the biomonitoring preparation technique and the efficiency of metal adsorption by various moss species is poorly known. This is especially true for in vitro-cultivated moss clones, which are promising candidates for a standardized moss-bag technique. We studied the adsorption of copper and zinc on naturally grown Sphagnum peat moss in comparison with in vitro-cultivated Sphagnum palustre samples in order to provide their physico-chemical characterization and to test the possibility of using cloned peat mosses as bioindicators within the protocol of moss-bag technique. We demonstrate that in vitro-grown clones of S. palustre exhibit acid-base properties similar to those of naturally grown Sphagnum samples, whereas the zinc adsorption capacity of the clones is approx. twice higher than that of the samples from the field. At the same time, the field samples adsorbed 30-50% higher amount of Cu(2+) compared to that of the clones. This contrast may be related to fine differences in the bulk chemical composition, specific surface area, morphological features, type and abundance of binding sites at the cell surfaces and in the aqueous solution of natural and cloned Sphagnum. The clones exhibited much lower concentration of most metal pollutants in their tissues relative to the natural samples thus making the former better indicators of low metal loading. Overall, in vitro-produced clones of S. palustre can be considered as an adequate, environmentally benign substitution for protected natural Sphagnum sp. samples to be used in moss-bags for atmospheric monitoring. PMID:26407060

  7. Comparative study on the adsorption capacity of raw and modified litchi pericarp for removing Cu(II) from solutions.

    PubMed

    Kong, Zhenglei; Li, Xiaochen; Tian, Jiyu; Yang, Jili; Sun, Shujuan

    2014-02-15

    The adsorption of Cu(II) onto raw litchi pericarp (LP) and modified litchi pericarp (MLP) as a function of pH, adsorbent dose and contact time, were investigated. Adsorption equilibrium isotherms, kinetics, and thermodynamics were studied to characterize the adsorption process. Leaching assays were also conducted to evaluate the potential contamination risk of LP and MLP to aqueous systems. The maximum adsorption of Cu(II) onto MLP was occurred at the pH of 6.0, adsorbent dose of 10.0 g/L, and contact time of 60 min, respectively. The adsorption process of Cu(II) onto LP and MLP were described well by both Langmuir and Freundlich isotherms, and the adsorption kinetics of Cu(II) on MLP was pseudo-second-order. Cu(II) adsorption onto LP and MLP are both exothermic, while it is spontaneous for MLP, and non-spontaneous for LP. The maximum adsorption capacity of Cu(II) onto MLP was 23.70 mg/g, which was about 2.7 times higher than that of LP. Additionally, as compared to LP, the leaching amounts of TOC, TN, and TP from MLP were significantly reduced by a percentage of 27.0%, 90.3%, and 35.3%, respectively. PMID:24473344

  8. Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J; Dai, Sheng; Oyola, Yatsandra

    2014-05-13

    A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  9. Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

    DOEpatents

    Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

    2016-09-06

    A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

  10. Porphyrin-Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue.

    PubMed

    Hou, Yuxia; Sun, Junshan; Zhang, Daopeng; Qi, Dongdong; Jiang, Jianzhuang

    2016-04-25

    A series of four porphyrin-alkaline earth metal- organic frameworks [Mg(HDCPP)2 (DMF)2 ]n ⋅(H2 O)7 n (1), [Ca(HDCPP)2 (H2 O)2 ]n (DMF)1.5 n (2), [Sr(DCPP)(H2 O)(DMA)]n (3), and [Ba(DCPP)(H2 O)(DMA)]n (4) was isolated for the first time from solvothermal reaction between metal-free 5,15-di(4- carboxyphenyl)porphyrin (H2 DCPP) and alkaline earth ions. Single-crystal X-ray diffraction analysis reveals the 2D and 3D supramolecular network with periodic nanosized porosity for 1/2 and 3/4, respectively. The whole series of MOFs, in particular, compounds 1 and 2 with intrinsic low molecular formula weight, exhibit superior adsorption performance for methylene blue (MB) with excellent capture capacity as represented by the thus far highest adsorption amount of 952 mg g(-1) for 2 and good selectivity, opening a new way for the potential application of the main group metal-based MOFs. PMID:27002679

  11. Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: kinetics, isotherms and thermodynamics.

    PubMed

    Yu, Fei; Wu, Yanqing; Ma, Jie; Zhang, Chi

    2013-01-01

    The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qmSSA) and SSA-normalized adsorption coefficient (Kd/SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (deltaG0) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (deltaH0), deltaG0 and free energy of adsorption (Ea), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and Kd/SSA or qm/SSA.

  12. Copper Accumulation, Availability and Adsorption Capacity in Sandy Soils of Vineyards with Different Cultivation Duration

    NASA Astrophysics Data System (ADS)

    Mallmann, F. J. K.; Miotto, A.; Bender, M. A.; Gubiani, E.; Rheinheimer, D. D. S.; Kaminski, J.; Ceretta, C. A.; Šimůnek, J.

    2015-12-01

    Bordeaux mixture is a copper-based (Cu) fungicide and bactericide applied in vineyards to control plant diseases. Since it is applied several times per year, it accumulates in large quantities on plants and in soil. This study evaluates the Cu accumulation in, and desorption kinetics and adsorption capability of a sandy Ultisol in a natural field and in 3 vineyards for 5 (V1), 11 (V2), and 31 (V3) years in South of Brazil. Soil samples were collected in 8 depths (0-60 cm) of all four soil profiles, which all displayed similar soil properties. The following soil properties were measured: pH, organic matter (OM), soil bulk density, Cu total concentration, and Cu desorption and adsorption curves. A two first-order reactions model and the Langmuir isotherm were fitted to the desorption and adsorption curves, respectively. An increase in the total mass of Cu in the vineyards followed a linear regression curve, with an average annual increase of 7.15 kg ha-1. Cu accumulated down to a depth of 5, 20, and 30 cm in V1, V2 and V3, respectively, with the highest Cu content reaching 138.4 mg kg-1 in the 0-5 cm soil layer of V3. Cu desorption parameters showed a high correlation with its total concentration. Approximately 57 and 19% of total Cu were immediately and slowly available, respectively, indicating a high potential for plant absorption and/or downward movement. Cu concentrations extracted by EDTA from soil layers not affected by anthropogenic Cu inputs were very low. The maximum Cu adsorption capacity of the 0-5 and 5-10 cm soil layers increased with the vineyard age, reaching concentrations higher than 900 mg kg-1. This increase was highly related to OM and pH, which both increased with cultivation duration. Despite of low clay content of these soils, there is low risk of groundwater Cu contamination for actual conditions. However, high Cu concentrations in the surface layer of the long-term vineyards could cause toxicity problems for this and for companion crops.

  13. Volumetric Interpretation of Protein Adsorption: Ion-Exchange Adsorbent Capacity, Protein pI, and Interaction Energetics

    PubMed Central

    Noh, Hyeran; Yohe, Stefan; Vogler, Erwin A.

    2008-01-01

    Adsorption of lysozyme (Lys), human serum albumin (HSA), and immunoglobulin G (IgG) to anion- and cation-exchange resins is dominated by electrostatic interactions between protein and adsorbent. The solution-depletion method of measuring adsorption shows, however, that these proteins do not irreversibly adsorb to ion-exchange surfaces, even when the charge disparity between adsorbent and protein inferred from protein pI is large. Net-positively-charged Lys (pI = 11) and net-negatively-charged HSA (pI = 5.5) adsorb so strongly to sulfopropyl sepharose (SP; a negatively-charged, strong cation exchange resin, −0.22 mmol/mL exchange capacity) that both resist displacement by net-neutral IgG (pI = 7.0) in simultaneous adsorption-competition experiments. By contrast, IgG readily displaces both Lys and HSA adsorbed either to quarternary-ammonium sepharose (Q; a positively-charged, strong anion exchanger, + 0.22 mmol/mL exchange capacity) or octadecyl sepharose (ODS, a neutral hydrophobic resin, 0 mmol/mL exchange capacity). Thus it is concluded that adsorption results do not sensibly correlate with protein pI and that pI is actually a rather poor predictor of affinity for ion-exchange surfaces. Adsorption of Lys, HSA, and IgG to ion-exchange resins from stagnant solution leads to adsorbed multi-layers, into-or-onto which IgG adsorbs in adsorption-competition experiments. Comparison of adsorption to ion-exchange resins and neutral ODS leads to the conclusion that the apparent standard free-energy-of-adsorption ΔGadso of Lys, HSA, and IgG is not large in comparison to thermal energy due to energy-compensating interactions between water, protein, and ion-exchange surfaces that leaves a small net ΔGadso. Thus water is found to control protein adsorption to a full range of substratum types spanning hydrophobic (poorly water wettable) surfaces, hydrophilic surfaces bearing relatively-weak Lewis acid/base functionalities that wet with (hydrogen bond to) water but do not

  14. Cu(II) and Zn(II) adsorption capacity of three different clay liner materials.

    PubMed

    Musso, T B; Parolo, M E; Pettinari, G; Francisca, F M

    2014-12-15

    Sorption of Cu(II) and Zn(II) on three natural clays meeting the international requirements for use as liners was evaluated by means of batch tests. The purpose of this research was to determine the retention capacities of the clays for metal cations commonly present in urban solid waste leachates. The pH and ionic strength conditions were set at values frequently found in real leachates. The changes observed in the XRD patterns and FTIR spectra upon adsorption can be considered an evidence of clay-metal electrostatic interaction. The Langmuir model was found to best describe the sorption processes, offering maximum sorption capacities from 8.16 to 56.89 mg/g for Cu(II) and from 49.59 to 103.83 mg/g for Zn(II). All samples remove more Zn(II) than Cu(II), which may be related to the different geometry of the hydrated Cu(II) cation. The total amount of metal sorption was strongly influenced by the total specific surface area, the presence of carbonates and the smectite content of the clays. In addition to their known quality as physical barriers, the adsorbed amounts obtained indicate the suitability of the tested clays to contribute to the retardation of Cu(II) and Zn(II) transport through clay liners.

  15. Synthesis, characterisation and adsorption properties of a porous copper(II) 3D coordination polymer exhibiting strong binding enthalpy and adsorption capacity for carbon dioxide.

    PubMed

    Eckold, Pierre; Gee, William J; Hill, Matthew R; Batten, Stuart R

    2012-11-21

    The synthesis and characterisation of microporous coordination polymers containing copper(II) or cobalt(II) and 2-(pyridin-4-yl)malonaldehyde (Hpma) is described and the gas adsorption properties evaluated. Single-crystal X-ray structure determinations identified the structures as [M(pma)(2)]·2X (M = Cu, 1; Co, 2; X = MeOH, MeCN), which contain 3D networks with rutile topology and continuous 1D rectangular channels with diameters ranging from 3 to 4 Å. The materials exhibit low BET surface areas of 143 m(2) g(-1), but possess large capacities for carbon dioxide capture of 14.1 wt%. The small pore channels are shown to account for this, delivering a particularly strong binding enthalpy to adsorbed CO(2) of 38 kJ mol(-1), and a very large adsorption capacity relative to the low surface area.

  16. Surface-Energetic Heterogeneity of Nanoporous Solids for CO2 and CO Adsorption: The Key to an Adsorption Capacity and Selectivity at Low Pressures.

    PubMed

    Kim, Moon Hyeon; Cho, Il Hum; Choi, Sang Ok; Lee, In Soo

    2016-05-01

    This study has been focused on surface energetic heterogeneity of zeolite (H-mordenite, "HM"), activated carbon ("RB2") and metal-organic framework family ("Z1200") materials and their isotherm features in adsorption of CO2 and CO at 25 degrees C and low pressures ≤ 850 Torr. The nanoporous solids showed not only distinctive shape of adsorption isotherms for CO2 with relatively high polarizability and quadrupole moment but also different capacities in the CO2 adsorption. These differences between the adsorbents could be well correlated with their surface nonuniformity. The most heterogeneous surfaces were found with the HM that gave the highest CO2 uptake at all pressures allowed, while the Z1200 consisted of completely homogeneous surfaces and even CO2 adsorption linearly increased with pressure. An intermediate character was indicated on the surface of RB2 and thus this sorbent possessed isotherm features between the HM and Z1200 in CO2 adsorption. Such different surface energetics was fairly consistent with changes in CO2/CO selectivity on the nanoporous adsorbents up to equilibrated pressures near 850 Torr. PMID:27483776

  17. EFFECT OF HEAT ON THE ADSORPTION CAPACITY OF AN ACTIVATED CARBON FOR DECOLORIZING/DEODORIZING YELLOW ZEIN

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Freundlich model was evaluated for use to assess the effect of heat on the adsorption capacity of an activated carbon for decolorizing/deodorizing corn zein. Because zein protein and its color/odor components are all adsorbed by activated carbon, a method to monitor their removal was needed. Y...

  18. EFFECT OF MOLECULAR OXYGEN ON ADSORPTIVE CAPACITY AND EXTRACTION EFFICIENCY OF GRANULATED ACTIVATED CARBON FOR THREE ORTHO-SUBSTITUTED PHENOLS

    EPA Science Inventory

    Adsorptive capacity of activated carbon for several organic compounds was found to be strongly influenced by the presence of molecular oxygen. This influence is manifested by the polymerization of adsorbate on the surface of activated carbon. As a result, GAC exhibits much high...

  19. Efficient Removal of Co2+ from Aqueous Solution by 3-Aminopropyltriethoxysilane Functionalized Montmorillonite with Enhanced Adsorption Capacity.

    PubMed

    Huang, Zhujian; Wu, Pingxiao; Gong, Beini; Dai, Yaping; Chiang, Pen-Chi; Lai, Xiaolin; Yu, Guangwei

    2016-01-01

    To achieve a satisfactory removal efficiency of heavy metal ions from wastewater, silane-functionalized montmorillonite with abundant ligand-binding sites (-NH2) was synthesized as an efficient adsorbent. Ca-montmorillonite (Ca-Mt) was functionalized with 3-aminopropyl triethoxysilane (APTES) to obtain the APTES-Mt products (APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt, APTES4.0CEC-Mt) with enhanced adsorption capacity for Co2+. The physico-chemical properties of the synthesized adsorbents were characterized by spectroscopic and microscopic methods, and the results demonstrated that APTES was successfully intercalated into the gallery of Ca-Mt or grafted onto the surface of Ca-Mt through Si-O bonds. The effect of solution pH, ionic strength, temperature, initial concentrations and contact time on adsorption of Co2+ by APTES-Mt was evaluated. The results indicated that adsorption of Co2+ onto Ca-Mt, APTES1.0CEC-Mt and APTES2.0CEC-Mt can be considered to be a pseudo-second-order process. In contrast, adsorption of Co2+ onto APTES3.0CEC-Mt and APTES4.0CEC-Mt fitted well with the pseudo-first-order kinetics. The adsorption isotherms were described by the Langmuir model, and the maximum adsorption capacities of APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt and APTES4.0CEC-Mt were 25.1, 33.8, 61.6, and 61.9 mg·g-1, respectively. In addition, reaction temperature had no impact on the adsorption capacity, while both the pH and ionic strength significantly affected the adsorption process. A synergistic effect of ion exchange and coordination interactions on adsorption was observed, thereby leading to a significant enhancement of Co2+ adsorption by the composites. Thus, APTES-Mt could be a cost-effective and environmental-friendly adsorbent, with potential for treating Co2+-rich wastewater. PMID:27448094

  20. Efficient Removal of Co2+ from Aqueous Solution by 3-Aminopropyltriethoxysilane Functionalized Montmorillonite with Enhanced Adsorption Capacity.

    PubMed

    Huang, Zhujian; Wu, Pingxiao; Gong, Beini; Dai, Yaping; Chiang, Pen-Chi; Lai, Xiaolin; Yu, Guangwei

    2016-01-01

    To achieve a satisfactory removal efficiency of heavy metal ions from wastewater, silane-functionalized montmorillonite with abundant ligand-binding sites (-NH2) was synthesized as an efficient adsorbent. Ca-montmorillonite (Ca-Mt) was functionalized with 3-aminopropyl triethoxysilane (APTES) to obtain the APTES-Mt products (APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt, APTES4.0CEC-Mt) with enhanced adsorption capacity for Co2+. The physico-chemical properties of the synthesized adsorbents were characterized by spectroscopic and microscopic methods, and the results demonstrated that APTES was successfully intercalated into the gallery of Ca-Mt or grafted onto the surface of Ca-Mt through Si-O bonds. The effect of solution pH, ionic strength, temperature, initial concentrations and contact time on adsorption of Co2+ by APTES-Mt was evaluated. The results indicated that adsorption of Co2+ onto Ca-Mt, APTES1.0CEC-Mt and APTES2.0CEC-Mt can be considered to be a pseudo-second-order process. In contrast, adsorption of Co2+ onto APTES3.0CEC-Mt and APTES4.0CEC-Mt fitted well with the pseudo-first-order kinetics. The adsorption isotherms were described by the Langmuir model, and the maximum adsorption capacities of APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt and APTES4.0CEC-Mt were 25.1, 33.8, 61.6, and 61.9 mg·g-1, respectively. In addition, reaction temperature had no impact on the adsorption capacity, while both the pH and ionic strength significantly affected the adsorption process. A synergistic effect of ion exchange and coordination interactions on adsorption was observed, thereby leading to a significant enhancement of Co2+ adsorption by the composites. Thus, APTES-Mt could be a cost-effective and environmental-friendly adsorbent, with potential for treating Co2+-rich wastewater.

  1. Efficient Removal of Co2+ from Aqueous Solution by 3-Aminopropyltriethoxysilane Functionalized Montmorillonite with Enhanced Adsorption Capacity

    PubMed Central

    Huang, Zhujian; Gong, Beini; Dai, Yaping; Chiang, Pen-Chi; Lai, Xiaolin; Yu, Guangwei

    2016-01-01

    To achieve a satisfactory removal efficiency of heavy metal ions from wastewater, silane-functionalized montmorillonite with abundant ligand-binding sites (-NH2) was synthesized as an efficient adsorbent. Ca-montmorillonite (Ca-Mt) was functionalized with 3-aminopropyl triethoxysilane (APTES) to obtain the APTES-Mt products (APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt, APTES4.0CEC-Mt) with enhanced adsorption capacity for Co2+. The physico-chemical properties of the synthesized adsorbents were characterized by spectroscopic and microscopic methods, and the results demonstrated that APTES was successfully intercalated into the gallery of Ca-Mt or grafted onto the surface of Ca-Mt through Si-O bonds. The effect of solution pH, ionic strength, temperature, initial concentrations and contact time on adsorption of Co2+ by APTES-Mt was evaluated. The results indicated that adsorption of Co2+ onto Ca-Mt, APTES1.0CEC-Mt and APTES2.0CEC-Mt can be considered to be a pseudo-second-order process. In contrast, adsorption of Co2+ onto APTES3.0CEC-Mt and APTES4.0CEC-Mt fitted well with the pseudo-first-order kinetics. The adsorption isotherms were described by the Langmuir model, and the maximum adsorption capacities of APTES1.0CEC-Mt, APTES2.0CEC-Mt, APTES3.0CEC-Mt and APTES4.0CEC-Mt were 25.1, 33.8, 61.6, and 61.9 mg·g-1, respectively. In addition, reaction temperature had no impact on the adsorption capacity, while both the pH and ionic strength significantly affected the adsorption process. A synergistic effect of ion exchange and coordination interactions on adsorption was observed, thereby leading to a significant enhancement of Co2+ adsorption by the composites. Thus, APTES-Mt could be a cost-effective and environmental-friendly adsorbent, with potential for treating Co2+-rich wastewater. PMID:27448094

  2. Effect of different carbon nanotubes on cadmium toxicity to Daphnia magna: The role of catalyst impurities and adsorption capacity.

    PubMed

    Wang, Xinghao; Qu, Ruijuan; Liu, Jiaoqin; Wei, Zhongbo; Wang, Liansheng; Yang, Shaogui; Huang, Qingguo; Wang, Zunyao

    2016-01-01

    Experiments were conducted to investigate the effect of four different carbon nanotubes single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) and hydroxylated and carboxylated multi-walled carbon nanotubes (OH-MWCNTs and COOH-MWCNTs) on Cd toxicity to the aquatic organism Daphnia magna. The acute toxicity results indicated that all CNTs could enhance the toxicity of Cd to D. magna. Furthermore, the filtrate toxicity and adsorption tests showed that the toxicity-increasing effect of SWCNTs and MWCNTs in the overall system was mainly caused by catalysts impurities from the pristine CNTs, whereas the greater adsorption of Cd onto OH-MWCNTs (30.52 mg/g) and COOH-MWCNTs (24.93 mg/g) was the key factor contributing to the enhanced toxicity. This result raised a concern that the metal catalyst impurities, adsorption capacities, and accumulation of waterborne CNTs were responsible for the toxicity of Cd to aquatic organism.

  3. Characterization of the cation-binding capacity of a potassium-adsorption filter used in red blood cell transfusion.

    PubMed

    Suzuki, Takao; Muto, Shigeaki; Miyata, Yukio; Maeda, Takao; Odate, Takayuki; Shimanaka, Kimio; Kusano, Eiji

    2015-06-01

    A K(+) -adsorption filter was developed to exchange K(+) in the supernatant of stored irradiated red blood cells with Na(+) . To date, however, the filter's adsorption capacity for K(+) has not been fully evaluated. Therefore, we characterized the cation-binding capacity of this filter. Artificial solutions containing various cations were continuously passed through the filter in 30 mL of sodium polystyrene sulfonate at 10 mL/min using an infusion pump at room temperature. The cation concentrations were measured before and during filtration. When a single solution containing K(+) , Li(+) , H(+) , Mg(2+) , Ca(2+) , or Al(3+) was continuously passed through the filter, the filter adsorbed K(+) and the other cations in exchange for Na(+) in direct proportion to the valence number. The order of affinity for cation adsorption to the filter was Ca(2+) >Mg(2+) >K(+) >H(+) >Li(+) . In K(+) -saturated conditions, the filter also adsorbed Na(+) . After complete adsorption of these cations on the filter, their concentration in the effluent increased in a sigmoidal manner over time. Cations that were bound to the filter were released if a second cation was passed through the filter, despite the different affinities of the two cations. The ability of the filter to bind cations, especially K(+) , should be helpful when it is used for red blood cell transfusion at the bedside. The filter may also be useful to gain a better understanding of the pharmacological properties of sodium polystyrene sulfonate.

  4. Novel hollow microspheres of hierarchical zinc-aluminum layered double hydroxides and their enhanced adsorption capacity for phosphate in water.

    PubMed

    Zhou, Jiabin; Yang, Siliang; Yu, Jiaguo; Shu, Zhan

    2011-09-15

    Hollow microspheres of hierarchical Zn-Al layered double hydroxides (LDHs) were synthesized by a simple hydrothermal method using urea as precipitating agent. The morphology and microstructure of the as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), nitrogen adsorption-desorption isotherms and fourier transform infrared (FTIR) spectroscopy. It was found that the morphology of hierarchical Zn-Al LDHs can be tuned from irregular platelets to hollow microspheres by simply varying concentrations of urea. The effects of initial phosphate concentration and contact time on phosphate adsorption using various Zn-Al LDHs and their calcined products (LDOs) were investigated from batch tests. Our results indicate that the equilibrium adsorption data were best fitted by Langmuir isothermal model, with the maximum adsorption capacity of 54.1-232 mg/g; adsorption kinetics follows the pseudo-second-order kinetic equation and intra-particle diffusion model. In addition, Zn-Al LDOs are shown to be effective adsorbents for removing phosphate from aqueous solutions due to their hierarchical porous structures and high specific surface areas.

  5. Predicting CH4 adsorption capacity of microporous carbon using N2 isotherm and a new analytical model

    USGS Publications Warehouse

    Sun, Jielun; Chen, S.; Rostam-Abadi, M.; Rood, M.J.

    1998-01-01

    A new analytical pore size distribution (PSD) model was developed to predict CH4 adsorption (storage) capacity of microporous adsorbent carbon. The model is based on a 3-D adsorption isotherm equation, derived from statistical mechanical principles. Least squares error minimization is used to solve the PSD without any pre-assumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers relatively realistic PSD description for select reference materials, including activated carbon fibers. N2 and CH4 adsorption data were correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms, based on N2 adsorption at 77 K, were in reasonable agreement with the experimental CH4 isotherms. Modeling results indicate that not all the pores contribute the same percentage Vm/Vs for CH4 storage due to different adsorbed CH4 densities. Pores near 8-9 A?? shows higher Vm/Vs on the equivalent volume basis than does larger pores.

  6. QM/MM Calculations on Proteins.

    PubMed

    Ryde, U

    2016-01-01

    In this chapter, I discuss combined quantum mechanics (QM) and molecular mechanics (MM; QM/MM) calculations for proteins. In QM/MM, a small but interesting part of the protein is treated by accurate QM methods, whereas the remainder is treated by faster MM methods. The prime problems with QM/MM calculations are bonds between the QM and MM systems, the selection of the QM system, and the local-minima problem. The two first problems can be solved by the big-QM approach, including in the QM calculation all groups within 4.5-6Å of the active site and all buried charges in the protein. The third problem can be solved by calculating free energies. It is important to study QM/MM energy components to ensure that the results are stable and reliable. They can also be used to understand the reaction and the effect of the surroundings, eg, by dividing the catalytic effect into bonded, van der Waals, electrostatic, and geometric components and to deduce which parts of the protein contribute most to the catalysis. It should be ensured that the QM calculations are reliable and converged by extending the basis set to quadruple-zeta quality, including a proper treatment of dispersion, as well as years experience and method development calculations with both pure and hybrid density functional theory methods. If the latter give differing results, calibration with high-level QM methods is needed. Reactions that change the net charge should be avoided. QM/MM calculations can be combined with experimental methods. PMID:27498637

  7. Hydrogen adsorption capacity of adatoms on double carbon vacancies of graphene: A trend study from first principles

    NASA Astrophysics Data System (ADS)

    Fair, K. M.; Cui, X. Y.; Li, L.; Shieh, C. C.; Zheng, R. K.; Liu, Z. W.; Delley, B.; Ford, M. J.; Ringer, S. P.; Stampfl, C.

    2013-01-01

    Structural stability and hydrogen adsorption capacity are two key quantities in evaluating the potential of metal-adatom decorated graphene for hydrogen storage and related devices. We have carried out extensive density functional theory calculations for the adsorption of hydrogen molecules on 12 different adatom (Ag, Au, Ca, Li, Mg, Pd, Pt, Sc, Sr, Ti, Y, and Zr) decorated graphene surfaces where the adatoms are found to be stabilized on double carbon vacancies, thus overcoming the “clustering problem” that occurs for adatoms on pristine graphene. Ca and Sr are predicted to bind the greatest number, namely six, of H2 molecules. We find an interesting correlation between the hydrogen capacity and the change of charge distribution with increasing H2 adsorption, where Ca, Li, Mg, Sc, Ti, Y, Sr, and Zr adatoms are partial electron donors and Ag, Au, Pd, and Pt are partial electron acceptors. The “18-electron rule” for predicting maximum hydrogen capacity is found not to be a reliable indicator for these systems.

  8. Effects of Igneous Intrusion on Microporosity and Gas Adsorption Capacity of Coals in the Haizi Mine, China

    PubMed Central

    2014-01-01

    This paper describes the effects of igneous intrusions on pore structure and adsorption capacity of the Permian coals in the Huaibei Coalfield, China. Twelve coal samples were obtained at different distances from a ~120 m extremely thick sill. Comparisons were made between unaltered and heat-affected coals using geochemical data, pore-fracture characteristics, and adsorption properties. Thermal alteration occurs down to ~1.3 × sill thickness. Approaching the sill, the vitrinite reflectance (Ro) increased from 2.30% to 2.78%, forming devolatilization vacuoles and a fine mosaic texture. Volatile matter (VM) decreased from 17.6% to 10.0% and the moisture decreased from 3.0% to 1.6%. With decreasing distance to the sill, the micropore volumes initially increased from 0.0054 cm3/g to a maximum of 0.0146 cm3/g and then decreased to 0.0079 cm3/g. The results show that the thermal evolution of the sill obviously changed the coal geochemistry and increased the micropore volume and adsorption capacity of heat-affected coal (60–160 m from the sill) compared with the unaltered coals. The trap effect of the sill prevented the high-pressure gas from being released, forming gas pocket. Mining activities near the sill created a low pressure zone leading to the rapid accumulation of methane and gas outbursts in the Haizi Mine. PMID:24723841

  9. Effects of igneous intrusion on microporosity and gas adsorption capacity of coals in the Haizi Mine, China.

    PubMed

    Jiang, Jingyu; Cheng, Yuanping

    2014-01-01

    This paper describes the effects of igneous intrusions on pore structure and adsorption capacity of the Permian coals in the Huaibei Coalfield, China. Twelve coal samples were obtained at different distances from a ~120 m extremely thick sill. Comparisons were made between unaltered and heat-affected coals using geochemical data, pore-fracture characteristics, and adsorption properties. Thermal alteration occurs down to ~1.3 × sill thickness. Approaching the sill, the vitrinite reflectance (R(o)) increased from 2.30% to 2.78%, forming devolatilization vacuoles and a fine mosaic texture. Volatile matter (VM) decreased from 17.6% to 10.0% and the moisture decreased from 3.0% to 1.6%. With decreasing distance to the sill, the micropore volumes initially increased from 0.0054 cm(3)/g to a maximum of 0.0146 cm(3)/g and then decreased to 0.0079 cm(3)/g. The results show that the thermal evolution of the sill obviously changed the coal geochemistry and increased the micropore volume and adsorption capacity of heat-affected coal (60-160 m from the sill) compared with the unaltered coals. The trap effect of the sill prevented the high-pressure gas from being released, forming gas pocket. Mining activities near the sill created a low pressure zone leading to the rapid accumulation of methane and gas outbursts in the Haizi Mine.

  10. Effects of igneous intrusion on microporosity and gas adsorption capacity of coals in the Haizi Mine, China.

    PubMed

    Jiang, Jingyu; Cheng, Yuanping

    2014-01-01

    This paper describes the effects of igneous intrusions on pore structure and adsorption capacity of the Permian coals in the Huaibei Coalfield, China. Twelve coal samples were obtained at different distances from a ~120 m extremely thick sill. Comparisons were made between unaltered and heat-affected coals using geochemical data, pore-fracture characteristics, and adsorption properties. Thermal alteration occurs down to ~1.3 × sill thickness. Approaching the sill, the vitrinite reflectance (R(o)) increased from 2.30% to 2.78%, forming devolatilization vacuoles and a fine mosaic texture. Volatile matter (VM) decreased from 17.6% to 10.0% and the moisture decreased from 3.0% to 1.6%. With decreasing distance to the sill, the micropore volumes initially increased from 0.0054 cm(3)/g to a maximum of 0.0146 cm(3)/g and then decreased to 0.0079 cm(3)/g. The results show that the thermal evolution of the sill obviously changed the coal geochemistry and increased the micropore volume and adsorption capacity of heat-affected coal (60-160 m from the sill) compared with the unaltered coals. The trap effect of the sill prevented the high-pressure gas from being released, forming gas pocket. Mining activities near the sill created a low pressure zone leading to the rapid accumulation of methane and gas outbursts in the Haizi Mine. PMID:24723841

  11. A theoretical and experimental study on the P-adsorption capacity of Phoslock™

    NASA Astrophysics Data System (ADS)

    Zamparas, Miltiadis; Gavriil, Gavriil; Coutelieris, Frank A.; Zacharias, Ierotheos

    2015-04-01

    The main objective of this study is to investigate the adsorption process from both experimental and modeling point of view of phosphate onto Phoslock™, an increasingly used worldwide restoration tool to control phosphorus from natural water ecosystems. Bench-scale batch experiments were performed to examine its efficiency as a phosphate adsorbent and detailed simulations were carried out, allowing for a deep insight of the removal process. The adsorption efficiency calculated by the simulations is 87.41%, being in excellent agreement with that experimentally measured (approx. 87%). However, it is important to notice the discrepancy between experimental measures and simulation estimates. Although the agreement is perfect for T = 25 °C, it becomes more and more poor as temperature decreases, approaching approx. 10% difference for the low temperature of 10 °C. This inconsistency between experiments and model can be attributed to the internal inefficiencies of unit cell approach, which in particular overestimates the adsorption efficiency.

  12. Age-dependent degradation of the protein adsorption capacity of titanium.

    PubMed

    Hori, N; Att, W; Ueno, T; Sato, N; Yamada, M; Saruwatari, L; Suzuki, T; Ogawa, T

    2009-07-01

    Reported bone-implant contact percentages are far below the ideal 100%. We tested a hypothesis that the protein adsorption capability of titanium, which is critical to the process of osseointegration, changes over time before its use. Machined, acid-etched, and sandblasted surfaces were prepared and stored under dark ambient conditions for 3 days, 1 week, or 4 weeks. For all surfaces, protein adsorption decreased as the storage time increased, and their decreasing rates were dependent on titanium topography. After 4 weeks, the amounts of albumin and fibronectin adsorbed by the acid-etched surface were only 20% and 35%, respectively, of that adsorbed by the fresh surface after 2 hours of incubation, and remained substantially low even after 24 hours. This time-dependent degradation in protein adsorption of titanium correlated with its naturally decreasing hydrophilicity, which was not observed for the nickel and chromium surfaces, indicating a titanium-specific biological aging.

  13. 2,4-D adsorption to biochars: effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data.

    PubMed

    Kearns, J P; Wellborn, L S; Summers, R S; Knappe, D R U

    2014-10-01

    Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications.

  14. 2,4-D adsorption to biochars: effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data.

    PubMed

    Kearns, J P; Wellborn, L S; Summers, R S; Knappe, D R U

    2014-10-01

    Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications. PMID:24934321

  15. Preparation of porous diatomite-templated carbons with large adsorption capacity and mesoporous zeolite K-H as a byproduct.

    PubMed

    Liu, Dong; Yuan, Weiwei; Deng, Liangliang; Yu, Wenbin; Sun, Hongjuan; Yuan, Peng

    2014-06-15

    In this study, KOH activation was performed to enhance the porosity of the diatomite-templated carbon and to increase its adsorption capacity of methylene blue (MB). In addition to serving as the activation agent, KOH was also used as the etchant to remove the diatomite templates. Zeolite K-H was synthesized as a byproduct via utilization of the resultant silicon- and potassium-containing solutions created from the KOH etching of the diatomite templates. The obtained diatomite-based carbons were composed of macroporous carbon pillars and tubes, which were derived from the replication of the diatomite templates and were well preserved after KOH activation. The abundant micropores in the walls of the carbon pillars and tubes were derived from the break and reconfiguration of carbon films during both the removal of the diatomite templates and KOH activation. Compared with the original diatomite-templated carbons and CO2-activated carbons, the KOH-activated carbons had much higher specific surface areas (988 m(2)/g) and pore volumes (0.675 cm(3)/g). Moreover, the KOH-activated carbons possessed larger MB adsorption capacity (the maximum Langmuir adsorption capacity: 645.2 mg/g) than those of the original carbons and CO2-activated carbons. These results showed that KOH activation was a high effective activation method. The zeolite K-H byproduct was obtained by utilizing the silicon- and potassium-containing solution as the silicon and potassium sources. The zeolite exhibited a stick-like morphology and possessed nanosized particles with a mesopore-predominant porous structure which was observed by TEM for the first time.

  16. PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR ORGANIC CONTAMINANTS FROM ADSORBENT AND ADSORBATE PROPERTIES

    EPA Science Inventory

    A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (βl

  17. Evaluation of phosphorus adsorption capacity of sesame straw biochar on aqueous solution: influence of activation methods and pyrolysis temperatures.

    PubMed

    Park, J H; Ok, Y S; Kim, S H; Cho, J S; Heo, J S; Delaune, R D; Seo, D C

    2015-12-01

    The phosphorus (P) adsorption characteristic of sesame straw biochar prepared with different activation agents and pyrolysis temperatures was evaluated. Between 0.109 and 0.300 mg L(-1) in the form of inorganic phosphate was released from raw sesame straw biochar in the first 1 h. The release of phosphate was significantly enhanced from 62.6 to 168.2 mg g(-1) as the pyrolysis temperature increased. Therefore, sesame straw biochar cannot be used as an adsorbent for P removal without change in the physicochemical characteristics. To increase the P adsorption of biochar in aqueous solution, various activation agents and pyrolysis temperatures were applied. The amount of P adsorbed from aqueous solution by biochar activated using different activation agents appeared in the order ZnCl2 (9.675 mg g(-1)) > MgO (8.669 mg g(-1)) ⋙ 0.1N-HCl > 0.1N-H2SO4 > K2SO4 ≥ KOH ≥ 0.1N-H3PO4, showing ZnCl2 to be the optimum activation agent. Higher P was adsorbed by the biochar activated using ZnCl2 under different pyrolysis temperatures in the order 600 °C > 500 °C > 400 °C > 300 °C. Finally, the amount of adsorbed P by activated biochar at different ratios of biochar to ZnCl2 appeared in the order 1:3 ≒ 1:1 > 3:1. As a result, the optimum ratio of biochar to ZnCl2 and pyrolysis temperature were found to be 1:1 and 600 °C for P adsorption, respectively. The maximum P adsorption capacity by activated biochar using ZnCl2 (15,460 mg kg(-1)) was higher than that of typical biochar, as determined by the Langmuir adsorption isotherm. Therefore, the ZnCl2 activation of sesame straw biochar was suitable for the preparation of activated biochar for P adsorption.

  18. Effects of sulfur impregnation temperature on the properties and mercury adsorption capacities of activated carbon fibers (ACFs).

    PubMed

    Hsi, H C; Rood, M J; Rostam-Abadi, M; Chen, S; Chang, R

    2001-07-01

    Laboratory studies were conducted to determine the role of sulfur functional groups and micropore surface area of carbon-based adsorbents on the adsorption of Hg0 from simulated coal combustion flue gases. In this study, raw activated carbon fibers that are microporous (ACF-20) were impregnated with elemental sulfur between 250 and 650 degrees C. The resulting samples were saturated with respect to sulfur content. Total sulfur content of the sulfur impregnated ACF samples decreased with increasing impregnation temperatures from 250 and 500 degrees C and then remained constant to 650 degrees C. Results from sulfur K-edge X-ray absorption near-edge structure (S-XANES) spectroscopy showed that sulfur impregnated on the ACF samples was in both elemental and organic forms. As sulfur impregnation temperature increased, however, the relative amounts of elemental sulfur decreased with a concomitant increase in the amount of organic sulfur. Thermal analyses and mass spectrometry revealed that sulfur functional groups formed at higher impregnation temperatures were more thermally stable. In general, sulfur impregnation decreased surface area and increased equilibrium Hg0 adsorption capacity when compared to the raw ACF sample. The ACF sample treated with sulfur at 400 degrees C had a surface area of only 94 m2/g compared to the raw ACF sample's surface area of 1971 m2/g, but at least 86% of this sample's surface area existed as micropores and it had the largest equilibrium Hg0 adsorption capacities (2211-11,343 micrograms/g). Such a result indicates that 400 degrees C is potentially an optimal sulfur impregnation temperature for this ACF. Sulfur impregnated on the ACF that was treated at 400 degrees C was in both elemental and organic forms. Thermal analyses and CS2 extraction tests suggested that elemental sulfur was the main form of sulfur affecting the Hg0 adsorption capacity. These findings indicate that both the presence of elemental sulfur on the adsorbent and a

  19. Effects of sulfur impregnation temperature on the properties and mercury adsorption capacities of activated carbon fibers (ACFs)

    USGS Publications Warehouse

    Hsi, H.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2001-01-01

    Laboratory studies were conducted to determine the role of sulfur functional groups and micropore surface area of carbon-based adsorbents on the adsorption of Hg0 from simulated coal combustion flue gases. In this study, raw activated carbon fibers that are microporous (ACF-20) were impregnated with elemental sulfur between 250 and 650 ??C. The resulting samples were saturated with respect to sulfur content. Total sulfur content of the sulfur impregnated ACF samples decreased with increasing impregnation temperatures from 250 and 500 ??C and then remained constant to 650 ??C. Results from sulfur K-edge X-ray absorption near-edge structure (S-XANES) spectroscopy showed that sulfur impregnated on the ACF samples was in both elemental and organic forms. As sulfur impregnation temperature increased, however, the relative amounts of elemental sulfur decreased with a concomitant increase in the amount of organic sulfur. Thermal analyses and mass spectrometry revealed that sulfur functional groups formed at higher impregnation temperatures were more thermally stable. In general, sulfur impregnation decreased surface area and increased equilibrium Hg0 adsorption capacity when compared to the raw ACF sample. The ACF sample treated with sulfur at 400 ??C had a surface area of only 94 m2/g compared to the raw ACF sample's surface area of 1971 m2/g, but at least 86% of this sample's surface area existed as micropores and it had the largest equilibrium Hg0adsorption capacities (2211-11343 ??g/g). Such a result indicates that 400 ??C is potentially an optimal sulfur impregnation temperature for this ACF. Sulfur impregnated on the ACF that was treated at 400 ??C was in both elemental and organic forms. Thermal analyses and CS2extraction tests suggested that elemental sulfur was the main form of sulfur affecting the Hg0 adsorption capacity. These findings indicate that both the presence of elemental sulfur on the adsorbent and a microporous structure are important properties for

  20. Synthesis, characterisation and methyl orange adsorption capacity of ferric oxide-biochar nano-composites derived from pulp and paper sludge

    NASA Astrophysics Data System (ADS)

    Chaukura, Nhamo; Murimba, Edna C.; Gwenzi, Willis

    2016-02-01

    A Fe2O3-biochar nano-composite (Fe2O3-BC) was prepared from FeCl3-impregnated pulp and paper sludge (PPS) by pyrolysis at 750 °C. The characteristics and methyl orange (MO) adsorption capacity of Fe2O3-BC were compared to that of unactivated biochar (BC). X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the composite material was nano-sized. Fourier transform infrared (FTIR) spectroscopy revealed the presence of hydroxyl and aromatic groups on BC and on Fe2O3-BC, but Brunauer-Emmett-Teller (BET) surface area and Barrett-Joyner-Halenda (BJH) porosity were lower for Fe2O3-BC than BC. Despite the lower BET surface area and porosity of Fe2O3-BC, its MO adsorption capacity was 52.79 % higher than that of BC. The equilibrium adsorption data were best represented by the Freundlich model with a maximum adsorption capacity of 20.53 mg g-1 at pH 8 and 30 min contact time. MO adsorption obeyed pseudo-second-order kinetics for both BC and Fe2O3-BC with R 2 values of 0.996 and 0.999, respectively. Higher MO adsorption capacity for Fe2O3-BC was attributed to the hybrid nature of the nano-composites; adsorption occurred on both biochar matrix and Fe2O3 nanocrystals. Gibbs free energy calculations confirmed the adsorption is energetically favourable and spontaneous with a high preference for adsorption on both adsorbents. The nano-composite can be used for the efficient removal of MO (>97 %) from contaminated wastewater.

  1. Determination of coalbed methane potential and gas adsorption capacity in Western Kentucky coals

    USGS Publications Warehouse

    Mardon, S.M.; Takacs, K.G.; Hower, J.C.; Eble, C.F.; Mastalerz, Maria

    2006-01-01

    The Illinois Basin has not been developed for Coalbed Methane (CBM) production. It is imperative to determine both gas content and other parameters for the Kentucky portion of the Illinois Basin if exploration is to progress and production is to occur in this area. This research is part of a larger project being conducted by the Kentucky Geological Survey to evaluate the CBM production of Pennsylvanian-age western Kentucky coals in Ohio, Webster, and Union counties using methane adsorption isotherms, direct gas desorption measurements, and chemical analyses of coal and gas. This research will investigate relationships between CBM potential and petrographic, surface area, pore size, and gas adsorption isotherm analyses of the coals. Maceral and reflectance analyses are being conducted at the Center for Applied Energy Research. At the Indiana Geological Survey, the surface area and pore size of the coals will be analyzed using a Micrometrics ASAP 2020, and the CO2 isotherm analyses will be conducted using a volumetric adsorption apparatus in a water temperature bath. The aforementioned analyses will be used to determine site specific correlations for the Kentucky part of the Illinois Basin. The data collected will be compared with previous work in the Illinois Basin and will be correlated with data and structural features in the basin. Gas composition and carbon and hydrogen isotopic data suggest mostly thermogenic origin of coalbed gas in coals from Webster and Union Counties, Kentucky, in contrast to the dominantly biogenic character of coalbed gas in Ohio County, Kentucky.

  2. Synthesis of bilayer MoS{sub 2} nanosheets by a facile hydrothermal method and their methyl orange adsorption capacity

    SciTech Connect

    Ye, Lijuan; Xu, Haiyan; Zhang, Dingke; Chen, Shijian

    2014-07-01

    Highlights: • Hexagonal phase of MoS{sub 2} nanosheets was synthesized by a facile hydrothermal method. • FE-SEM and TEM images show the sheets-like morphology of MoS{sub 2}. • Bilayer MoS{sub 2} can be grown under the optimized mole ratio of 2:1 of S:Mo at 180 °C for 50 h. • The MoS{sub 2} nanosheets possess high methyl orange adsorption capacity due to the large surface area. - Abstract: Molybdenum disulfide (MoS{sub 2}) nanosheets have received significant attention recently due to the potential applications for exciting physics and technology. Here we show that MoS{sub 2} nanosheets can be prepared by a facile hydrothermal method. The study of the properties of the MoS{sub 2} nanosheets prepared at different conditions suggests that the mole ratio of precursors and hydrothermal time significantly influences the purity, crystalline quality and thermal stability of MoS{sub 2}. X-ray diffraction, Raman spectra and transmission electron microscopy results indicate that bilayer MoS{sub 2} can be grown under an optimized mole ratio of 2:1 of S:Mo at 180 °C for 50 h. Moreover, such ultrathin nanosheets exhibit a prominent photoluminescence and possess high methyl orange adsorption capacity due to the large surface area, which can be potentially used in photodevice and photochemical catalyst.

  3. Zeolite Y Adsorbents with High Vapor Uptake Capacity and Robust Cycling Stability for Potential Applications in Advanced Adsorption Heat Pumps.

    PubMed

    Li, Xiansen; Narayanan, Shankar; Michaelis, Vladimir K; Ong, Ta-Chung; Keeler, Eric G; Kim, Hyunho; McKay, Ian S; Griffin, Robert G; Wang, Evelyn N

    2015-01-01

    Modular and compact adsorption heat pumps (AHPs) promise an energy-efficient alternative to conventional vapor compression based heating, ventilation and air conditioning systems. A key element in the advancement of AHPs is the development of adsorbents with high uptake capacity, fast intracrystalline diffusivity and durable hydrothermal stability. Herein, the ion exchange of NaY zeolites with ingoing Mg(2+) ions is systematically studied to maximize the ion exchange degree (IED) for improved sorption performance. It is found that beyond an ion exchange threshold of 64.1%, deeper ion exchange does not benefit water uptake capacity or characteristic adsorption energy, but does enhance the vapor diffusivity. In addition to using water as an adsorbate, the uptake properties of Mg,Na-Y zeolites were investigated using 20 wt.% MeOH aqueous solution as a novel anti-freeze adsorbate, revealing that the MeOH additive has an insignificant influence on the overall sorption performance. We also demonstrated that the labscale synthetic scalability is robust, and that the tailored zeolites scarcely suffer from hydrothermal stability even after successive 108-fold adsorption/desorption cycles. The samples were analyzed using N2 sorption, (27)Al/(29)Si MAS NMR spectroscopy, ICP-AES, dynamic vapor sorption, SEM, Fick's 2(nd) law and D-R equation regressions. Among these, close examination of sorption isotherms for H2O and N2 adsorbates allows us to decouple and extract some insightful information underlying the complex water uptake phenomena. This work shows the promising performance of our modified zeolites that can be integrated into various AHP designs for buildings, electronics, and transportation applications.

  4. Zeolite Y Adsorbents with High Vapor Uptake Capacity and Robust Cycling Stability for Potential Applications in Advanced Adsorption Heat Pumps.

    PubMed

    Li, Xiansen; Narayanan, Shankar; Michaelis, Vladimir K; Ong, Ta-Chung; Keeler, Eric G; Kim, Hyunho; McKay, Ian S; Griffin, Robert G; Wang, Evelyn N

    2015-01-01

    Modular and compact adsorption heat pumps (AHPs) promise an energy-efficient alternative to conventional vapor compression based heating, ventilation and air conditioning systems. A key element in the advancement of AHPs is the development of adsorbents with high uptake capacity, fast intracrystalline diffusivity and durable hydrothermal stability. Herein, the ion exchange of NaY zeolites with ingoing Mg(2+) ions is systematically studied to maximize the ion exchange degree (IED) for improved sorption performance. It is found that beyond an ion exchange threshold of 64.1%, deeper ion exchange does not benefit water uptake capacity or characteristic adsorption energy, but does enhance the vapor diffusivity. In addition to using water as an adsorbate, the uptake properties of Mg,Na-Y zeolites were investigated using 20 wt.% MeOH aqueous solution as a novel anti-freeze adsorbate, revealing that the MeOH additive has an insignificant influence on the overall sorption performance. We also demonstrated that the labscale synthetic scalability is robust, and that the tailored zeolites scarcely suffer from hydrothermal stability even after successive 108-fold adsorption/desorption cycles. The samples were analyzed using N2 sorption, (27)Al/(29)Si MAS NMR spectroscopy, ICP-AES, dynamic vapor sorption, SEM, Fick's 2(nd) law and D-R equation regressions. Among these, close examination of sorption isotherms for H2O and N2 adsorbates allows us to decouple and extract some insightful information underlying the complex water uptake phenomena. This work shows the promising performance of our modified zeolites that can be integrated into various AHP designs for buildings, electronics, and transportation applications. PMID:25395877

  5. Zeolite Y adsorbents with high vapor uptake capacity and robust cycling stability for potential applications in advanced adsorption heat pumps

    SciTech Connect

    Li, XS; Narayanan, S; Michaelis, VK; Ong, TC; Keeler, EG; Kim, H; Mckay, IS; Griffin, RG; Wang, EN

    2015-01-01

    Modular and compact adsorption heat pumps (AHPs) promise an energy-efficient alternative to conventional vapor compression based heating, ventilation and air conditioning systems. A key element in the advancement of AHPs is the development of adsorbents with high uptake capacity, fast intracrystalline diffusivity and durable hydrothermal stability. Herein, the ion exchange of NaY zeolites with ingoing Mg2+ ions is systematically studied to maximize the ion exchange degree (IED) for improved sorption performance. It is found that beyond an ion exchange threshold of 64.1%, deeper ion exchange does not benefit water uptake capacity or characteristic adsorption energy, but does enhance the vapor diffusivity. In addition to using water as an adsorbate, the uptake properties of Mg, Na-Y zeolites were investigated using 20 wt.% MeOH aqueous solution as a novel anti-freeze adsorbate, revealing that the MeOH additive has an insignificant influence on the overall sorption performance. We also demonstrated that the lab-scale synthetic scalability is robust, and that the tailored zeolites scarcely suffer from hydrothermal stability even after successive 108-fold adsorption/desorption cycles. The samples were analyzed using N-2 sorption, Al-27/Si-29 MAS NMR spectroscopy, ICP-AES, dynamic vapor sorption, SEM, Fick's 2nd law and D-R equation regressions. Among these, close examination of sorption isotherms for H2O and N-2 adsorbates allows us to decouple and extract some insightful information underlying the complex water uptake phenomena. This work shows the promising performance of our modified zeolites that can be integrated into various AHP designs for buildings, electronics, and transportation applications. (C) 2014 Elsevier Inc. All rights reserved.

  6. Zeolite Y Adsorbents with High Vapor Uptake Capacity and Robust Cycling Stability for Potential Applications in Advanced Adsorption Heat Pumps

    PubMed Central

    Li, Xiansen; Narayanan, Shankar; Michaelis, Vladimir K.; Ong, Ta-Chung; Keeler, Eric G.; Kim, Hyunho; McKay, Ian S.; Griffin, Robert G.; Wang, Evelyn N.

    2014-01-01

    Modular and compact adsorption heat pumps (AHPs) promise an energy-efficient alternative to conventional vapor compression based heating, ventilation and air conditioning systems. A key element in the advancement of AHPs is the development of adsorbents with high uptake capacity, fast intracrystalline diffusivity and durable hydrothermal stability. Herein, the ion exchange of NaY zeolites with ingoing Mg2+ ions is systematically studied to maximize the ion exchange degree (IED) for improved sorption performance. It is found that beyond an ion exchange threshold of 64.1%, deeper ion exchange does not benefit water uptake capacity or characteristic adsorption energy, but does enhance the vapor diffusivity. In addition to using water as an adsorbate, the uptake properties of Mg,Na-Y zeolites were investigated using 20 wt.% MeOH aqueous solution as a novel anti-freeze adsorbate, revealing that the MeOH additive has an insignificant influence on the overall sorption performance. We also demonstrated that the labscale synthetic scalability is robust, and that the tailored zeolites scarcely suffer from hydrothermal stability even after successive 108-fold adsorption/desorption cycles. The samples were analyzed using N2 sorption, 27Al/29Si MAS NMR spectroscopy, ICP-AES, dynamic vapor sorption, SEM, Fick’s 2nd law and D-R equation regressions. Among these, close examination of sorption isotherms for H2O and N2 adsorbates allows us to decouple and extract some insightful information underlying the complex water uptake phenomena. This work shows the promising performance of our modified zeolites that can be integrated into various AHP designs for buildings, electronics, and transportation applications. PMID:25395877

  7. Introduction to QM/MM simulations.

    PubMed

    Groenhof, Gerrit

    2013-01-01

    Hybrid quantum mechanics/molecular mechanics (QM/MM) simulations have become a popular tool for investigating chemical reactions in condensed phases. In QM/MM methods, the region of the system in which the chemical process takes place is treated at an appropriate level of quantum chemistry theory, while the remainder is described by a molecular mechanics force field. Within this approach, chemical reactivity can be studied in large systems, such as enzymes. In the first part of this contribution, the basic methodology is briefly reviewed. The two most common approaches for partitioning the two subsystems are presented, followed by a discussion on the different ways of treating interactions between the subsystems. Special attention is given on how to deal with situations in which the boundary between the QM and MM subsystems runs through one or more chemical bonds. The second part of this contribution discusses what properties of larger system can be obtained within the QM/MM framework and how. Finally, as an example of a QM/MM application in practice, the third part presents an overview of recent QM/MM molecular dynamics simulations on photobiological systems. In addition to providing quantities that are experimentally accessible, such as structural intermediates, fluorescence lifetimes, quantum yields and spectra, the QM/MM simulations also provide information that is much more difficult to measure experimentally, such as reaction mechanisms and the influence of individual amino acid residues.

  8. Adsorption of lead (II) ions onto novel cassava starch 5-choloromethyl-8-hydroxyquinoline polymer from an aqueous medium.

    PubMed

    Shah, Prapti U; Raval, Nirav P; Vekariya, Mayur; Wadhwani, Poonam M; Shah, Nisha K

    2016-01-01

    Adsorption of lead (II) ions onto cassava starch 5-choloromethyl-8-hydroxyquinoline polymer (CSCMQ) was investigated with the variation in the parameters of pH, contact time, lead (II) ions concentration, temperature and the adsorbent dose. The Langmuir and Freundlich models have been applied. CSCMQ was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Results showed that the adsorption process was better described by the Langmuir model. Adsorption kinetics data obtained for the metal ions sorption were investigated using pseudo-first-order, pseudo-second-order and intraparticle diffusion model. The maximum adsorption capacities (qm) were 46.512, 43.859 and 42.735 mg/g at 25, 35 and 45 °C, respectively. The dynamical data fit well with the second-order kinetics model. The results indicate that CSCMQ could be employed as low-cost material for the adsorption of Pb(II) ions from aqueous medium. PMID:27533869

  9. High surface-area amidoxime-based polymer fibers co-grafted with various acid monomers yielding increased adsorption capacity for the extraction of uranium from seawater.

    PubMed

    Oyola, Yatsandra; Dai, Sheng

    2016-06-01

    Uranium is dissolved in the ocean at a uniform concentration of 3.34 ppb, which translates to approximately 4-5 billion tons of uranium. The development of adsorbents that can extract uranium from seawater has been a long term goal, but the extremely dilute uranium concentration along with the competition of other metal salts (which are at higher concentrations) has hindered the development of an economical adsorption process. Several acid monomers were co-grafted with acrylonitrile (AN) to help increase the hydrophilicity of the adsorbent to improve access to the metal adsorption sites. Grafting various acid monomers on PE fibers was found to significantly affect the uranium adsorption in simulated seawater in the following order: acrylic acid (AA) < vinyl sulfonic acid (VSA) < methacrylic acid (MAA) < itaconic acid (ITA) < vinyl phosphonic acid (VPA). Interestingly, the uranium adsorption capacity significantly increased when Mohr's salt was added with acrylic acid, most likely due to the reduction of co-polymerization of the monomers. When testing under more realistic conditions, the acid-grafted PE fiber adsorbents were exposed to natural seawater (more dilute uranium), the uranium adsorption capacity increased in the following order: MAA < AA (Mohr's salt) < VSA < ITA (Mohr's salt) < ITA < VPA, which agreed well with the simulated seawater results. Characterization of the adsorbents indicated that the increase in uranium adsorption capacity with each acid monomer was related to higher grafting of AN and therefore a higher conversion to amidoxime (AO). PMID:27145863

  10. SO 2 adsorption capacity of K 2CO 3-impregnated activated carbon as a function of K 2CO 3 content loaded by soaking and incipient wetness

    NASA Astrophysics Data System (ADS)

    Fortier, H.; Zelenietz, C.; Dahn, T. R.; Westreich, P.; Stevens, D. A.; Dahn, J. R.

    2007-01-01

    The SO 2 adsorption capacity of K 2CO 3-impregnated activated carbons, prepared by soaking carbon in large volumes of K 2CO 3 in solution of various concentrations, varies linearly with respect to the loading of K 2CO 3 on the carbon up to about 12% K 2CO 3 by weight. Above 12%, the capacity for SO 2 levels out and then decreases. This suggests that at high loadings the K 2CO 3 either aggregates and/or blocks pores of the activated carbon. In contrast, the adsorption capacity of carbons prepared by repeatedly (maximum of three times total) loading K 2CO 3 via incipient wetness is much larger than that of the soaked samples, up to 70% more, when the loading of K 2CO 3 is greater than 12%. Static and dynamic adsorption, DSC, SEM, EDX and incipient wetness studies of the samples show that the impregnant aggregates but does not block carbon pores.

  11. Effects of Mn, Cu doping concentration to the properties of magnetic nanoparticles and arsenic adsorption capacity in wastewater

    NASA Astrophysics Data System (ADS)

    Thi, Tran Minh; Trang, Nguyen Thi Huyen; Van Anh, Nguyen Thi

    2015-06-01

    The research results of Fe3O4 and Mn, Cu doped Fe3O4 nanomaterials synthesized by a chemical method for As(III) wastewater treatment are presented in this paper. The X-ray diffraction patterns and transmission electron microscopy images showed that samples had the cubic spinel structure with the grain sizes were varied from 9.4 nm to 18.1 nm. The results of vibrating sample magnetometer measurements at room temperature showed that saturation magnetic moments of Fe1-xCuxFe2O4 and Fe1-xMnxFe2O4 samples decreased from 65.9 emu/g to 53.2 emu/g and 65.9 emu/g to 61.5 emu/g, respectively, with the increase of Cu, Mn concentrations from 0.0 to 0.15. The nitrogen adsorption-desorption isotherm of a typical Fe3O4 sample at 77 K was studied in order to investigate the surface and porous structure of nanoparticles by BET method. The specific surface area of Fe3O4 magnetic nanoparticles was calculated about of 100.2 m2/g. The pore size distribution of about 15-20 nm calculated by the BJH (Barrett, Joyner, and Halendar) method at a relative pressure P/P0 of about 1. Although the saturation magnetic moments of samples decreased when the increase of doping concentration, but the arsenic adsorption capacity of Cu doped Fe3O4 nanoparticles is better than that of Fe3O4 and Mn doped Fe3O4 nanoparticles in a solution with pH = 7. In the solution with a pH > 14, the arsenic adsorption of magnetic nanoparticles is insignificant.

  12. MOF-derived ZnO and ZnO@C composites with high photocatalytic activity and adsorption capacity.

    PubMed

    Yang, Seung Jae; Im, Ji Hyuk; Kim, Taehoon; Lee, Kunsil; Park, Chong Rae

    2011-02-15

    Nanostructured ZnO materials have unique and highly attractive properties and have inspired interest in their research and development. This paper presents a facile method for the preparation of novel ZnO-based nanostructured architectures using a metal organic framework (MOF) as a precursor. In this approach, ZnO nanoparticles and ZnO@C hybrid composites were produced under several heating and atmospheric (air or nitrogen) conditions. The resultant ZnO nanoparticles formed hierarchical aggregates with a three-dimensional cubic morphology, whereas ZnO@C hybrid composites consisted of faceted ZnO crystals embedded within a highly porous carbonaceous species, as determined by several characterization methods. The newly synthesized nanomaterials showed relatively high photocatalytic decomposition activity and significantly enhanced adsorption capacities for organic pollutants.

  13. Estimating prion adsorption capacity of soil by BioAssay of Subtracted Infectivity from Complex Solutions (BASICS).

    PubMed

    Wyckoff, A Christy; Lockwood, Krista L; Meyerett-Reid, Crystal; Michel, Brady A; Bender, Heather; VerCauteren, Kurt C; Zabel, Mark D

    2013-01-01

    Prions, the infectious agent of scrapie, chronic wasting disease and other transmissible spongiform encephalopathies, are misfolded proteins that are highly stable and resistant to degradation. Prions are known to associate with clay and other soil components, enhancing their persistence and surprisingly, transmissibility. Currently, few detection and quantification methods exist for prions in soil, hindering an understanding of prion persistence and infectivity in the environment. Variability in apparent infectious titers of prions when bound to soil has complicated attempts to quantify the binding capacity of soil for prion infectivity. Here, we quantify the prion adsorption capacity of whole, sandy loam soil (SLS) typically found in CWD endemic areas in Colorado; and purified montmorillonite clay (Mte), previously shown to bind prions, by BioAssay of Subtracted Infectivity in Complex Solutions (BASICS). We incubated prion positive 10% brain homogenate from terminally sick mice infected with the Rocky Mountain Lab strain of mouse-adapted prions (RML) with 10% SLS or Mte. After 24 hours samples were centrifuged five minutes at 200 × g and soil-free supernatant was intracerebrally inoculated into prion susceptible indicator mice. We used the number of days post inoculation to clinical disease to calculate the infectious titer remaining in the supernatant, which we subtracted from the starting titer to determine the infectious prion binding capacity of SLS and Mte. BASICS indicated SLS bound and removed ≥ 95% of infectivity. Mte bound and removed lethal doses (99.98%) of prions from inocula, effectively preventing disease in the mice. Our data reveal significant prion-binding capacity of soil and the utility of BASICS to estimate prion loads and investigate persistence and decomposition in the environment. Additionally, since Mte successfully rescued the mice from prion disease, Mte might be used for remediation and decontamination protocols.

  14. High adsorption capacity of two Zn-based metal-organic frameworks by ultrasound assisted synthesis.

    PubMed

    Masoomi, Mohammad Yaser; Bagheri, Minoo; Morsali, Ali

    2016-11-01

    Micro- and nano-rods and plates of two 3D, porous Zn(II)-based metal-organic frameworks [Zn(oba)(4-bpdh)0.5]n·(DMF)1.5 (TMU-5) and [Zn(oba)(4-bpmb)0.5]n (DMF)1.5 (TMU-6) were prepared by sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction and IR spectroscopy. These MOFs were synthesized using a non-linear dicarboxylate (H2oba=4,4-oxybisbenzoic acid) and two linear N-donor (4-bpdh=2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and 4-bpmb=N(1),N(4)-bis((pyridin-4-yl)methylene)benzene-1,4-diamine) ligands by ultrasonic irradiation. Sonication time and concentration of initial reagents influencing size and morphology of nano-structured MOFs, were also studied. Calcination of TMU-5 and TMU-6 at 550°C under air atmosphere yields ZnO nanoparticles. TMU-5 and TMU-6 exhibited maximum percent adsorption of 96.2% and 92.8% of 100ppm rhodamine B dye, respectively, which obeys first order reaction kinetics.

  15. [Study on the co-adsorption mechanism of Pb (II) and chlorpyrifos on arid loess in northwestern China].

    PubMed

    Fan, Chun-Hui; Zhang, Ying-Chao; Wang, Jia-Hong

    2013-08-01

    The co-adsorption characteristics of Pb(II) and chlorpyrifos on arid loess were investigated with batch adsorption procedures, and the co-adsorption mechanism was studied with approaches of SEM, FT-IR, XRD and theoretical analysis. The experimental results indicated that the adsorption process of Pb(II) and chlorpyrifos on loess fit better the Langmuir isotherm, the maximum adsorption capacity of q(m) is 12.5 and 0.64 mg x g(-1) for Pb(II) and chlorpyrifos on loess, respectively, and the reaction could be illustrated with pseudo-second order kinetic equation. The SEM micrograph of loess surface varies little after the adsorption process of Pb(II) and chlorpyrifos, and certain wave peaks of FTIR spectra red-shift, disappears or intensity-decrease, with the XRD pattern and theoretical analysis, the adsorption mechanism is described as follows: the adsorption of Pb (II) on arid loess is the chemical-effect of coordination-complexation and Van der Waals force; the physical-adsorption on chlorpyrifos involves the interception function, hydrogen bonds and Van der Waals force, and chemical adsorption effect to some extent. The organic matter in arid loess plays an important role in Pb(II) and chlorpyrifos adsorption.

  16. Competitive adsorption, displacement, and transport of organic matter on iron oxide: I. Competitive adsorption

    NASA Astrophysics Data System (ADS)

    Gu, Baohua; Mehlhorn, Tonia L.; Liang, Liyuan; McCarthy, John F.

    1996-06-01

    Different organic compounds or fractions of natural organic matter (NOM) show different adsorption affinities ( K) and capacities ( qm) on mineral surfaces. We hypothesize that these different organic compounds or fractions compete for adsorption when surface adsorption sites are limited. In this study, competitive adsorption of binary mixtures of Suwannee River NOM (SR-NOM), polyacrylic acid (PAA), phthalic acid, and salicylic acid on iron oxide was investigated at a constant solid:solution ratio, temperature, and pressure, but at varying C weight fractions, pH, and solution concentrations of the mixture. Results revealed that, in general, PAA is the most competitive whereas SR-NOM is more competitive than phthalic and salicylic acids. The competitive adsorption of these organic compounds is pH-dependent. At pH < 4, PAA becomes less competitive than SR-NOM or phthalic and salicylic acids. The competition among these organic compounds may be related to their carboxyl functional groups and their molecular structure. The overall strong competitiveness of PAA at pH > 4 in comparison with other organics is attributed to its high carboxyl density and linear molecular structure, which promote strong surface complexation with iron oxide. Because of the heterogeneity or polydispersity of NOM, this research indicates that NOM partitioning and transport in the subsurface soil environment are influenced by the dynamic competitive interactions between NOM subcomponents (or fractions). This process ultimately influences the distribution, interaction, and cotransport of contaminants and mineral colloids that are associated with NOM.

  17. Convergence in the QM-only and QM/MM modeling of enzymatic reactions: A case study for acetylene hydratase.

    PubMed

    Liao, Rong-Zhen; Thiel, Walter

    2013-10-15

    We report systematic quantum mechanics-only (QM-only) and QM/molecular mechanics (MM) calculations on an enzyme-catalyzed reaction to assess the convergence behavior of QM-only and QM/MM energies with respect to the size of the chosen QM region. The QM and MM parts are described by density functional theory (typically B3LYP/def2-SVP) and the CHARMM force field, respectively. Extending our previous work on acetylene hydratase with QM regions up to 157 atoms (Liao and Thiel, J. Chem. Theory Comput. 2012, 8, 3793), we performed QM/MM geometry optimizations with a QM region M4 composed of 408 atoms, as well as further QM/MM single-point calculations with even larger QM regions up to 657 atoms. A charge deletion analysis was conducted for the previously used QM/MM model (M3a, with a QM region of 157 atoms) to identify all MM residues with strong electrostatic contributions to the reaction energetics (typically more than 2 kcal/mol), which were then included in M4. QM/MM calculations with this large QM region M4 lead to the same overall mechanism as the previous QM/MM calculations with M3a, but there are some variations in the relative energies of the stationary points, with a mean absolute deviation (MAD) of 2.7 kcal/mol. The energies of the two relevant transition states are close to each other at all levels applied (typically within 2 kcal/mol), with the first (second) one being rate-limiting in the QM/MM calculations with M3a (M4). QM-only gas-phase calculations give a very similar energy profile for QM region M4 (MAD of 1.7 kcal/mol), contrary to the situation for M3a where we had previously found significant discrepancies between the QM-only and QM/MM results (MAD of 7.9 kcal/mol). Extension of the QM region beyond M4 up to M7 (657 atoms) leads to only rather small variations in the relative energies from single-point QM-only and QM/MM calculations (MAD typically about 1-2 kcal/mol). In the case of acetylene hydratase, a model with 408 QM atoms thus seems

  18. Adsorption of ciprofloxacin, bisphenol and 2-chlorophenol on electrospun carbon nanofibers: in comparison with powder activated carbon.

    PubMed

    Li, Xiaona; Chen, Shuo; Fan, Xinfei; Quan, Xie; Tan, Feng; Zhang, Yaobin; Gao, Jinsuo

    2015-06-01

    Carbon nanofibers (CNFs) were prepared by electrospun polyacrylonitrile (PAN) polymer solutions followed by thermal treatment. For the first time, the influence of stabilization procedure on the structure properties of CNFs was explored to improve the adsorption capacity of CNFs towards the environmental pollutants from aqueous solution. The adsorption of three organic chemicals including ciprofloxacin (CIP), bisphenol (BPA) and 2-chlorophenol (2-CP) on electrospun CNFs with high surface area of 2326m(2)/g and micro/mesoporous structure characteristics were investigated. The adsorption affinities were compared with that of the commercial powder activated carbon (PAC). The adsorption kinetics and isotherms showed that the maximum adsorption capacities (qm) of CNFs towards the three pollutants are sequenced in the order of CIP>BPA>2-CP, which are 2.6-fold (CIP), 1.6-fold (BPA) and 1.1-fold (2-CP) increase respectively in comparison with that of PAC adsorption. It was assumed that the micro/mesoporous structure of CNFs, molecular size of the pollutants and the π electron interaction play important roles on the high adsorption capacity exhibited by CNFs. In addition, electrostatic interaction and hydrophobic interaction also contribute to the adsorption of CNFs. This study demonstrates that the electrospun CNFs are promising adsorbents for the removal of pollutants from aqueous solutions.

  19. CO2 Adsorption in Low-Rank Coals: Progress Toward Assessing the National Capacity to Store CO2 in the Subsurface

    NASA Astrophysics Data System (ADS)

    Stanton, R. W.; Burruss, R. C.; Flores, R. M.; Warwick, P. D.

    2001-05-01

    Subsurface environments for geologic storage of CO2 from combustion of fossil fuel include saline formations, depleted oil and gas reservoirs, and unmineable coalbeds. Of these environments, storage in petroleum reservoirs and coal beds offers a potential economic benefit of enhanced recovery of energy resources. Meaningful assessment of the volume and geographic distribution of storage sites requires quantitative estimates of geologic factors that control storage capacity. The factors that control the storage capacity of unmineable coalbeds are poorly understood. In preparation for a USGS assessment of CO2 storage capacity we have begun new measurements of CO2 and CH4 adsorption isotherms of low-rank coal samples from 4 basins. Initial results for 13 samples of low-rank coal beds from the Powder River Basin (9 subbituminous coals), Greater Green River Basin (1 subbituminous coal), Williston Basin (2 lignites) and the Gulf Coast (1 lignite) indicate that their adsorption capacity is up to 10 times higher than it is for CH4. These values contrast with published measurements of the CO2 adsorption capacity of bituminous coals from the Fruitland Formation, San Juan basin, and Gates Formation, British Columbia, that indicate about twice as much carbon dioxide as methane can be adsorbed on coals. Because CH4 adsorption isotherms are commonly measured on coals, CO2 adsorption capacity can be estimated if thecorrect relationship between the gases is known. However, use a factor to predict CO2 adsorption that is twice that of CH4 adsorption, which is common in the published literature, grossly underestimates the storage capacity of widely distributed, thick low-rank coal beds. Complete petrographic and chemical characterization of these low-rank coal samples is in progress. Significant variations in adsorption measurements among samples are depicted depending on the reporting basis used. Properties were measured on an "as received" (moist) basis but can be converted to a

  20. Direct observation of solid-phase adsorbate concentration profile in powdered activated carbon particle to elucidate mechanism of high adsorption capacity on super-powdered activated carbon.

    PubMed

    Ando, Naoya; Matsui, Yoshihiko; Matsushita, Taku; Ohno, Koichi

    2011-01-01

    Decreasing the particle size of powdered activated carbon (PAC) by pulverization increases its adsorption capacities for natural organic matter (NOM) and polystyrene sulfonate (PSS, which is used as a model adsorbate). A shell adsorption mechanism in which NOM and PSS molecules do not completely penetrate the adsorbent particle and instead preferentially adsorb near the outer surface of the particle has been proposed as an explanation for this adsorption capacity increase. In this report, we present direct evidence to support the shell adsorption mechanism. PAC particles containing adsorbed PSS were sectioned with a focused ion beam, and the solid-phase PSS concentration profiles of the particle cross-sections were directly observed by means of field emission-scanning electron microscopy/energy-dispersive X-ray spectrometry (FE-SEM/EDXS). X-ray emission from sulfur, an index of PSS concentration, was higher in the shell region than in the inner region of the particles. The X-ray emission profile observed by EDXS did not agree completely with the solid-phase PSS concentration profile predicted by shell adsorption model analysis of the PSS isotherm data, but the observed and predicted profiles were not inconsistent when the analytical errors were considered. These EDXS results provide the first direct evidence that PSS is adsorbed mainly in the vicinity of the external surface of the PAC particles, and thus the results support the proposition that the increase in NOM and PSS adsorption capacity with decreasing particle size is due to the increase in external surface area on which the molecules can be adsorbed. PMID:20851447

  1. Electrochemically enhanced adsorption of nonylphenol on carbon nanotubes: Kinetics and isotherms study.

    PubMed

    Li, Xiaona; Chen, Shuo; Li, Liying; Quan, Xie; Zhao, Huimin

    2014-02-01

    Removal of nonylphenol (NP) from aqueous solution has attracted widely attention due to its aquatic toxicity and potential to disrupt the endocrine system. In an effort to develop the effective and environment-friendly treatment method for NP, adsorption of 4-n-nonylphenol (4-NP) on multi-walled carbon nanotubes (MWCNTs) under electrochemical assistance was studied. The adsorption kinetics and isotherms were investigated at different polarization potentials and compared with those of open circuit (OC) and powder MWCNTs adsorption. The adsorption kinetics was simulated by the model including pseudo-first-order model, pseudo-second-order model and intraparticle diffusion model. The isotherm was simulated with Langmuir model and Freudlich model, respectively. Experimental results indicated that 4-NP is able to be efficiently removed at a potential of -0.6V. Comparing with that of powder MWCNTs adsorption, the initial adsorption rate υ0 at -0.6V increased 7.9-fold according to pseudo-second-order model and the maximum adsorption capacity qm improved 1.7-fold according to Langmuir model. The improved adsorption effect at negative potential was ascribed to enhanced π-π electron-donor-acceptor (EDA) interaction between 4-NP and MWCNTs under electrochemical assistance.

  2. The role of counter ions in nano-hematite synthesis: Implications for surface area and selenium adsorption capacity.

    PubMed

    Lounsbury, Amanda W; Yamani, Jamila S; Johnston, Chad P; Larese-Casanova, Philip; Zimmerman, Julie B

    2016-06-01

    Nano metal oxides are of interest for aqueous selenium (Se) remediation, and as such, nano-hematite (nα-Fe2O3) was examined for use as a Se adsorbent. The effect of surface area on adsorption was also studied. nα-Fe2O3 particles were synthesized from Fe(NO3)3 and FeCl3 via forced hydrolysis. The resulting particles have similar sizes, morphologies, aggregate size, pore size, and PZC. The nα-Fe2O3 from FeCl3 (nα-Fe2O3-C) differs from the nα-Fe2O3 from Fe(NO3)3 (nα-Fe2O3-N) with a ∼25±2m(2)/g greater surface area. Selenite Se(IV) adsorption capacity on nα-Fe2O3 has a qmax ∼17mg/g for the freeze-dried and re-suspended nα-Fe2O3. The Δqmax for nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension was 4.6mg/g. For selenate Se(VI), the freeze-dried and re-suspended particles realize a Δqmax= 1.5mg/g for nα-Fe2O3 from Fe(NO3)3 and FeCl3. The nα-Fe2O3 from Fe(NO3)3 and FeCl3 that remained in suspension demonstrated Se(VI) Δqmax=5.4mg/g. In situ ATR-FTIR isotherm measurements completed for Se(VI) at a pH 6 suggest that Se(VI) forms primarily outer-sphere complexes with nα-Fe2O3 synthesized from both salts. PMID:26905609

  3. A one-step thermal decomposition method to prepare anatase TiO2 nanosheets with improved adsorption capacities and enhanced photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Li, Wenting; Shang, Chunli; Li, Xue

    2015-12-01

    Anatase TiO2 nanosheets (NSs) with high surface area have been prepared via a one-step thermal decomposition of titanium tetraisopropoxide (TTIP) in oleylamine (OM), and their adsorption capacities and photocatalytic activities are investigated by using methylene blue (MB) and methyl orange (MO) as model pollutants. During the synthesis procedure, only one type of surfactant, oleylamine (OM), is used as capping agents and no other solvents are added. Structure and properties of the TiO2 NSs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption analysis, UV-vis spectrum, X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) methods. The results indicate that the TiO2 NSs possess high surface area up to 378 m2 g-1. The concentration of capping agents is found to be a key factor controlling the morphology and crystalline structure of the product. Adsorption and photodegradation experiments reveal that the prepared TiO2 NSs possess high adsorption capacities of model pollutants MB and high photocatalytic activity, showing that TiO2 NSs can be used as efficient pollutant adsorbents and photocatalytic degradation catalysts of MB in wastewater treatment.

  4. Use of lipophilic ion adsorption isotherms to determine the surface area and the monolayer capacity of a chromatographic packing, as well as the thermodynamic equilibrium constant for its adsorption.

    PubMed

    Cecchi, T

    2005-04-29

    A method that champions the approaches of two independent research groups, to quantitate the chromatographic stationary phase surface available for lipophilic ion adsorption, is presented. For the first time the non-approximated expression of the electrostatically modified Langmuir adsorption isotherm was used. The non approximated Gouy-Chapman (G-C) theory equation was used to give the rigorous surface potential. The method helps model makers, interested in ionic interactions, determine whether the potential modified Langmuir isotherm can be linearized, and, accordingly, whether simplified retention equations can be properly used. The theory cultivated here allows the estimates not only of the chromatographically accessible surface area, but also of the thermodynamic equilibrium constant for the adsorption of the amphiphile, the standard free energy of its adsorption, and the monolayer capacity of the packing. In addition, it establishes the limit between a theoretical and an empirical use of the Freundlich isotherm to determine the surface area. Estimates of the parameters characterising the chromatographic system are reliable from the physical point of view, and this greatly validates the present comprehensive approach.

  5. Improved QM Methods and Their Application in QM/MM Studies of Enzymatic Reactions

    NASA Astrophysics Data System (ADS)

    Jorgensen, William L.

    2007-03-01

    Quantum mechanics (QM) and Monte Carlo statistical mechanics (MC) simulations have been used by us since the early 1980s to study reaction mechanisms and the origin of solvent effects on reaction rates. A goal was always to perform the QM and MC/MM calculations simultaneously in order to obtain free-energy surfaces in solution with no geometrical restrictions. This was achieved by 2002 and complete free-energy profiles and surfaces with full sampling of solute and solvent coordinates can now be obtained through one job submission using BOSS [JCC 2005, 26, 1689]. Speed and accuracy demands also led to development of the improved semiempirical QM method, PDDG-PM3 [JCC 1601 (2002); JCTC 817 (2005)]. The combined PDDG-PM3/MC/FEP methodology has provided excellent results for free energies of activation for many reactions in numerous solvents. Recent examples include Cope, Kemp and E1cb eliminations [JACS 8829 (2005), 6141 (2006); JOC 4896 (2006)], as well as enzymatic reactions catalyzed by the putative Diels-Alderase, macrophomate synthase, and fatty-acid amide hydrolase [JACS 3577 (2005); JACS (2006)]. The presentation will focus on the accuracy that is currently achievable in such QM/MM studies and the accuracy of the underlying QM methodology including extensive comparisons of results from PDDG-PM3 and ab initio DFT methods.

  6. Exploring the Dependence of QM/MM Calculations of Enzyme Catalysis on the Size of the QM Region

    PubMed Central

    2016-01-01

    Although QM/MM calculations are the primary current tool for modeling enzymatic reactions, the reliability of such calculations can be limited by the size of the QM region. Thus, we examine in this work the dependence of QM/MM calculations on the size of the QM region, using the reaction of catechol-O-methyl transferase (COMT) as a test case. Our study focuses on the effect of adding residues to the QM region on the activation free energy, obtained with extensive QM/MM sampling. It is found that the sensitivity of the activation barrier to the size of the QM is rather limited, while the dependence of the reaction free energy is somewhat larger. Of course, the results depend on the inclusion of the first solvation shell in the QM regions. For example, the inclusion of the Mg2+ ion can change the activation barrier due to charge transfer effects. However, such effects can easily be included in semiempirical approaches by proper parametrization. Overall, we establish that QM/MM calculations of activation barriers of enzymatic reactions are not highly sensitive to the size of the QM region, beyond the immediate region that describes the reacting atoms. PMID:27552257

  7. Highly efficient ultrasonic-assisted removal of Hg(II) ions on graphene oxide modified with 2-pyridinecarboxaldehyde thiosemicarbazone: Adsorption isotherms and kinetics studies.

    PubMed

    Tadjarodi, Azadeh; Moazen Ferdowsi, Somayeh; Zare-Dorabei, Rouholah; Barzin, Ahmad

    2016-11-01

    A novel adsorbent, based on modifying graphene oxide (GO) chemically with 2-pyridinecarboxaldehyde thiosemicarbazone (2-PTSC) as ligand, was designed by facile process for removal of Hg(II) from aqueous solution. Characterization of the adsorbent was performed using various techniques, such as FT-IR, XRD, XPS, SEM and AFM analysis. The adsorption capacity was affected by variables such as adsorbent dosage, pH solution, Hg(2+) initial concentration and sonicating time. These variables were optimized by rotatable central composite design (CCD) under response surface methodology (RSM). The predictive model for Hg(II) adsorption was constructed and applied to find the best conditions at which the responses were maximized. In this conditions, the adsorption capacity of this adsorbent for Hg(2+) ions was calculated to be 309mgg(-1) that was higher than that of GO. Appling the ultrasound power combined with adsorption method was very efficient in shortening the removal time of Hg(2+) ions by enhancing the dispersion of adsorbent and metal ions in solution and effective interactions among them. The adsorption process was well described by second-order kinetic and Langmuir isotherm model in which the maximum adsorption capacity (Qm) was found to be 555mgg(-1) for adsorption of Hg(2+) ions over the obtained adsorbent. The performance of adsorbent was examined on the real wastewaters and confirmed the applicability of adsorbent for practical applications. PMID:27245963

  8. New Methods for Exploring QM:MM Potential Energy Landscapes

    NASA Astrophysics Data System (ADS)

    Hratchian, Hrant P.

    2010-06-01

    In recent years, the applicability of quantum chemical methods for large system studies has been greatly enhanced by the development of hybrid QM:MM techniques. Despite these advancements, exploring the associated potential energy surfaces continues to present two key challenges. First, the QM energy and derivative evaluations may be too costly for simulations; and second, the system size for many QM:MM cases are too large to effectively store or use second-order information, an approach often used in QM studies to allow for larger integration steps and fewer QM evaluations of the potential energy surface. Our most recent work is focused on overcoming both computational bottlenecks. Using surface fitting models together with direct Hessian-vector and diagonalization algorithms, we are developing models that can accurately and efficiently explore QM:MM potential energy landscapes for very large systems. Our current development status and results from initial applications will be described.

  9. Study of the adsorption of Cr(VI) by tannic acid immobilised powdered activated carbon from micro-polluted water in the presence of dissolved humic acid.

    PubMed

    Gong, Xujin; Li, Weiguang; Wang, Ke; Hu, Jinhua

    2013-08-01

    The adsorption of Cr(VI) (0.500 mg/L) onto food-grade tannic-acid immobilised powdered activated carbon (TA-PAC) in the presence of dissolved humic acid (DHA) was investigated at 280 K as a function of pH, along with the adsorption capacities and the adsorption isotherms for chromium ions. The results showed that the presence of DHA improved the adsorption capacities of Cr(VI) and its reduction product (Cr(III)) over a wide pH range (4.0-8.0). The main mechanism for metal-DHA complexation in the Cr(VI) system was the reduction of Cr(VI) followed by complexation between Cr(III) and DHA. The Freundlich isotherms yielded the best fits to all data (R(2)=0.9951, qm=5.639 mg/g) in the presence of DHA. The adsorption mechanisms of Cr(VI) onto TA-PAC in the presence of DHA were summarized into three categories: (i) binding by anion adsorption, (ii) Cr(VI) reduction followed by Cr(III) adsorption, and (iii) adsorption of Cr(III)-DHA complexes.

  10. Study of the adsorption of Cr(VI) by tannic acid immobilised powdered activated carbon from micro-polluted water in the presence of dissolved humic acid.

    PubMed

    Gong, Xujin; Li, Weiguang; Wang, Ke; Hu, Jinhua

    2013-08-01

    The adsorption of Cr(VI) (0.500 mg/L) onto food-grade tannic-acid immobilised powdered activated carbon (TA-PAC) in the presence of dissolved humic acid (DHA) was investigated at 280 K as a function of pH, along with the adsorption capacities and the adsorption isotherms for chromium ions. The results showed that the presence of DHA improved the adsorption capacities of Cr(VI) and its reduction product (Cr(III)) over a wide pH range (4.0-8.0). The main mechanism for metal-DHA complexation in the Cr(VI) system was the reduction of Cr(VI) followed by complexation between Cr(III) and DHA. The Freundlich isotherms yielded the best fits to all data (R(2)=0.9951, qm=5.639 mg/g) in the presence of DHA. The adsorption mechanisms of Cr(VI) onto TA-PAC in the presence of DHA were summarized into three categories: (i) binding by anion adsorption, (ii) Cr(VI) reduction followed by Cr(III) adsorption, and (iii) adsorption of Cr(III)-DHA complexes. PMID:23453800

  11. Characterization of immunoglobulin adsorption on dextran-grafted hydrophobic charge-induction resins: Cross-effects of ligand density and pH/salt concentration.

    PubMed

    Liu, Tao; Lin, Dong-Qiang; Zhang, Qi-Lei; Yao, Shan-Jing

    2015-05-29

    Hydrophobic charge-induction chromatography (HCIC) is a promising technology for antibody purification. New HCIC resins MMI-B-XL with dextran-grafted agarose gel as the matrix and 2-mercapto-1-methyl-imidazole (MMI) as the functional ligand were prepared with different ligand densities. The adsorption behaviors (static adsorption equilibrium and adsorption kinetics) of human immunoglobulin G (hIgG) on series of MMI-B-XL resins at varying pHs and salt concentrations were investigated. The cross-effects of solid phase property (ligand density) and liquid phase conditions (pH and salt concentration) were focused. The results showed that the new resins had typical pH-dependent and salt-tolerant characteristics for hIgG adsorption, but differences were found for the resins with different ligand densities. For MMI-B-XL resins with higher ligand density, an obvious higher saturated adsorption capacity (Qm) and effective pore diffusivity (De) could be obtained, which were less affected at pH 7.0∼8.9 but dropped drastically at pH 5.0. Salt addition had less influence on protein adsorption onto MMI-B-XL with higher ligand density. Qm and De both reached minimum values at 0.2mol/L NaCl for all MMI-B-XL resins tested. The results of dynamic binding in the column demonstrated that MMI-B-XL with higher ligand density had better performance for hIgG adsorption, especially under high linear velocities. The mechanism of the cross-effects of ligand density and pH/salt concentration on IgG adsorption was discussed, which provides new insights into protein adsorption and mass transport for dextran-grafted HCIC resins. PMID:25892639

  12. Surfactant-free synthesis of octahedral ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption capacity of malachite green.

    PubMed

    Liu, Jue; Zeng, Min; Yu, Ronghai

    2016-01-01

    A new octahedral ZnO/ZnFe2O4 heterostructure has been fabricated through a facile surfactant-free solvothermal method followed by thermal treatment. It exhibits a record-high adsorption capacity (up to 4983.0 mg·g(-1)) of malachite green (MG), which is a potentially harmful dye in prevalence and should be removed from wastewater and other aqueous solutions before discharging into the environment. The octahedral ZnO/ZnFe2O4 heterostructure also demonstrates strong selective adsorption towards MG from two kinds of mixed solutions: MG/methyl orange (MO) and MG/rhodamine B (RhB) mixtures, indicating its promise in water treatment.

  13. Surfactant-free synthesis of octahedral ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption capacity of malachite green

    PubMed Central

    Liu, Jue; Zeng, Min; Yu, Ronghai

    2016-01-01

    A new octahedral ZnO/ZnFe2O4 heterostructure has been fabricated through a facile surfactant-free solvothermal method followed by thermal treatment. It exhibits a record-high adsorption capacity (up to 4983.0 mg·g−1) of malachite green (MG), which is a potentially harmful dye in prevalence and should be removed from wastewater and other aqueous solutions before discharging into the environment. The octahedral ZnO/ZnFe2O4 heterostructure also demonstrates strong selective adsorption towards MG from two kinds of mixed solutions: MG/methyl orange (MO) and MG/rhodamine B (RhB) mixtures, indicating its promise in water treatment. PMID:27142194

  14. Surfactant-free synthesis of octahedral ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption capacity of malachite green

    NASA Astrophysics Data System (ADS)

    Liu, Jue; Zeng, Min; Yu, Ronghai

    2016-05-01

    A new octahedral ZnO/ZnFe2O4 heterostructure has been fabricated through a facile surfactant-free solvothermal method followed by thermal treatment. It exhibits a record-high adsorption capacity (up to 4983.0 mg·g‑1) of malachite green (MG), which is a potentially harmful dye in prevalence and should be removed from wastewater and other aqueous solutions before discharging into the environment. The octahedral ZnO/ZnFe2O4 heterostructure also demonstrates strong selective adsorption towards MG from two kinds of mixed solutions: MG/methyl orange (MO) and MG/rhodamine B (RhB) mixtures, indicating its promise in water treatment.

  15. Surfactant-free synthesis of octahedral ZnO/ZnFe2O4 heterostructure with ultrahigh and selective adsorption capacity of malachite green.

    PubMed

    Liu, Jue; Zeng, Min; Yu, Ronghai

    2016-01-01

    A new octahedral ZnO/ZnFe2O4 heterostructure has been fabricated through a facile surfactant-free solvothermal method followed by thermal treatment. It exhibits a record-high adsorption capacity (up to 4983.0 mg·g(-1)) of malachite green (MG), which is a potentially harmful dye in prevalence and should be removed from wastewater and other aqueous solutions before discharging into the environment. The octahedral ZnO/ZnFe2O4 heterostructure also demonstrates strong selective adsorption towards MG from two kinds of mixed solutions: MG/methyl orange (MO) and MG/rhodamine B (RhB) mixtures, indicating its promise in water treatment. PMID:27142194

  16. Ultrasond-assisted synthesis of Fe3O4/SiO2 core/shell with enhanced adsorption capacity for diazinon removal

    NASA Astrophysics Data System (ADS)

    Farmany, Abbas; Mortazavi, Seyede Shima; Mahdavi, Hossein

    2016-10-01

    Fe3O4/SiO2 core/shell nanocrystals were synthesized by ultrasond-assisted procedure. The core/shell nanocrystals were characterized using XRD, FT-IR spectroscopy, SEM and BET. The BET analysis confirmed that iron oxide nanocrystal with the surface area of 208.0 m2/g can be used as an excellent adsorbent for organic and inorganic pollutants. The core/shell nanocrystal was used as an adsorbent for removal of insecticide O,O-diethyl-O[2-isopropyl-6-methylpyridimidinyl] phosphorothioate (diazinon). In continue the influence of different parameters such as pH, adsorbent dosage and shaking time on the adsorption capacity were studied. The experimental data were fitted well with the pseudo-second-order kinetic model (R2=0.9706). The adsorption isotherm was described well by Langmuir isotherm.

  17. Methane and carbon dioxide adsorption capacity of bituminous coals from the Ostrava-Karvina Coal District, Upper Silesian Basin, Czech Republic

    NASA Astrophysics Data System (ADS)

    Weniger, P.; Busch, A.; Krooss, B. M.; Francu, J.; Francu, E.

    2009-04-01

    In the context of a joint Czech-German project, experimental and analytical methods are being applied to improve the understanding of compositional variation of coal-related gas in the SW part of the Upper Silesian Basin (Czech Republic). According to present understanding, the gas composition is controlled by generation (thermal vs. microbial), migration and adsorption/desorption processes. In particular the effects of the sorption processes on the chemical and isotopic composition of coal gases are only poorly explored. During the first stage of this project, the gas adsorption capacity has been determined for coal samples representing the paralic Ostrava Formation (Namurian A) and the limnic Karviná Formation (Namurian B-C). For this purpose, high pressure adsorption isotherms have been measured for methane and carbon dioxide on medium and low volatile bituminous coal (VRr 1.2-1.8%) from the production face of two collieries in the study area. Adsorption isotherms have been measured for pressures up to 25 MPa for CO2 and up to 17 MPa for methane at 20˚ C and 45˚ C. Isotherms were measured on dry, moisture-equilibrated and "as received" samples (moisture content: 0.5-1.7%, mineral-matter-free) using a manometric method. Sorption capacities for CH4 at 45˚ C ranged from 18 to 27 Std. cm3/g (0.7 to 1.1 mmol/g) coal, dry ash-free (daf), showing an increase of sorption capacity with increasing coal rank. For CO2, sorption capacities were generally higher than for methane, ranging from 35-40 Std. cm3/g (1.4-1.7 mmol/g) coal (daf). Equilibrium moisture contents, determined by a modified ASTM method, were significantly higher than the "as received" moisture. Sorption capacities measured on moisture-equilibrated samples were generally lower than those measured on dry or "as received" samples. Methane excess sorption isotherms show a type I Langmuir form and could be approximated using the Langmuir function. Excess sorption isotherms for CO2 show a decrease in

  18. Derivation of Reliable Geometries in QM Calculations of DNA Structures: Explicit Solvent QM/MM and Restrained Implicit Solvent QM Optimizations of G-Quadruplexes.

    PubMed

    Gkionis, Konstantinos; Kruse, Holger; Šponer, Jiří

    2016-04-12

    Modern dispersion-corrected DFT methods have made it possible to perform reliable QM studies on complete nucleic acid (NA) building blocks having hundreds of atoms. Such calculations, although still limited to investigations of potential energy surfaces, enhance the portfolio of computational methods applicable to NAs and offer considerably more accurate intrinsic descriptions of NAs than standard MM. However, in practice such calculations are hampered by the use of implicit solvent environments and truncation of the systems. Conventional QM optimizations are spoiled by spurious intramolecular interactions and severe structural deformations. Here we compare two approaches designed to suppress such artifacts: partially restrained continuum solvent QM and explicit solvent QM/MM optimizations. We report geometry relaxations of a set of diverse double-quartet guanine quadruplex (GQ) DNA stems. Both methods provide neat structures without major artifacts. However, each one also has distinct weaknesses. In restrained optimizations, all errors in the target geometries (i.e., low-resolution X-ray and NMR structures) are transferred to the optimized geometries. In QM/MM, the initial solvent configuration causes some heterogeneity in the geometries. Nevertheless, both approaches represent a decisive step forward compared to conventional optimizations. We refine earlier computations that revealed sizable differences in the relative energies of GQ stems computed with AMBER MM and QM. We also explore the dependence of the QM/MM results on the applied computational protocol. PMID:26914292

  19. Derivation of Reliable Geometries in QM Calculations of DNA Structures: Explicit Solvent QM/MM and Restrained Implicit Solvent QM Optimizations of G-Quadruplexes.

    PubMed

    Gkionis, Konstantinos; Kruse, Holger; Šponer, Jiří

    2016-04-12

    Modern dispersion-corrected DFT methods have made it possible to perform reliable QM studies on complete nucleic acid (NA) building blocks having hundreds of atoms. Such calculations, although still limited to investigations of potential energy surfaces, enhance the portfolio of computational methods applicable to NAs and offer considerably more accurate intrinsic descriptions of NAs than standard MM. However, in practice such calculations are hampered by the use of implicit solvent environments and truncation of the systems. Conventional QM optimizations are spoiled by spurious intramolecular interactions and severe structural deformations. Here we compare two approaches designed to suppress such artifacts: partially restrained continuum solvent QM and explicit solvent QM/MM optimizations. We report geometry relaxations of a set of diverse double-quartet guanine quadruplex (GQ) DNA stems. Both methods provide neat structures without major artifacts. However, each one also has distinct weaknesses. In restrained optimizations, all errors in the target geometries (i.e., low-resolution X-ray and NMR structures) are transferred to the optimized geometries. In QM/MM, the initial solvent configuration causes some heterogeneity in the geometries. Nevertheless, both approaches represent a decisive step forward compared to conventional optimizations. We refine earlier computations that revealed sizable differences in the relative energies of GQ stems computed with AMBER MM and QM. We also explore the dependence of the QM/MM results on the applied computational protocol.

  20. Modeling emission features of salicylidene aniline molecular crystals: A QM/QM' approach.

    PubMed

    Presti, Davide; Labat, Frédéric; Pedone, Alfonso; Frisch, Michael J; Hratchian, Hrant P; Ciofini, Ilaria; Cristina Menziani, Maria; Adamo, Carlo

    2016-04-01

    A new computational protocol relying on the use of electrostatic embedding, derived from QM/QM' ONIOM calculations, to simulate the effect of the crystalline environment on the emission spectra of molecular crystals is here applied to the β-form of salicylidene aniline (SA). The first singlet excited states (S1 ) of the SA cis-keto and trans-keto conformers, surrounded by a cluster of other molecules representing the crystalline structure, were optimized by using a QM/QM' ONIOM approach with and without electronic embedding. The model system consisting of the central salicylidene aniline molecule was treated at the DFT level by using either the B3LYP, PBE0, or the CAM-B3LYP functional, whereas the real system was treated at the HF level. The CAM-B3LYP/HF level of theory provides emission energies in good agreement with experiment with differences of -20/-32 nm (cis-keto form) and -8/-14 nm (trans-keto form), respectively, whereas notably larger differences are obtained using global hybrids. Though such differences on the optical properties arise from the density functional choice, the contribution of the electronic embedding is rather independent of the functional used. This plays in favor of a more general applicability of the present protocol to other crystalline molecular systems. PMID:26919703

  1. PREDICTING THE ADSORPTION CAPACITY OF ACTIVATED CARBON FOR EMERGING ORGANIC CONTAMINANTS FROM FUNDAMENTAL ADSORBENT AND ADSORBATE PROPERTIES - PRESENTATION

    EPA Science Inventory

    A quantitative structure-property relationship (QSPR) was developed and combined with the Polanyi-Dubinin-Manes model to predict adsorption isotherms of emerging contaminants on activated carbons with a wide range of physico-chemical properties. Affinity coefficients (βl

  2. Enhanced semiempirical QM methods for biomolecular interactions.

    PubMed

    Yilmazer, Nusret Duygu; Korth, Martin

    2015-01-01

    Recent successes and failures of the application of 'enhanced' semiempirical QM (SQM) methods are reviewed in the light of the benefits and backdraws of adding dispersion (D) and hydrogen-bond (H) correction terms. We find that the accuracy of SQM-DH methods for non-covalent interactions is very often reported to be comparable to dispersion-corrected density functional theory (DFT-D), while computation times are about three orders of magnitude lower. SQM-DH methods thus open up a possibility to simulate realistically large model systems for problems both in life and materials science with comparably high accuracy. PMID:25848495

  3. Enhanced semiempirical QM methods for biomolecular interactions

    PubMed Central

    Yilmazer, Nusret Duygu; Korth, Martin

    2015-01-01

    Recent successes and failures of the application of ‘enhanced’ semiempirical QM (SQM) methods are reviewed in the light of the benefits and backdraws of adding dispersion (D) and hydrogen-bond (H) correction terms. We find that the accuracy of SQM-DH methods for non-covalent interactions is very often reported to be comparable to dispersion-corrected density functional theory (DFT-D), while computation times are about three orders of magnitude lower. SQM-DH methods thus open up a possibility to simulate realistically large model systems for problems both in life and materials science with comparably high accuracy. PMID:25848495

  4. Preparation of hybrid organic-inorganic mesoporous silicas applied to mercury removal from aqueous media: Influence of the synthesis route on adsorption capacity and efficiency.

    PubMed

    Pérez-Quintanilla, Damián; Sánchez, Alfredo; Sierra, Isabel

    2016-06-15

    New hybrid organic-inorganic mesoporous silicas were prepared by employing three different synthesis routes and mercury adsorption studies were done in aqueous media using the batch technique. The organic ligands employed for the functionalization were derivatives of 2-mercaptopyrimidine or 2-mercaptothiazoline, and the synthesis pathways used were post-synthesis, post-synthesis with surface ion-imprinting and co-condensation with ion-imprinting. The incorporation of functional groups and the presence of ordered mesopores in the organosilicas was confirmed by XRD, TEM and SEM, nitrogen adsorption-desorption isotherms, (13)C MAS-NMR, (29)Si MAS-NMR, elemental and thermogravimetric analysis. The highest adsorption capacity and selectivity observed was for the material functionalized with 2-mercaptothiazoline ligand by means the co-condensation with ion-imprinting route (1.03 mmol g(-1) at pH 6). The prepared material could be potential sorbent for the extraction of this heavy metal from environmental and drinking waters. PMID:27023632

  5. Preparation of hybrid organic-inorganic mesoporous silicas applied to mercury removal from aqueous media: Influence of the synthesis route on adsorption capacity and efficiency.

    PubMed

    Pérez-Quintanilla, Damián; Sánchez, Alfredo; Sierra, Isabel

    2016-06-15

    New hybrid organic-inorganic mesoporous silicas were prepared by employing three different synthesis routes and mercury adsorption studies were done in aqueous media using the batch technique. The organic ligands employed for the functionalization were derivatives of 2-mercaptopyrimidine or 2-mercaptothiazoline, and the synthesis pathways used were post-synthesis, post-synthesis with surface ion-imprinting and co-condensation with ion-imprinting. The incorporation of functional groups and the presence of ordered mesopores in the organosilicas was confirmed by XRD, TEM and SEM, nitrogen adsorption-desorption isotherms, (13)C MAS-NMR, (29)Si MAS-NMR, elemental and thermogravimetric analysis. The highest adsorption capacity and selectivity observed was for the material functionalized with 2-mercaptothiazoline ligand by means the co-condensation with ion-imprinting route (1.03 mmol g(-1) at pH 6). The prepared material could be potential sorbent for the extraction of this heavy metal from environmental and drinking waters.

  6. Changing the adsorption capacity of coal-based honeycomb monoliths for pollutant removal from liquid streams by controlling their porosity

    NASA Astrophysics Data System (ADS)

    Gatica, José M.; Harti, Sanae; Vidal, Hilario

    2010-09-01

    Coal-based honeycomb monoliths extruded using methods developed for ceramic materials have been used to retain methylene blue and p-nitrophenol from aqueous solutions. The influence of the filters' thermal treatment on their textural properties and performance as adsorbents was examined. Characterization by N 2 physisorption, mercury porosimetry and scanning electron microscopy along with adsorption tests under dynamic conditions suggest that, depending on the pollutant and its initial concentration, it can be more convenient to previously submit the monoliths to a simple carbonization or to an additional activation, with or without preoxidation, as a consequence of their different resulting pore structures. Infrared spectroscopy indicates that their different adsorption behaviour seems not to be related to differences in their surface chemical groups. In addition, axial crushing tests show that the monoliths have an acceptable mechanical resistance for the application investigated.

  7. Hydrogen adsorption capacities of multi-walled boron nitride nanotubes and nanotube arrays: a grand canonical Monte Carlo study.

    PubMed

    Ahadi, Zohreh; Shadman, Muhammad; Yeganegi, Saeed; Asgari, Farid

    2012-07-01

    Hydrogen adsorption in multi-walled boron nitride nanotubes and their arrays was studied using grand canonical Monte Carlo simulation. The results show that hydrogen storage increases with tube diameter and the distance between the tubes in multi-walled boron nitride nanotube arrays. Also, triple-walled boron nitride nanotubes present the lowest level of hydrogen physisorption, double-walled boron nitride nanotubes adsorb hydrogen better when the diameter of the inner tube diameter is sufficiently large, and single-walled boron nitride nanotubes adsorb hydrogen well when the tube diameter is small enough. Boron nitride nanotube arrays adsorb hydrogen, but the percentage of adsorbed hydrogen (by weight) in boron nitride nanotube arrays is rather similar to that found in multi-walled boron nitride nanotubes. Also, when the Langmuir and Langmuir-Freundlich equations were fitted to the simulated data, it was found that multi-layer adsorptivity occurs more prominently as the number of walls and the tube diameter increase. However, in single-walled boron nitride nanotubes with a small diameter, the dominant mechanism is monolayer adsorptivity.

  8. Hydrogen adsorption capacities of multi-walled boron nitride nanotubes and nanotube arrays: a grand canonical Monte Carlo study.

    PubMed

    Ahadi, Zohreh; Shadman, Muhammad; Yeganegi, Saeed; Asgari, Farid

    2012-07-01

    Hydrogen adsorption in multi-walled boron nitride nanotubes and their arrays was studied using grand canonical Monte Carlo simulation. The results show that hydrogen storage increases with tube diameter and the distance between the tubes in multi-walled boron nitride nanotube arrays. Also, triple-walled boron nitride nanotubes present the lowest level of hydrogen physisorption, double-walled boron nitride nanotubes adsorb hydrogen better when the diameter of the inner tube diameter is sufficiently large, and single-walled boron nitride nanotubes adsorb hydrogen well when the tube diameter is small enough. Boron nitride nanotube arrays adsorb hydrogen, but the percentage of adsorbed hydrogen (by weight) in boron nitride nanotube arrays is rather similar to that found in multi-walled boron nitride nanotubes. Also, when the Langmuir and Langmuir-Freundlich equations were fitted to the simulated data, it was found that multi-layer adsorptivity occurs more prominently as the number of walls and the tube diameter increase. However, in single-walled boron nitride nanotubes with a small diameter, the dominant mechanism is monolayer adsorptivity. PMID:22160758

  9. Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd(II), Zn(II) and Ni(II) and characterization with cavity microelectrode.

    PubMed

    Terbouche, Achour; Ramdane-Terbouche, Chafia Ait; Hauchard, Didier; Djebbar, Safia

    2011-01-01

    The adsorption capacities of new humic acids isolated from Yakouren forest (YHA) and Sahara (Tamenrasset: THA) soils (Algeria) and commercial humic acid (PFHA) on polyaniline emeraldine base (PEB) were studied at pH 6.6. Also the adsorption of heavy metals such as Cd2+, Zn2+ and Ni2+ on humic acid-polyaniline systems (HA-PEB) was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy (SEM), infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd2+, Zn2+ and Ni2+ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities (q(max)) of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that q(max) of Cd2+, Zn2+ and Ni2+ on HA-PEB followed the order: THA-PEB > YHA-PEB > PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.

  10. CTAB-assisted synthesis of mesoporous F-N-codoped TiO{sub 2} powders with high visible-light-driven catalytic activity and adsorption capacity

    SciTech Connect

    Xie Yi Zhao Xiujian Li Yuanzhi; Zhao Qingnan; Zhou Xuedong; Yuan Qihua

    2008-08-15

    This article describes the preparation of mesoporous rod-like F-N-codoped TiO{sub 2} powder photocatalysts with anatase phase via a sol-gel route at the temperature of 373 K, using cetyltrimethyl ammonium bromide (CTAB) as surfactant. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-vis DRS). The results showed that the photocatalysts possessed a homogeneous pore diameter and a high surface area of 106.3-160.7 m{sup 3} g{sup -1}. The increasing CTAB reactive concentration extended the visible-light absorption up to 600 nm. The F-N-codoped TiO{sub 2} powders exhibited significant higher adsorption capacity for methyl orange (MO) than that of Degussa P25 and showed more than 6 times higher visible-light-induced catalytic degradation for MO than that of P25. - Graphical abstract: The introduction of surfactant CTAB not only extended the visible light absorption of mesoporous F-N-codoped TiO{sub 2} up to 600 nm but also significantly enhanced the adsorption capacity and visible-light-induced degradation for methyl orange. Mesoporous rod-like F-N-codoped TiO{sub 2} powder photocatalysts were synthesized via a sol-gel route at low temperature of 373 K.

  11. Molecular dynamics simulations of ion solvation by flexible-boundary QM/MM: on-the-fly partial charge transfer between QM and MM subsystems.

    PubMed

    Pezeshki, Soroosh; Lin, Hai

    2014-09-15

    The flexible-boundary (FB) quantum mechanical/molecular mechanical (QM/MM) scheme accounts for partial charge transfer between the QM and MM subsystems. Previous calculations have demonstrated excellent performance of FB-QM/MM in geometry optimizations. This article reports an implementation to extend FB-QM/MM to molecular dynamics simulations. To prevent atoms from getting unreasonably close, which can lead to polarization catastrophe, empirical correcting functions are introduced to provide additive penalty energies for the involved atom pairs and to improve the descriptions of the repulsive exchange forces in FB-QM/MM calculations. Test calculations are carried out for chloride, lithium, sodium, and ammonium ions solvated in water. Comparisons with conventional QM/MM calculations suggest that the FB treatment provides reasonably good results for the charge distributions of the atoms in the QM subsystems and for the solvation shell structural properties, albeit smaller QM subsystems have been used in the FB-QM/MM dynamics simulations.

  12. A modified QM/MM Hamiltonian with the Self-Consistent-Charge Density-Functional-Tight-Binding Theory for highly charged QM regions

    PubMed Central

    Hou, Guanhua; Zhu, Xiao; Elstner, Marcus; Cui, Qiang

    2012-01-01

    To improve the description of electrostatic interaction between QM and MM atoms when the QM is SCC-DFTB, we adopt a Klopman-Ohno (KO) functional form which considers the finite size of the QM and MM charge distributions. Compared to the original implementation that used a simple Coulombic interaction between QM Mulliken and MM point charges, the KO based QM/MM scheme takes charge penetration effect into consideration and therefore significantly improves the description of QM/MM interaction at short range, especially when the QM region is highly charged. To be consistent with the third-order formulation of SCC-DFTB, the Hubbard parameter in the KO functional is dependent on the QM charge. As a result, the effective size of the QM charge distribution naturally adjusts as the QM region undergoes chemical transformations, making the KO based QM/MM scheme particularly attractive for describing chemical reactions in the condensed phase. Together with the van der Waals parameters for the QM atom, the KO based QM/MM model introduces four parameters for each element type. They are fitted here based on microsolvation models of small solutes, focusing on negatively charged molecular ions, for elements O, C, H and P with a specific version of SCC-DFTB (SCC-DFTBPR). Test calculations confirm that the KO based QM/MM scheme significantly improves the interactions between QM and MM atoms over the original point charge based model and it is transferable due to the small number of parameters. The new form of QM/MM Hamiltonian will greatly improve the applicability of SCC-DFTB based QM/MM methods to problems that involve highly charged QM regions, such as enzyme catalyzed phosphoryl transfers. PMID:23275762

  13. Polyamine-Cladded 18-Ring-Channel Gallium Phosphites with High-Capacity Hydrogen Adsorption and Carbon Dioxide Capture.

    PubMed

    Sie, Ming-Jhe; Lin, Chia-Her; Wang, Sue-Lein

    2016-06-01

    In this study, we synthesized a unique inorganic framework bearing the largest 18-membered-ring channels in gallium phosphites, denoted as NTHU-15, which displayed genuine porosity even though large organic templates were present. The idea of using the "template-cladded" strategy succeeded in releasing channel space of up to ∼24% of the unit-cell volume as highly positive-charged organic templates were manipulated to cling to the anionic inorganic walls. NTHU-15 showed both high H2 uptake of 3.8 mmol/g at 77 K and effective CO2 adsorption of ∼2.4 mmol/g at 298 K, which surpassed those of all other known extra-large-channel inorganic framework structures. NTHU-15 has been successful at overcoming the long-standing problem of organic-templated extra-large-channel structures as opposed to a "true open" framework. Moreover, it realized practical gas sorption functionality in innovated metal phosphites. In view of its high stability in hot water and high selectivity for CO2 adsorption, NTHU-15 may be the first novel inorganic framework material to be applied to the field of flue gas cleaning. PMID:27181272

  14. Effect of cetyl trimethyl ammonium bromide concentration on structure, morphology and carbon dioxide adsorption capacity of calcium hydroxide based sorbents

    NASA Astrophysics Data System (ADS)

    Hlaing, Nwe Ni; Vignesh, K.; Sreekantan, Srimala; Pung, Swee-Yong; Hinode, Hirofumi; Kurniawan, Winarto; Othman, Radzali; Thant, Aye Aye; Mohamed, Abdul Rahman; Salim, Chris

    2016-02-01

    Calcium hydroxide (Ca(OH)2) has been proposed as an important material for industrial, architectural, and environmental applications. In this study, calcium acetate was used as a precursor and cetyl trimethyl ammonium bromide (CTAB) was used as a surfactant to synthesize Ca(OH)2 based adsorbents for carbon dioxide (CO2) capture. The effect of CTAB concentration (0.2-0.8 M) on the structure, morphology and CO2 adsorption performance of Ca(OH)2 was studied in detail. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), BET surfaced area and thermogravimetry-differential thermal analysis (TG-DTA) techniques. The phase purity, crystallite size, Brunauer-Emmett-Teller (BET) surface area and CO2 adsorption performance of Ca(OH)2 precursor adsorbents were significantly increased when the concentration of CTAB was increased. XRD results showed that pure Ca(OH)2 phase was obtained at the CTAB concentration of 0.8 M. TGA results exhibited that 0.8 M of CTAB-assisted Ca(OH)2 precursor adsorbent possessed a residual carbonation conversion of ∼56% after 10 cycles.

  15. Comparison between the loading capacities of columns packed with partially and totally porous fine particles. What is the effective surface area available for adsorption?

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2007-12-28

    The adsorption isotherms of phenol, caffeine, insulin, and lysozyme were measured on two C(18)-bonded silica columns. The first one was packed with classical totally porous particles (3 microm Luna(2)-C(18)from Phenomenex, Torrance, CA, USA), the second one with shell particles (2.7 microm Halo-C(18) from Advanced Materials Technology, Wilmington, DE, USA). The measurements were made at room temperature (T=295+/-1K), using mainly frontal analysis (FA) and also elution by characteristic points (FACP) when necessary. The adsorption energy distributions (AEDs) were estimated by the iterative numerical expectation-maximization (EM) procedure and served to justify the choice of the best adsorption isotherm model for each compound. The best isotherm parameters were derived from either the best fit of the experimental data to a multi-Langmuir isotherm model (MLRA) or from the AED results (equilibrium constants and saturation capacities), when the convergence of the EM program was achieved. The experiments show than the loading capacity of the Luna column is more than twice that of the Halo column for low-molecular-weight compounds. This result was expected; it is in good agreement with the values of the accessible surface area of these two materials, which were calculated from the pore size volume distributions. The pore size volume distributions are validated by the excellent agreement between the calculated and measured exclusion volumes of polystyrene standards by inverse size exclusion chromatography (ISEC). In contrast, the loading capacity ratio of the two columns is 1.5 or less with insulin and lysozyme. This is due to a significant exclusion of these two proteins from the internal pore volumes of the two packing materials. This result raises the problem of the determination of the effective surface area of the packing material, particularly in the case of proteins. This area is about 40 and 30% of the total surface area for insulin and for lysozyme, respectively

  16. Capacity of adsorption of Pb2+ and Ni2+ from aqueous solutions by chitosan produced from silkworm chrysalides in different degrees of deacetylation.

    PubMed

    Paulino, Alexandre T; Guilherme, Marcos R; Reis, Adriano V; Tambourgi, Elias B; Nozaki, Jorge; Muniz, Edvani C

    2007-08-17

    The binding capacities of chitin (CT) and chitosan (CS) produced from silkworm chrysalides were investigated aiming at their future application in the removal of Pb2+ and Ni2+ from wastewaters. CS with 75% deacetylation degree (DD) exhibited good binding performance for Pb(2+), but bad efficiency for Ni2+. The maximum binding capacity obtained from isotherms for CS-Pb was 141.10 mg g(-1) and 52.81 mg g(-1) for CS-Ni. The binding capacities for CT were 32.01 mg g(-1) for Pb2+ and 61.24 mg g(-1) for Ni2+. The authors attribute these behaviors to two main factors: (i) the large ionic size of Pb2+ and (ii) the steric hindrance due to CT acetyl groups. Metal binding onto CS was evaluated by the Freundlich and Langmuir isotherm models. The parameter values obtained from the isotherm analysis confirmed that Pb2+ and Ni2+ interact differently with CS and that various factors influence their adsorption. Thermogravimetric analysis (TGA) showed that the thermal behavior of CS with 75% deacetylation degree was in the same profile of standard CS; however, the binding of the metals onto its structure affects the curve profile. PMID:17258857

  17. Arsenic(III) Removal from Contaminated Water using Silica Ceramic: A Batch Adsorption Study

    NASA Astrophysics Data System (ADS)

    Salim, Md.; Munekage, Yukihiro; Naing, Kyaw Min

    The silica ceramic (S-K) has been used as a potential low-cost adsorbent for the removal of As(III) from contaminated water in batch studies. Results showed that an adsorbent dose at 90 g L1 could effectively remove 96% of As(III) from initial concentration of 0.5 mg L1 within 3 h. It was also reveled that As(III) uptake increased with increasing contact time and As(III) concentration decreased with increasing adsorbent dosage. It was observed that As(III) removal is relatively dependent on pH and temperature variations. High adsorption of As(III) was found at pH 7.5 and at 25°C. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. The Freundlich isotherm provided the best correlation for the adsorption of As(III) onto the silica ceramic. The maximum capacity of adsorption was found (qm) 1.1041 mg g1 at different concentrations at 40 g L1 fixed adsorption dosage. The results suggest that silica ceramic (S-K) is a potential adsorbent for removal As(III) ions effectively from contaminated water.

  18. Adsorption mechanism of magnetically separable Fe3O4/graphene oxide hybrids

    NASA Astrophysics Data System (ADS)

    Ouyang, Ke; Zhu, Chuanhe; Zhao, Ya; Wang, Leichao; Xie, Shan; Wang, Qun

    2015-11-01

    A reclaimable Fe3O4/graphene oxide (GO) magnetic hybrid was successfully synthesized via a facile one-pot polyol approach and employed as a recyclable adsorbent for Bisphenol A (BPA) in aqueous solutions. The maximum adsorption capacity (qm) of the Fe3O4/GO hybrid for BPA was 72.80 mg/g at 273 K. The kinetics of the adsorption process and the adsorption isotherm data were fitted using the Freundlich equation and a pseudo-second-order kinetic model. The results of the thermodynamic parameters ΔH°, ΔS° and ΔG° showed that the adsorption process was exothermic and spontaneous. Furthermore, the reusability of the samples was investigated, and the results indicated that the samples exhibited high stability. The magnetic characterization demonstrated that hybrids were superparamagnetic and could be recovered conveniently by magnetic separation. The strong π-π interaction was determined to be the predominant driving force behind the adsorption of BPA onto the Fe3O4/GO hybrid. Therefore, the Fe3O4/GO hybrid could be regarded as a potential adsorbent for wastewater treatment and purification processes.

  19. [Adsorption behavior of copper ion and methylene blue on citric acid- esterified wheat straw].

    PubMed

    Sun, Jin; Zhong, Ke-Ding; Feng, Min; Liu, Xing-Yan; Gong, Ren-Min

    2008-03-01

    A cationic adsorbent with carboxyl groups derived from citric acid- esterified wheat straw (EWS) was prepared by the method of solid phase preparation, and a batch experiment was conducted to study the adsorption behaviors of Cu (II) and methylene blue (MB) in aqueous solution on the EWS under conditions of different initial pH, adsorbent dosage, adsorbate concentration, and contact time. The results showed that the maximum adsorption of Cu (II) and MB was obtained when the initial solution pH was > or = 4.0. 96% of Cu (II) in 100 mg x L(-1) Cu solution and 99% of MB in 250 mg x L(-1) dye solution could be removed by > or = 2.0 g x L(-1) of EWS. The adsorption of Cu (II) and MB fitted the Langmuir sorption isothermal model. The maximum removal capacity (Qm) of EWS was 79.37 mg x g(-1) for Cu (II) and 312.50 mg x g(-1) for MB, and the adsorption equilibrium of Cu (II) and MB was reached within 75 min and 5 h, respectively. The adsorption processes of Cu (II) and MB could be described by pseudo-first order and pseudo-second order kinetic functions, respectively.

  20. Preparation and characterization of poly(AA co PVP)/PGS composite and its application for methylene blue adsorption.

    PubMed

    Yang, Cai-xia; Lei, Lei; Zhou, Peng-xin; Zhang, Zhe; Lei, Zi-qiang

    2015-04-01

    Poly (AA co PVP)/PGS (PAPP) composite adsorbent was prepared by radical polymerization from Acrylic acid (AA), Polyvinylpyrrolidone (PVP) and Palygorskite (PGS), using N,N-methylenebisacrylamide (MBA) as cross-linker and potassium persulfate (KPS) as initiator. The PAPP was characterized with Fourier transform infrared (FT-IR), thermogravimetric analysis (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). PAPP was used as adsorbent for the removal of methylene blue from aqueous solutions. The influences of pH, adsorption temperature and adsorption time on the adsorption properties of the composite to the dye were also investigated. Meanwhile, the adsorption rate data and adsorption equilibrium date were analyzed based on the pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models, respectively. The results indicating that the kinetic behavior better fit with the pseudo-second-order kinetic model. The maximum equilibrium adsorption capacity (q(m)) is 1815 mg/g at 289 K. The isotherm behavior can be explained by the Langmuir isotherm models. The activation energy was also evaluated for the removal of methylene blue onto PAPP. These results demonstrate that this composite material could be used as a good adsorbent for the removal of cationic dyes from wastewater. PMID:25540826

  1. Preparation and characterization of poly(AA co PVP)/PGS composite and its application for methylene blue adsorption.

    PubMed

    Yang, Cai-xia; Lei, Lei; Zhou, Peng-xin; Zhang, Zhe; Lei, Zi-qiang

    2015-04-01

    Poly (AA co PVP)/PGS (PAPP) composite adsorbent was prepared by radical polymerization from Acrylic acid (AA), Polyvinylpyrrolidone (PVP) and Palygorskite (PGS), using N,N-methylenebisacrylamide (MBA) as cross-linker and potassium persulfate (KPS) as initiator. The PAPP was characterized with Fourier transform infrared (FT-IR), thermogravimetric analysis (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). PAPP was used as adsorbent for the removal of methylene blue from aqueous solutions. The influences of pH, adsorption temperature and adsorption time on the adsorption properties of the composite to the dye were also investigated. Meanwhile, the adsorption rate data and adsorption equilibrium date were analyzed based on the pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models, respectively. The results indicating that the kinetic behavior better fit with the pseudo-second-order kinetic model. The maximum equilibrium adsorption capacity (q(m)) is 1815 mg/g at 289 K. The isotherm behavior can be explained by the Langmuir isotherm models. The activation energy was also evaluated for the removal of methylene blue onto PAPP. These results demonstrate that this composite material could be used as a good adsorbent for the removal of cationic dyes from wastewater.

  2. Protein adsorption to poly(ethylenimine)-modified Sepharose FF: III. Comparison between different proteins.

    PubMed

    Hong, Yan; Liu, Na; Wei, Wei; Yu, Lin-Ling; Ma, Guanghui; Sun, Yan

    2014-05-16

    Previously, we studied bovine serum albumin (BSA) uptake to poly(ethylenimine) (PEI)-grafted Sepharose resins, and an ionic capacity (IC) range (600-740mmol/L) for steep increases of both protein capacity (qm) and effective pore diffusion coefficient (De) was found. In this work, seven PEI-grafted Sepharose FF resins at IC range of 270-1030mmol/L were synthesized to investigate the effect of protein properties on the adsorption and uptake kinetics using BSA and γ-globulin as two model proteins. For BSA, the change trends of qm and De values with IC were well consistent with the previous results. For γ-globulin, the qm values increased slowly till reaching a maximum value at IC=560mmol/L and then decreased rapidly at IC>560mol/L. The De values nearly kept unchanged at low ICs (IC<460mmol/L), and increased steeply at IC>460mmol/L till reaching a maximum at 680mmol/L (De/D0=0.48±0.01). After that increase, the De values for γ-globulin dropped quickly at IC>680mol/L, which was not observed for BSA. It is interesting to note that in the narrow IC range of 460-680mmol/L, the De values of γ-globulin increased dramatically for more than four folds. Moreover, it is notable that the IC range where the hopping of De values occurred for γ-globulin was earlier than that for BSA (460 vs. 560mmol/L). The earlier hopping of γ-globulin uptake rate was attributed to its larger size and less net charge, which facilitated the happenings of the "chain delivery" effect. The quick drops of both qm and De values for γ-globulin at IC>680mmol/L were considered due to its large size, which led to the significant decrease of its effective pore volume. The results indicate that both PEI layer and protein size played important roles in protein adsorption to PEI-grafted resins, and further prove the "chain delivery" effect did contributed significantly to the uptake rate hopping in the PEI-grafted resins. This work could also help the design and selection of resins based on protein

  3. Hexavalent chromium removal performance of anionic functionalized monolithic polymers: column adsorption, regeneration and modelling.

    PubMed

    Barlik, Necla; Keskinler, Bülent; Kocakerim, M Muhtar

    2016-01-01

    Anionic functionalized monolithic macro-porous polymers were used for the removal of hexavalent chromium(VI) anions from aqueous solution in column experiments. At a flux of 1.0 cm min and 30 mg Cr(VI) L(-1) feed concentration, breakthrough capacity and apparent capacity were 0.066 g Cr(VI) g(-1) anionic monolith and 0.144 g Cr(VI) g(-1) anionic monolith, respectively. The degree of column utilization was found to lie in the range 41-46%. Two kinetic models, theoretical and Thomas models, were applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The simulation of the whole breakthrough curve was effective with the models. At a flux of 1.0 cm min and 30 mg Cr(VI) L(-1) feed concentration, the dispersion coefficient and adsorption equilibrium constant (K) were 3.14 × 10(-7) m s(-1) and 3,840, respectively. Also, Thomas model parameters k1 (rate constant of adsorption) and qm (equilibrium solid-phase concentration of sorbed solute) were 1.08 × 10(-3) L mg(-1) min(-1) and 0.124 g g(-1), respectively. After reaching equilibrium adsorption capacity, the monoliths were regenerated using 1 N HCl and were subsequently re-tested. It was found that the regeneration efficiency reduced from 98% after second usage to 97% after the third usage. PMID:27003067

  4. [Preparation of porous ceramics based on waste ceramics and its Ni2+ adsorption characteristics].

    PubMed

    Zhang, Yong-Li; Wang, Cheng-Zhi; Shi, Ce; Shang, Ling-Ling; Ma, Rui; Dong, Wan-Li

    2013-07-01

    The preparation conditions of porous ceramics were determined by SEM, XRD and FT-IR characterizations as well as the nickel removal ability of porous ceramics to be: the mass fraction w of sesbania powder doped was 4%, and the calcination temperature was 800 degrees C. SEM and pore structure characterization illustrated that calcination caused changes in the structure and morphology of waste ceramics. With the increase of calcination temperature, the specific surface area and pore volume decreased, while the aperture increased. EDS analyses showed that the main elements of both the original waste porcelain powder and the porous ceramics were Si, Al and O. The SEM, XRD and FT-IR characterization of porous ceramics illustrated that the structure of porous ceramics was stable before and after adsorption. The series of experiments of Ni2+ adsorption using these porous ceramics showed that when the dosage of porous ceramics was 10 g x L(-1), the adsorption time was 60 min, the pH value was 6.32, and the concentration of nickel-containing wastewater was below 100 mg x L(-1), the Ni2+ removal of wastewater reached 89.7%. Besides, the porous ceramics showed higher removal efficiency on nickel in the wastewater. The Ni(2+)-containing wastewater was processed by the porous ceramics prepared, and the adsorption dynamics and adsorption isotherms of Ni2+ in wastewater by porous ceramics were investigated. The research results showed that the Ni2+ adsorption process of porous ceramics was in accordance with the quasi second-order kinetic model (R2 = 0.999 9), with Q(e) of 9.09 mg x g(-1). The adsorption process can be described by the Freundlich equation and Langmuir equation, and when the temperature increased from 20 degrees C to 40 degrees C, the maximum adsorption capacity Q(m) increased from 14.49 mg x g(-1) to 15.38 mg x g(-1). PMID:24028001

  5. [Preparation of porous ceramics based on waste ceramics and its Ni2+ adsorption characteristics].

    PubMed

    Zhang, Yong-Li; Wang, Cheng-Zhi; Shi, Ce; Shang, Ling-Ling; Ma, Rui; Dong, Wan-Li

    2013-07-01

    The preparation conditions of porous ceramics were determined by SEM, XRD and FT-IR characterizations as well as the nickel removal ability of porous ceramics to be: the mass fraction w of sesbania powder doped was 4%, and the calcination temperature was 800 degrees C. SEM and pore structure characterization illustrated that calcination caused changes in the structure and morphology of waste ceramics. With the increase of calcination temperature, the specific surface area and pore volume decreased, while the aperture increased. EDS analyses showed that the main elements of both the original waste porcelain powder and the porous ceramics were Si, Al and O. The SEM, XRD and FT-IR characterization of porous ceramics illustrated that the structure of porous ceramics was stable before and after adsorption. The series of experiments of Ni2+ adsorption using these porous ceramics showed that when the dosage of porous ceramics was 10 g x L(-1), the adsorption time was 60 min, the pH value was 6.32, and the concentration of nickel-containing wastewater was below 100 mg x L(-1), the Ni2+ removal of wastewater reached 89.7%. Besides, the porous ceramics showed higher removal efficiency on nickel in the wastewater. The Ni(2+)-containing wastewater was processed by the porous ceramics prepared, and the adsorption dynamics and adsorption isotherms of Ni2+ in wastewater by porous ceramics were investigated. The research results showed that the Ni2+ adsorption process of porous ceramics was in accordance with the quasi second-order kinetic model (R2 = 0.999 9), with Q(e) of 9.09 mg x g(-1). The adsorption process can be described by the Freundlich equation and Langmuir equation, and when the temperature increased from 20 degrees C to 40 degrees C, the maximum adsorption capacity Q(m) increased from 14.49 mg x g(-1) to 15.38 mg x g(-1).

  6. Long-Life and High-Areal-Capacity Li-S Batteries Enabled by a Light-Weight Polar Host with Intrinsic Polysulfide Adsorption.

    PubMed

    Pang, Quan; Nazar, Linda F

    2016-04-26

    Lithium-sulfur batteries are attractive electrochemical energy storage systems due to their high theoretical energy density and very high natural abundance of sulfur. However, practically, Li-S batteries suffer from short cycling life and low sulfur utilization, particularly in the case of high-sulfur-loaded cathodes. Here, we report on a light-weight nanoporous graphitic carbon nitride (high-surface-area g-C3N4) that enables a sulfur electrode with an ultralow long-term capacity fade rate of 0.04% per cycle over 1500 cycles at a practical C/2 rate. More importantly, it exhibits good high-sulfur-loading areal capacity (up to 3.5 mAh cm(-2)) with stable cell performance. We demonstrate the strong chemical interaction of g-C3N4 with polysulfides using a combination of spectroscopic experimental studies and first-principles calculations. The 53.5% concentration of accessible pyridinic nitrogen polysulfide adsorption sites is shown to be key for the greatly improved cycling performance compared to that of N-doped carbons. PMID:26841116

  7. [Simulation study on the effect of salinity on the adsorption behavior of mercury in wastewater-irrigated area].

    PubMed

    Zheng, Shun-An; Li, Xiao-Hua; Xu, Zhi-Yu

    2014-05-01

    This study was designed to pinpoint the impact of salinity ( NaCl and Na2SO4, added at salinity levels of 0-5%, respectively) on the adsorption behavior of mercury in wastewater-irrigated areas of Tianjin City by batch and kinetic experiments. The results showed that, the Langmuir isotherm and the Elovich equation can well fitted batch and kinetic experimental data, respectively. As NaCI spiked in soil, Hg( II) adsorption capacity and strength had marked decreases, from 868.64 mgkg-1 and 1. 32 at control to 357.48 mgkg-1 and 0.63 at 5% salinity level of NaCI, respectively. As Na2SO4 spiked in soil, Hg(II) adsorption capacity (parameter qm in Langmuir isotherm) and strength (parameter k in Langmuir isotherm) changed slightly, from 868.64 mg kg-1 and 1.32 at control to 739.44 mg.kg-1 and 1. 18 at 5% salinity level of Na2 SO4, respectively. Kinetic data showed that, Hg( II) adsorption rate (parameter b in Elovich equation) in soil was not influenced by Na2SO, addition. However, the addition of NaC1 had a great effect on mercury adsorption rate. Hg(II ) adsorption capacity as a function of CI- or SO(2-)(4) content in soil could be simulated by the natural logarithm model, while Hg( II ) adsorption rate as a function of CI- content in soil could be simulated by the linear model. The study manifested that NaCI can significantly increase migration of Hg( II ) in the soil irrigated with wastewater, which may enhance Hg( II) bioavailability in the soil and cause a hazard to surface water. Especially, it will be harmful to human body through the food chain. PMID:25055690

  8. Condensed phase QM/MM simulations utilizing the exchange core functions to describe exchange repulsions at the QM boundary region

    NASA Astrophysics Data System (ADS)

    Umino, Satoru; Takahashi, Hideaki; Morita, Akihiro

    2016-08-01

    In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion Eex between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining Eex on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems including a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμex from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron.

  9. Condensed phase QM/MM simulations utilizing the exchange core functions to describe exchange repulsions at the QM boundary region.

    PubMed

    Umino, Satoru; Takahashi, Hideaki; Morita, Akihiro

    2016-08-28

    In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion Eex between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining Eex on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems including a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμex from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron. PMID:27586904

  10. Adsorption of Cu2+ ions using chitosan-modified magnetic Mn ferrite nanoparticles synthesized by microwave-assisted hydrothermal method

    NASA Astrophysics Data System (ADS)

    Meng, Yuying; Chen, Deyang; Sun, Yitao; Jiao, Dongling; Zeng, Dechang; Liu, Zhongwu

    2015-01-01

    Chitosan-modified Mn ferrite nanoparticles were synthesized by a one-step microwave-assisted hydrothermal method. These Mn ferrite magnetic composite nanoparticles were employed to absorb Cu2+ ions in water. XRD verified the spinel structure of the MnFe2O4 nanoparticles. Chitosan modification does not result in any phase change of MnFe2O4. FTIR and zeta potentials curves for all samples suggest that chitosan can be successfully coated on the Mn ferrites. TEM characterization showed that the modified MnFe2O4 nanoparticles have a cubic shape with a mean diameter of ∼100 nm. For adsorption behavior, the effects of experiment parameters such as solution pH value, contact time and initial Cu2+ ions concentration on the adsorption efficiency were systematically investigated. The results showed that increasing solution pH value and extending contact time are favorable for improving adsorption efficiency. Especially, adsorption efficiency can reach up to 100% and 96.7% after 500 min adsorption at pH 6.5 for the solutions with initial Cu2+ ions concentration of 50 mg/L and 100 mg/L. Adsorption data fits well with the Langmuir isotherm models with a maximum adsorption capacity (qm) and a Langmuir adsorption equilibrium constant (K) of 65.1 mg/g and 0.090 L/mg, respectively. The adsorption kinetic agrees well with pseudo second order model with the pseudo second rate constants (K2) of 0.0468 and 0.00189 g/mg/min for solutions with initial Cu2+ ions of 50 and 100 mg/L, respectively.

  11. Mobility and adsorption capacity of Pb and Zn in a polluted soil from a road environment: laboratory batch experiments.

    PubMed

    Delmas, C; Larpin, L; Legret, M; Astruc, M

    2002-04-01

    A study of the mobility of lead and zinc in a contaminated soil from a road environment was conducted in order to evaluate the risk of groundwater contamination due to rainwater infiltration. The mobility of trace metals was evaluated using single chemical extractions and single-element sorption experiments. The distribution of trace metallic elements on the various soil fractions investigated with the use of sequential extractions, both before and after single extraction or sorption experiments, enabled the monitoring of changes in their localization. Metals are slightly extracted by sodium chloride solutions. High extraction yield was obtained for lead using EDTA. Lead was removed from the "acid-soluble", "reducible" and "oxidizable" fractions. In contrast, zinc was less dissolved by means of complexation with EDTA, yet it showed very high sensitivity to variations in pH. Following single extractions, metals were redistributed in the "exchangeable" fraction. Sorption experiments evaluated the capacity of the soil to retain additional lead and zinc inputs. The results reveal that pH influences the sorption of these metals and the initial pollution present in the soil may induce desorption phenomena with respect to zinc. The high initial concentrations present in the soil do not seem to prevent the retention of additional metal in significant quantities. Added metals were located in the "exchangeable", "add-soluble" and "reducible" fractions.

  12. Selective adsorption for removal of nitrogen compounds from hydrocarbon streams over carbon-based adsorbents

    NASA Astrophysics Data System (ADS)

    Almarri, Masoud S.

    The ultimate goal of this thesis is to develop a fundamental understanding of the role of surface oxygen functional groups on carbon-based adsorbents in the adsorption of nitrogen compounds that are known to be present in liquid fuels. N2 adsorption was used to characterize pore structures. The surface chemical properties of the adsorbents were characterized by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques with a mass spectrometer to identify and quantify the type and concentration of oxygen functional groups on the basis of CO2 and CO evolution profiles. It was found that although surface area and pore size distribution are important for the adsorption process, they are not primary factors in the adsorption of nitrogen compounds. On the other hand, both the type and concentration of surface oxygen-containing functional groups play an important role in determining adsorptive denitrogenation performance. Higher concentrations of the oxygen functional groups on the adsorbents resulted in a higher adsorption capacity for the nitrogen compounds. A fundamental insight was gained into the contributions of different oxygen functional groups by analyzing the changes in the monolayer maximum adsorption capacity, qm, and the adsorption constant, K, for nitrogen compounds on different activated carbons. Acidic functional groups such as carboxylic acids and carboxylic anhydrides appear to contribute more to the adsorption of quinoline, while the basic oxygen functional groups such as carbonyls and quinones enhance the adsorption of indole. Despite the high number of publications on the adsorptive desulfurization of liquid hydrocarbon fuels, these studies did not consider the presence of coexisting nitrogen compounds. It is well-known that, to achieve ultraclean diesel fuel, sulfur must be reduced to a very low level, where the concentrations of nitrogen and sulfur compounds are comparable. The adsorptive denitrogenation and

  13. QM/MM X-ray Refinement of Zinc Metalloenzymes

    PubMed Central

    Li, Xue; Hayik, Seth A.; Merz, Kenneth M.

    2010-01-01

    Zinc metalloenzymes play an important role in biology. However, due to the limitation of molecular force field energy restraints used in X-ray refinement at medium or low resolutions, the precise geometry of the zinc coordination environment can be difficult to distinguish from ambiguous electron density maps. Due to the difficulties involved in defining accurate force fields for metal ions, the QM/MM (Quantum-Mechanical /Molecular-Mechanical) method provides an attractive and more general alternative for the study and refinement of metalloprotein active sites. Herein we present three examples that indicate that QM/MM based refinement yields a superior description of the crystal structure based on R and Rfree values and on the inspection of the zinc coordination environment. It is concluded that QM/MM refinement is a useful general tool for the improvement of the metal coordination sphere in metalloenzyme active sites. PMID:20116858

  14. Poly(amic acid)-modified biomass of baker's yeast for enhancement adsorption of methylene blue and basic magenta.

    PubMed

    Yu, Jun-xia; Li, Bu-hai; Sun, Xiao-mei; Yuan, Jun; Chi, Ru-an

    2010-03-01

    In this study, poly(amic acid)-modified biomass was prepared to improve the adsorption capacities for two cationic dyes, methylene blue and basic magenta. X-ray photoelectron spectroscopy and potentiometric titration demonstrated that a large number of imide, amine, and carboxyl groups were introduced on the biomass surface, and the concentrations of these functional groups were calculated to be 0.27, 1.08, and 1.08 mmol g(-1) by using the first derivative method. According to the Langmuir equation, the maximum uptake capacities (q(m)) for methylene blue and basic magenta were 680.3 and 353.4 mg g(-1), respectively, which were 13- and sevenfold than that obtained on the unmodified biomass. Adsorption kinetics study showed that the completion of the adsorption process needed only 40 min, which is faster than the common sorbent such as activated carbon and resin. Experimental results showed that pH and ionic strength had little effect on the capacity of the modified biomass, indicating that the modified biomass had good potential for practical use.

  15. Periodic Boundary Conditions in QM/MM Calculations: Implementation and Tests.

    PubMed

    Vasilevskaya, Tatiana; Thiel, Walter

    2016-08-01

    Quantum mechanics/molecular mechanics (QM/MM) simulations of reactions in solutions and in solvated enzymes can be performed using the QM/MM-Ewald approach with periodic boundary conditions (PBC) or a nonperiodic treatment with a finite solvent shell (droplet model). To avoid the changes in QM codes that are required in standard QM/MM-Ewald implementations, we present a general method (Gen-Ew) for periodic QM/MM calculations that can be used with any QM method in the QM/MM framework. The Gen-Ew approach approximates the QM/MM-Ewald method by representing the PBC potential by virtual charges on a sphere and the QM density by electrostatic potential (ESP) charges. Test calculations show that the deviations between Gen-Ew and QM/MM-Ewald results are generally small enough to justify the application of the Gen-Ew method in the absence of a suitable QM/MM-Ewald implementation. We compare the results from periodic QM/MM calculations (QM/MM-Ewald, Gen-Ew) to their nonperiodic counterparts (droplet model) for five test reactions in water and for the Claisen rearrangement in chorismate mutase. The periodic and nonperiodic QM/MM treatments give similar free energy profiles for the reactions in solution (umbrella sampling, free energy deviations of the order of 1 kcal/mol) and essentially the same energy profile (constrained geometry optimizations) for the Claisen rearrangement in chorismate mutase. In all cases considered, long-range electrostatic interactions are thus well captured by nonperiodic QM/MM calculations in a water droplet of reasonable size (radius of 15-20 Å). This provides further justification for the widespread use of the computationally efficient droplet model in QM/MM studies of reactions in solution and in enzymes. PMID:27420296

  16. Using Web 2.0 Technologies to Meet Quality Matters[TM] (QM) Requirements

    ERIC Educational Resources Information Center

    Pollacia, Lissa; McCallister, Terrie

    2009-01-01

    Quality Matters[TM] (QM) is a set of standards to measure the quality of instruction and design in online or hybrid courses. Adopted by a growing number of institutions nationwide, QM is based on best practices and instructional design research. To meet or exceed QM standards requires that resources and learning activities in an online course…

  17. QM-8 final performance evaluation report: SEALS, volume 4

    NASA Technical Reports Server (NTRS)

    Nelsen, L. V.

    1989-01-01

    The Space Shuttle Redesigned Solid Rocket Motor (RSRM) static test of Qualification Motor-8 (QM-8) was conducted. The QM-8 test article was the fifth full-scale, full-duration test, and the third qualification motor to incorporate the redesigned case field joint and nozzle-to-case joint. This was the second static test conducted in the T-97 test facility, which is equipped with actuators for inducing external side loads to a 360 degree external tank (ET) attach ring during test motor operation, and permits heating/cooling of an entire motor. The QM-8 motor was cooled to a temperature which ensured that the maximum propellant mean bulk temperature (PMBT) of 40 F was achieved at firing. All test results are not included, but rather, the performance of the metal case, field joints, and nozzle-to-case joint is addressed. The involvement is studied of the Structural Applications and Structural Design Groups with the QM-8 test which includes: assembly procedures of the field and nozzle-to-case joints, joint leak check results, structural test results, and post-test inspection evaluations.

  18. Molecular dynamics simulations of ion solvation by flexible-boundary QM/MM: on-the-fly partial charge transfer between QM and MM subsystems.

    PubMed

    Pezeshki, Soroosh; Lin, Hai

    2014-09-15

    The flexible-boundary (FB) quantum mechanical/molecular mechanical (QM/MM) scheme accounts for partial charge transfer between the QM and MM subsystems. Previous calculations have demonstrated excellent performance of FB-QM/MM in geometry optimizations. This article reports an implementation to extend FB-QM/MM to molecular dynamics simulations. To prevent atoms from getting unreasonably close, which can lead to polarization catastrophe, empirical correcting functions are introduced to provide additive penalty energies for the involved atom pairs and to improve the descriptions of the repulsive exchange forces in FB-QM/MM calculations. Test calculations are carried out for chloride, lithium, sodium, and ammonium ions solvated in water. Comparisons with conventional QM/MM calculations suggest that the FB treatment provides reasonably good results for the charge distributions of the atoms in the QM subsystems and for the solvation shell structural properties, albeit smaller QM subsystems have been used in the FB-QM/MM dynamics simulations. PMID:25056247

  19. Effect of charge distribution on RDX adsorption in IRMOF-10

    SciTech Connect

    Xiong, Ruichang; Keffer, David J.; Fuentes-Cabrera, Miguel A; Nicholson, Don M; Michalkova, Andrea; Petrova, Tetyana; Leszczynski, Jerzy; Odbadrakh, Khorgolkhuu; Doss, Bryant; Lewis, James

    2010-01-01

    Quantum mechanical (QM) calculations, classical grand canonical Monte Carlo (GCMC) simulations, and classical molecular dynamics (MD) simulations are performed to test the effect of charge distribution on hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) adsorption and diffusion in IRMOF-10. Several different methods for mapping QM electron distributions onto atomic point charges are explored, including the electrostatic potential (ESP) method, Mulliken population analysis, L{sub 0}wdin population analysis, and natural bond orbital analysis. Classical GCMC and MD simulations of RDX in IRMOF-10 are performed using 15 combinations of charge sources of RDX and IRMOF-10. As the charge distributions vary, interaction potential energies, the adsorption loading, and the self-diffusivities are significantly different. None of the 15 combinations are able to quantitatively capture the dependence of the energy of adsorption on local configuration of RDX as observed in the QM calculations. We observe changes in the charge distributions of RDX and IRMOF-10 with the introduction of an RDX molecule into the cage. We also observe a large dispersion contribution to the interaction energy from QM calculations that is not reproduced in the classical simulations, indicating that the source of discrepancy may not lie exclusively with the assignment of charges.

  20. Carbonaceous materials for adsorptive refrigerators

    NASA Astrophysics Data System (ADS)

    Buczek, B.; Wolak, E.

    2012-06-01

    Carbon monoliths prepared from hard coal precursors were obtained. The porous structure of the monoliths was evaluated on the basis of nitrogen adsorption — desorption equilibrium data. The investigated monoliths have a well-developed microporous structure with significant specific surface area (S BET ). Equilibrium studies of methanol vapour adsorption were used to characterize the methanol adsorptive capacity that was determined using a volumetric method. The heat of wetting by methanol was determined in order to estimate the energetic effects of the adsorption process. The results of the investigations show that all monoliths exhibit high adsorption capacity and high heat of wetting with methanol.

  1. Electronic storage capacity of ceria: role of peroxide in Aux supported on CeO2(111) facet and CO adsorption.

    PubMed

    Liu, Yinli; Li, Huiying; Yu, Jun; Mao, Dongsen; Lu, Guanzhong

    2015-11-01

    Density functional theory (DFT+U) was used to study the adsorption of Aux (x = 1-4) clusters on the defective CeO2(111) facet and CO adsorption on the corresponding Aux/CeO2-x catalyst, in this work Aux clusters are adsorbed onto the CeO2-x + superoxide/peroxide surface. When Au1 is supported on the CeO2(111) facet with an O vacancy, the strong electronegative Au(δ-) formed is not favorable for CO adsorption. When peroxide is adsorbed on the CeO2(111) facet with the O vacancy, Aux was oxidized, resulting in stable Aux adsorption on the defective ceria surface with peroxide, which promotes CO adsorption on the Aux/CeO2-x catalyst. With more Au atoms in supported Aux clusters, CO adsorption on this surface becomes stronger. During both the Au being supported on CeO2-x and CO being adsorbed on Aux/CeO2-x, CeO2 acts as an electron buffer that can store/release the electrons. These results provide a scientific understanding for the development of high-performance rare earth catalytic materials.

  2. Insights into the adsorption capacity and breakthrough properties of a synthetic zeolite against a mixture of various sulfur species at low ppb levels.

    PubMed

    Vellingiri, Kowsalya; Kim, Ki-Hyun; Kwon, Eilhann E; Deep, Akash; Jo, Sang-Hee; Szulejko, Jan E

    2016-01-15

    The sorptive removal properties of a synthetic A4 zeolite were evaluated against sulfur dioxide (SO2) and four reference reduced sulfur compounds (RSC: hydrogen sulfide (H2S), methanethiol (CH3SH), dimethyl sulfide (DMS, (CH3)2S), and dimethyl disulfide (DMDS, CH3SSCH3). To this end, a sorbent bed of untreated (as-received) A4 zeolite was loaded with gaseous standards at four concentration levels (10-100 part-per-billion (ppb (v/v)) at four different volumes (0.1, 0.2, 0.5, and 1 L increments) in both increasing (IO: 0.1-1.0 L) and decreasing volume order (DO: 1.0 to 0.1 L). Morphological properties were characterized by PXRD, FTIR, and BET analysis. The removal efficiency of SO2 decreased from 100% for all concentrations at 0.1 L (initial sample volume) to ∼82% (100 ppb) or ∼96% (10 ppb) at 3.6 L. In contrast, removal efficiency of RSC was near 100% at small loading volumes but then fell sharply, irrespective of concentration (10-100 ppb) (e.g., 32% (DMS) to 52% (H2S) at 100 ppb). The adsorption capacity of zeolite, if expressed in terms of solid-gas partition coefficient (e.g., similar to the Henry's law constant (mmol kg(-1) Pa(-1))), showed moderate variabilities with the standard concentration levels and S compound types such as the minimum of 2.03 for CH3SH (at 20 ppb) to the maximum of 13.9 for SO2 (at 10 ppb). It clearly demonstrated a notable distinction in the removal efficiency of A4 zeolite among the different S species in a mixture with enhanced removal efficiency of SO2 compared to the RSCs.

  3. QM-8 field joint protection system, volume 7

    NASA Technical Reports Server (NTRS)

    Hale, Elgie

    1989-01-01

    The pre-launch functioning data of the Field Joint Protection System (JPS) used on QM-8 are presented. Also included is the post fire condition of the JPS components following the test firing of the motor. The JPS components are: field joint heaters; field joint sensors; field joint moisture seal; moisture seal kevlar retaining straps; field joint external extruded cork insulation; vent valve; power cables; and igniter heater.

  4. Enhancing Paradynamics for QM/MM Sampling of Enzymatic Reactions.

    PubMed

    Lameira, Jerônimo; Kupchencko, Ilya; Warshel, Arieh

    2016-03-10

    Despite the enormous increase in computer power, it is still extremely challenging to obtain computationally converging sampling of ab initio QM/MM (QM(ai)/MM) free energy surfaces in condensed phases. The sampling problem can be significantly reduced by the use of the reference potential paradynamics (PD) approach, but even this approach still requires major computer time in studies of enzymatic reactions. To further reduce the sampling problem we developed here a new PD version where we use an empirical valence bond reference potential that has a minimum rather than a maximum at the transition state region of the target potential (this is accomplished conveniently by shifting the EVB of the product state). Hence, we can map the TS region in a more efficient way. Here, we introduce and validate the inverted EVB PD approach. The validation involves the study of the S(N)2 step of the reaction catalyzed by haloakene dehalogenase (DhlA) and the GTP hydrolysis in the RasGAP system. In addition, we have also studied the corresponding reaction in water for each of the systems described here and the reaction involving trimethylsulfonium and dimethylamine in solution. The results are encouraging and the new strategy appears to provide a powerful way of evaluating QM(ai)/MM activation free energies. PMID:26866994

  5. The Representation of Mixtures in the ESR Model for QM

    SciTech Connect

    Garola, Claudio; Sozzo, Sandro

    2010-05-04

    The extended semantic realism(ESR)model proposes a new theoretical perspective which embodies the mathematical formalism of Hilbert space quantum mechanics (QM) into a broader noncontextual, hence local, framework, reinterpreting quantum probabilities as conditional(in a nonstandard sense). We have proven in a previous paper that each generalized observable introduced by the ESR model is represented by a family of positive operator valued measures(POVM) parametrized by the pure states of the physical system OMEGA that is considered. We show here that each mixture is represented in the ESR model by a family of density operators parametrized by the physical properties characterizing OMEGA. This representation implies predictions that may differ from those of QM and avoids some deep problems that arise in the interpretation of mixtures provided by QM. We also show that the state transformations induced by idealized nondestructive measurements can be obtained by means of a nontrivial generalization of the Lueders postulate, and discuss our results in the special case of discrete generalized observables.

  6. Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution.

    PubMed

    Udoetok, Inimfon A; Dimmick, Raquel M; Wilson, Lee D; Headley, John V

    2016-01-20

    Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si.

  7. Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution.

    PubMed

    Udoetok, Inimfon A; Dimmick, Raquel M; Wilson, Lee D; Headley, John V

    2016-01-20

    Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si

  8. Multiscale Free Energy Simulations: An Efficient Method for Connecting Classical MD Simulations to QM or QM/MM Free Energies Using Non-Boltzmann Bennett Reweighting Schemes.

    PubMed

    König, Gerhard; Hudson, Phillip S; Boresch, Stefan; Woodcock, H Lee

    2014-04-01

    THE RELIABILITY OF FREE ENERGY SIMULATIONS (FES) IS LIMITED BY TWO FACTORS: (a) the need for correct sampling and (b) the accuracy of the computational method employed. Classical methods (e.g., force fields) are typically used for FES and present a myriad of challenges, with parametrization being a principle one. On the other hand, parameter-free quantum mechanical (QM) methods tend to be too computationally expensive for adequate sampling. One widely used approach is a combination of methods, where the free energy difference between the two end states is computed by, e.g., molecular mechanics (MM), and the end states are corrected by more accurate methods, such as QM or hybrid QM/MM techniques. Here we report two new approaches that significantly improve the aforementioned scheme; with a focus on how to compute corrections between, e.g., the MM and the more accurate QM calculations. First, a molecular dynamics trajectory that properly samples relevant conformational degrees of freedom is generated. Next, potential energies of each trajectory frame are generated with a QM or QM/MM Hamiltonian. Free energy differences are then calculated based on the QM or QM/MM energies using either a non-Boltzmann Bennett approach (QM-NBB) or non-Boltzmann free energy perturbation (NB-FEP). Both approaches are applied to calculate relative and absolute solvation free energies in explicit and implicit solvent environments. Solvation free energy differences (relative and absolute) between ethane and methanol in explicit solvent are used as the initial test case for QM-NBB. Next, implicit solvent methods are employed in conjunction with both QM-NBB and NB-FEP to compute absolute solvation free energies for 21 compounds. These compounds range from small molecules such as ethane and methanol to fairly large, flexible solutes, such as triacetyl glycerol. Several technical aspects were investigated. Ultimately some best practices are suggested for improving methods that seek to connect

  9. Molecular characterization and structure analysis of RPL10/QM-like protein from the red drum Sciaenops ocellatus (Sciaenidae).

    PubMed

    Chen, X; Wu, C-W; Zhong, S-P; Zeng, F-R; Zhang, J-S; Wang, J; Niu, S-F

    2011-01-01

    The QM-like gene encodes a ribosomal protein L10. Besides housekeeping roles in protein synthesis, QM-like proteins have multiple extraribosomal functions during cell growth, cell differentiation and apoptosis. We obtained the full-length cDNA of QM-like protein (designated as SoQM) from the salt water game fish Sciaenops ocellatus, using RACE-PCR. The sequence consists of 740 bp, encoding 215-amino acid residues with 24.60 kDa. The AA sequence of the SoQM protein contains a series of functional motifs that belong to the QM family signature, which is conserved among different species. The SoQM gene contains five introns and six exons. The expression pattern of SoQM as determined by RT-PCR indicated that SoQM mRNA was expressed in all tissues tested, including brain, gill, head-kidney, intestine, stomach, heart, spleen, blood, muscle, and gonads. The phylogenetic tree constructed with MEGA 4.0 showed that SoQM clusters together with that of other fish. It was found that the sequences of the SoQM gene are highly conserved, suggesting the fundamental and critical functions of SoQM in S. ocellatus. The three-dimensional structure of the SoQM protein core domain (4~169) was predicted by the Swiss-Model program. Compared with QM proteins in other species, the main structure of SoQM protein was conserved, while the C-terminal domain was different from other QM-like proteins. Prediction of the three-dimensional structure of SoQM would provide valuable insight into the molecular basis of protein function, allowing an effective design of experiments, such as site-directed mutagenesis, studies of disease-related mutations or structure-based design of specific inhibitors. PMID:21491368

  10. Molecular characterization and immune response expression of the QM gene from the scallop Chlamys farreri.

    PubMed

    Chen, Guofu; Zhang, Chunyun; Wang, Yue; Wang, Yuanyuan; Guo, Changlu; Wang, Chongming

    2015-08-01

    The scallop Chlamys farreri is an important aquaculture species in northern China. However, the sustainable development of the scallop industry is currently threatened by several pathogens that cause mass mortality of this mollusk. Therefore, a complete understanding of the immune response mechanisms involved in host-virus interactions is necessary. This study reports a novel QM gene from C. farreri. This gene was first identified as a putative tumor suppressor gene from human and then confirmed to participate in several functions, including immune response. The QM gene from C. farreri (CfQM) was identified by suppression subtractive hybridization, and its full-length (763 bp) cDNA was obtained through rapid amplification of cDNA ends. The cDNA of CfQM contained a short 5'-UTR of 22 bp and a 3'-UTR of 84 bp. Its ORF comprised 657 nucleotides that encode 218 amino acids with a molecular weight of approximately 28.3 kDa and an isoelectric point of 10.06. The deduced amino acid sequence of CfQM contained a series of conserved functional motifs that belong to the QM family. Phylogenetic analysis revealed that CfQM was closely related to other mollusk QM proteins, and altogether they form a mollusk QM protein subfamily that displays evolutionary conservation from yeast to human. The tissue-specific expression and transcriptional regulation of CfQM were investigated by quantitative real-time PCR in response to bacterial (Vibrio anguillarum) and viral (acute viral necrobiotic virus) challenges. The transcript level of CfQM was high in all of the examined tissues in a constitutive manner. The highest and lowest expression levels of CfQM were measured in the hepatopancreas and hemocyte, respectively. Upon bacterial and viral challenges, the relative mRNA expression of CfQM sharply increased at 6 h post-infection (hpi) and then normalized at 48 hpi. These findings suggest that CfQM can respond to and protect against pathogen challenge. To the best of our knowledge, this

  11. Bond breaking in epoxy systems: A combined QM/MM approach.

    PubMed

    Barr, Stephen A; Kedziora, Gary S; Ecker, Allison M; Moller, James C; Berry, Rajiv J; Breitzman, Tim D

    2016-06-28

    A novel method to combine quantum mechanics (QM) and molecular mechanics has been developed to accurately and efficiently account for covalent bond breaking in polymer systems under high strain without the use of predetermined break locations. Use of this method will provide a better fundamental understanding of the mechano-chemical origins of fracture in thermosets. Since classical force fields cannot accurately account for bond breaking, and QM is too demanding to simulate large systems, a hybrid approach is required. In the method presented here, strain is applied to the system using a classical force field, and all bond lengths are monitored. When a bond is stretched past a threshold value, a zone surrounding the bond is used in a QM energy minimization to determine which, if any, bonds break. The QM results are then used to reconstitute the system to continue the classical simulation at progressively larger strain until another QM calculation is triggered. In this way, a QM calculation is only computed when and where needed, allowing for efficient simulations. A robust QM method for energy minimization has been determined, as well as appropriate values for the QM zone size and the threshold bond length. Compute times do not differ dramatically from classical molecular mechanical simulations. PMID:27369541

  12. Bond breaking in epoxy systems: A combined QM/MM approach

    NASA Astrophysics Data System (ADS)

    Barr, Stephen A.; Kedziora, Gary S.; Ecker, Allison M.; Moller, James C.; Berry, Rajiv J.; Breitzman, Tim D.

    2016-06-01

    A novel method to combine quantum mechanics (QM) and molecular mechanics has been developed to accurately and efficiently account for covalent bond breaking in polymer systems under high strain without the use of predetermined break locations. Use of this method will provide a better fundamental understanding of the mechano-chemical origins of fracture in thermosets. Since classical force fields cannot accurately account for bond breaking, and QM is too demanding to simulate large systems, a hybrid approach is required. In the method presented here, strain is applied to the system using a classical force field, and all bond lengths are monitored. When a bond is stretched past a threshold value, a zone surrounding the bond is used in a QM energy minimization to determine which, if any, bonds break. The QM results are then used to reconstitute the system to continue the classical simulation at progressively larger strain until another QM calculation is triggered. In this way, a QM calculation is only computed when and where needed, allowing for efficient simulations. A robust QM method for energy minimization has been determined, as well as appropriate values for the QM zone size and the threshold bond length. Compute times do not differ dramatically from classical molecular mechanical simulations.

  13. Analysis of Peer Review Comments: QM Recommendations and Feedback Intervention Theory

    ERIC Educational Resources Information Center

    Schwegler, Andria F.; Altman, Barbara W.

    2015-01-01

    Because feedback is a critical component of the continuous improvement cycle of the Quality Matters (QM) peer review process, the present research analyzed the feedback that peer reviewers provided to course developers after a voluntary, nonofficial QM peer review of online courses. Previous research reveals that the effects of feedback on…

  14. Quantum supercharger library: hyper-parallel integral derivatives algorithms for ab initio QM/MM dynamics.

    PubMed

    Renison, C Alicia; Fernandes, Kyle D; Naidoo, Kevin J

    2015-07-01

    This article describes an extension of the quantum supercharger library (QSL) to perform quantum mechanical (QM) gradient and optimization calculations as well as hybrid QM and molecular mechanical (QM/MM) molecular dynamics simulations. The integral derivatives are, after the two-electron integrals, the most computationally expensive part of the aforementioned calculations/simulations. Algorithms are presented for accelerating the one- and two-electron integral derivatives on a graphical processing unit (GPU). It is shown that a Hartree-Fock ab initio gradient calculation is up to 9.3X faster on a single GPU compared with a single central processing unit running an optimized serial version of GAMESS-UK, which uses the efficient Schlegel method for s- and l-orbitals. Benchmark QM and QM/MM molecular dynamics simulations are performed on cellobiose in vacuo and in a 39 Å water sphere (45 QM atoms and 24843 point charges, respectively) using the 6-31G basis set. The QSL can perform 9.7 ps/day of ab initio QM dynamics and 6.4 ps/day of QM/MM dynamics on a single GPU in full double precision. © 2015 Wiley Periodicals, Inc.

  15. Quantum supercharger library: hyper-parallel integral derivatives algorithms for ab initio QM/MM dynamics.

    PubMed

    Renison, C Alicia; Fernandes, Kyle D; Naidoo, Kevin J

    2015-07-01

    This article describes an extension of the quantum supercharger library (QSL) to perform quantum mechanical (QM) gradient and optimization calculations as well as hybrid QM and molecular mechanical (QM/MM) molecular dynamics simulations. The integral derivatives are, after the two-electron integrals, the most computationally expensive part of the aforementioned calculations/simulations. Algorithms are presented for accelerating the one- and two-electron integral derivatives on a graphical processing unit (GPU). It is shown that a Hartree-Fock ab initio gradient calculation is up to 9.3X faster on a single GPU compared with a single central processing unit running an optimized serial version of GAMESS-UK, which uses the efficient Schlegel method for s- and l-orbitals. Benchmark QM and QM/MM molecular dynamics simulations are performed on cellobiose in vacuo and in a 39 Å water sphere (45 QM atoms and 24843 point charges, respectively) using the 6-31G basis set. The QSL can perform 9.7 ps/day of ab initio QM dynamics and 6.4 ps/day of QM/MM dynamics on a single GPU in full double precision. © 2015 Wiley Periodicals, Inc. PMID:25975864

  16. QM/MM Molecular Dynamics Studies of Metal Binding Proteins

    PubMed Central

    Vidossich, Pietro; Magistrato, Alessandra

    2014-01-01

    Mixed quantum-classical (quantum mechanical/molecular mechanical (QM/MM)) simulations have strongly contributed to providing insights into the understanding of several structural and mechanistic aspects of biological molecules. They played a particularly important role in metal binding proteins, where the electronic effects of transition metals have to be explicitly taken into account for the correct representation of the underlying biochemical process. In this review, after a brief description of the basic concepts of the QM/MM method, we provide an overview of its capabilities using selected examples taken from our work. Specifically, we will focus on heme peroxidases, metallo-β-lactamases, α-synuclein and ligase ribozymes to show how this approach is capable of describing the catalytic and/or structural role played by transition (Fe, Zn or Cu) and main group (Mg) metals. Applications will reveal how metal ions influence the formation and reduction of high redox intermediates in catalytic cycles and enhance drug metabolism, amyloidogenic aggregate formation and nucleic acid synthesis. In turn, it will become manifest that the protein frame directs and modulates the properties and reactivity of the metal ions. PMID:25006697

  17. Robotic QM/MM-driven maturation of antibody combining sites

    PubMed Central

    Smirnov, Ivan V.; Golovin, Andrey V.; Chatziefthimiou, Spyros D.; Stepanova, Anastasiya V.; Peng, Yingjie; Zolotareva, Olga I.; Belogurov, Alexey A.; Kurkova, Inna N.; Ponomarenko, Natalie A.; Wilmanns, Matthias; Blackburn, G. Michael; Gabibov, Alexander G.; Lerner, Richard A.

    2016-01-01

    In vitro selection of antibodies from large repertoires of immunoglobulin (Ig) combining sites using combinatorial libraries is a powerful tool, with great potential for generating in vivo scavengers for toxins. However, addition of a maturation function is necessary to enable these selected antibodies to more closely mimic the full mammalian immune response. We approached this goal using quantum mechanics/molecular mechanics (QM/MM) calculations to achieve maturation in silico. We preselected A17, an Ig template, from a naïve library for its ability to disarm a toxic pesticide related to organophosphorus nerve agents. Virtual screening of 167,538 robotically generated mutants identified an optimum single point mutation, which experimentally boosted wild-type Ig scavenger performance by 170-fold. We validated the QM/MM predictions via kinetic analysis and crystal structures of mutant apo-A17 and covalently modified Ig, thereby identifying the displacement of one water molecule by an arginine as delivering this catalysis. PMID:27774510

  18. Dehydration of Methanediol in Aqueous Solution: An ONIOM(QM/MM) Study.

    PubMed

    Inaba, Satoshi; Sameera, W M C

    2016-08-25

    We used ONIOM(QM/MM) method to examine the dehydration of a methanediol in aqueous solution. A methanediol and a small number of water molecules in the proximity of the methanediol are calculated with quantum mechanics (QM), while a number of water molecules far from the methanediol are calculated with molecular mechanics (MM). A molecular dynamical simulation shows that 12 water molecules are located within the hydration shell of a methanediol. The energy barrier for the dehydration of a methanediol decreases when we increase the number of water molecules in the QM region and converges toward a finite value when 12 water molecules are included in the QM region. This indicates a significant effect of water molecules within the hydration shell on the dehydration process of a methanediol in aqueous solution. The dehydration rate calculated with the ONIOM(QM/MM) method agrees well with that obtained from a laboratory experiment. PMID:27490867

  19. Determination of binding capacity and adsorption enthalpy between Human Glutamate Receptor (GluR1) peptide fragments and kynurenic acid by surface plasmon resonance experiments.

    PubMed

    Csapó, E; Majláth, Z; Juhász, Á; Roósz, B; Hetényi, A; Tóth, G K; Tajti, J; Vécsei, L; Dékány, I

    2014-11-01

    The interaction between kynurenic acid (KYNA) and two peptide fragments (ca. 30 residues) of Human Glutamate Receptor 201-300 (GluR1) using surface plasmon resonance (SPR) spectroscopy was investigated. Because of the medical interest in the neuroscience, GluR1 is one of the important subunits of the α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptors (AMPAR). AMPARs are ionotoropic glutamate receptors, which are mediating fast synaptic transmission and are crucial for plasticity in the brain. On the other hand, KYNA has been suggested to have neuroprotective activity and it has been considered for apply in therapy in certain neurobiological disorders. In this article the adsorption of the GluR1201-230 and GluR1231-259 peptides were studied on gold biosensor chip. The peptides were chemically bonded onto the gold surface via thiol group of L-cysteine resulted in the formation of peptide monolayer on the SPR chip surface. Because the GluR1231-259 peptide does not contain L-cysteine the Val256 was replaced by Cys256. The cross sectional area and the surface orientation of the studied peptides were determined by SPR and theoretical calculations (LOMETS) as well. The binding capability of KYNA on the peptide monolayer was studied in the concentration range of 0.1-5.0 mM using 150 mM NaCl ionic strength at pH 7.4 (±0.02) in phosphate buffer solutions. In order to determine the binding enthalpy the experiments were carried out between +10°C and +40°C. The heat of adsorption was calculated by using adsorption isotherms at different surface loading of KYNA on the SPR chip.

  20. Comparison of Methods To Reweight from Classical Molecular Simulations to QM/MM Potentials.

    PubMed

    Dybeck, Eric C; König, Gerhard; Brooks, Bernard R; Shirts, Michael R

    2016-04-12

    We examine methods to reweight classical molecular mechanics solvation calculations to more expensive QM/MM energy functions. We first consider the solvation free energy difference between ethane and methanol in a QM/MM Hamiltonian from configurations generated in a cheaper MM potential. The solute molecules in the QM/MM Hamiltonian are treated with B3LYP/6-31G*, and the solvent water molecules are treated classically. The free energy difference in the QM/MM Hamiltonian is estimated using Boltzmann reweighting with both the non-Boltzmann Bennett method (NBB) and the multistate Bennett acceptance ratio (MBAR), and the variance of each method is directly compared for an identical data set. For this system, MBAR-derived methods are found to produce smaller overall uncertainties than NBB-based methods. Additionally, we show that to reduce the variance in the overall free energy difference estimate in this system for a fixed amount of QM/MM calculations, the energy re-evaluations in the Boltzmann reweighting step should be concentrated on the physical MM states with the highest overlap to the QM/MM states, rather than allocated equally over all sampled MM states. We also show that reallocating the QM/MM re-evaluations can be used to diagnose poor overlap between the sampled and target state. The solvation free energies for molecules in the SAMPL4 solvation data set are also calculated in the QM/MM Hamiltonian with NBB and MBAR, and the variances are marginally smaller for MBAR. Overall, NBB and MBAR produce similar variances for systems with poor sampling efficiency, and MBAR provides smaller variances than NBB in systems with high sampling efficiency. Both NBB and MBAR converge to identical solvation free energy estimates in the QM/MM Hamiltonian, and the RMSD to experimental values for molecules in the SAMPL4 solvation data set decreases by approximately 28% when switching from the MM Hamiltonian to the QM/MM Hamiltonian. PMID:26928941

  1. Molecular analysis of the QM gene from Penaeus monodon and its expression on the different ovarian stages of development.

    PubMed

    Zhou, FaLin; Jiang, ShiGui; Huang, JianHua; Qiu, LiHua; Zhang, DianChang; Su, TiannFeng

    2011-03-01

    In present study, a QM gene was obtained from the ovary and neurosecretory organ in eyestalk cDNA library of black tiger prawn (Penaeus monodon). The full-length black tiger prawn QM (PmQM) cDNA contained a 5'-UTR of 41 bp, an ORF of 663 bp encoding a polypeptide of 220 amino acids with molecular weight 25.5 kDa, and a 3'-UTR of 54 bp. Homology analysis of the deduced amino acid sequence of the PmQM with other known QM sequences by MatGAT software revealed that the PmQM was high homology with other invertebrates. A conserved signature sequence of the QM family was found in the PmQM deduced amino acid sequence. Analysis of the tissue expression pattern of the PmQM gene showed that the PmQM mRNA was expressed in all tissues tested, with highest levels in ovary. Furthermore, the PmQM expression was found to be different in three important ovarian stages of development. The results indicated PmQM might play an important role in ovarian development.

  2. Preparation of char from lotus seed biomass and the exploration of its dye removal capacity through batch and column adsorption studies.

    PubMed

    Nethaji, S; Sivasamy, A; Kumar, R Vimal; Mandal, A B

    2013-06-01

    Char was obtained from lotus seed biomass by a simple single-step acid treatment process. It was used as an adsorbent for the removal of malachite green dye (MG) from simulated dye bath effluent. The adsorbent was characterized for its surface morphology, surface functionalities, and zero point charge. Batch studies were carried out by varying the parameters such as initial aqueous pH, adsorbent dosage, adsorbent particle size, and initial adsorbate concentration. Langmuir and Freundlich isotherms were used to test the isotherm data and the Freundlich isotherm best fitted the data. Thermodynamic studies were carried out and the thermodynamic parameters such as ∆G, ∆H, and ∆S were evaluated. Adsorption kinetics was carried out and the data were tested with pseudofirst-order model, pseudosecond-order model, and intraparticle diffusion model. Adsorption of MG was not solely by intraparticle diffusion but film diffusion also played a major role. Continuous column experiments were also conducted using microcolumn and the spent adsorbent was regenerated using ethanol and was repeatedly used for three cycles in the column to determine the reusability of the regenerated adsorbent. The column data were modeled with the modeling equations such as Adam-Bohart model, Bed Depth Service Time (BDST) model, and Yoon-Nelson model for all the three cycles.

  3. N-body:Many-body QM:QM vibrational frequencies: application to small hydrogen-bonded clusters.

    PubMed

    Howard, J Coleman; Tschumper, Gregory S

    2013-11-14

    We present an efficient method for reproducing CCSD(T) (i.e., the coupled-cluster method with single, double and perturbative connected triple excitations) optimized geometries and harmonic vibrational frequencies for molecular clusters with the N-body:Many-body QM:QM technique. In this work, all 1-body through N-body interactions are obtained from CCSD(T) computations, and the higher-order interactions are captured at the MP2 level. The linear expressions from the many-body expansion facilitate a straightforward evaluation of geometrical derivative properties (e.g., gradients and Hessians). For (H2O)n clusters (n = 3-7), optimized structures obtained with the 2-body:Many-body CCSD(T):MP2 method are virtually identical to CCSD(T) optimized geometries. Harmonic vibrational frequencies calculated with this 2-body:Many-body approach differ from CCSD(T) frequencies by at most a few cm(-1). These deviations can be systematically reduced by including more terms from the many-body expansion at the CCSD(T) level. Maximum deviations between CCSD(T) and 3-body:Many-body CCSD(T):MP2 frequencies are typically only a few tenths of a cm(-1) for the H2O clusters examined in this work. These results are obtained at a fraction of the wall time of the supermolecular CCSD(T) computation, and the approach is well-suited for parallelization on relatively modest computational hardware. PMID:24320260

  4. QM/MM Minimum Free Energy Path: Methodology and Application to Triosephosphate Isomerase.

    PubMed

    Hu, Hao; Lu, Zhenyu; Yang, Weitao

    2007-03-01

    Structural and energetic changes are two important characteristic properties of a chemical reaction process. In the condensed phase, studying these two properties is very challenging because of the great computational cost associated with the quantum mechanical calculations and phase space sampling. Although the combined quantum mechanics/molecular mechanics (QM/MM) approach significantly reduces the amount of the quantum mechanical calculations and facilitates the simulation of solution phase and enzyme catalyzed reactions, the required quantum mechanical calculations remain quite expensive and extensive sampling can be achieved routinely only with semiempirical quantum mechanical methods. QM/MM simulations with ab initio QM methods, therefore, are often restricted to narrow regions of the potential energy surface such as the reactant, product and transition state, or the minimum energy path. Such ab initio QM/MM calculations have previously been performed with the QM/MM-Free Energy (QM/MM-FE) method of Zhang et al.1 to generate the free energy profile along the reaction coordinate using free energy perturbation calculations at fixed structures of the QM subsystems. Results obtained with the QM/MM-FE method depend on the determination of the minimum energy reaction path, which is based on local conformations of the protein/solvent environment and can be difficult to obtain in practice. To overcome the difficulties associated with the QM/MM-FE method and to further enhance the sampling of the MM environment conformations, we develop here a new method to determine the QM/MM minimum free energy path (QM/MM-MFEP) for chemical reaction processes in solution and in enzymes. Within the QM/MM framework, we express the free energy of the system as a function of the QM conformation, thus leading to a simplified potential of mean force (PMF) description for the thermodynamics of the system. The free energy difference between two QM conformations is evaluated by the QM

  5. fireball/amber: An Efficient Local-Orbital DFT QM/MM Method for Biomolecular Systems.

    PubMed

    Mendieta-Moreno, Jesús I; Walker, Ross C; Lewis, James P; Gómez-Puertas, Paulino; Mendieta, Jesús; Ortega, José

    2014-05-13

    In recent years, quantum mechanics/molecular mechanics (QM/MM) methods have become an important computational tool for the study of chemical reactions and other processes in biomolecular systems. In the QM/MM technique, the active region is described by means of QM calculations, while the remainder of the system is described using a MM approach. Because of the complexity of biomolecules and the desire to achieve converged sampling, it is important that the QM method presents a good balance between accuracy and computational efficiency. Here, we report on the implementation of a QM/MM technique that combines a DFT approach specially designed for the study of complex systems using first-principles molecular dynamics simulations (fireball) with the amber force fields and simulation programs. We also present examples of the application of this QM/MM approach to three representative biomolecular systems: the analysis of the effect of electrostatic embedding in the behavior of a salt bridge between an aspartic acid and a lysine residue, a study of the intermediate states for the triosephosphate isomerase catalyzed conversion of dihydroxyacetone phosphate into glyceraldehyde 3-phosphate, and the detailed description, using DFT QM/MM molecular dynamics, of the cleavage of a phosphodiester bond in RNA catalyzed by the enzyme RNase A.

  6. APT a next generation QM-based reactive force field model

    NASA Astrophysics Data System (ADS)

    Rappé, A. K.; Bormann-Rochotte, L. M.; Wiser, D. C.; Hart, J. R.; Pietsch, M. A.; Casewit, C. J.; Skiff, W. M.

    Modelling reactivity at the nanoscale is a major computational challenge. Both reactive force field and combined QM-MM methodologies have been and are being developed to study reactivity at this boundary between molecules and the solid state. There have been more than 1500 publications since the mid-1990s, on combined QM-MM methodologies. Limitations in current models include the distortional characteristics of force field potential terms, the smooth transit from one potential surface to another, rather than surface hopping, and the blending of electrostatics between QM and MM portions of a QM-MM model. Functional forms, potential surface coupling terms, and parameterization strategies for the Approximate Pair Theory (APT), a next generation reactive force field model, are described. The APT model has been developed to correct a number of limitations in current reactive force field models as well as providing a foundation for a next generation QM-MM model. Chemical bonding concepts are used to develop fully dissociative bond stretch, bend, torsion, and inversion valence terms. Quantum mechanics also provides functional forms for potential surface coupling terms that permit a general description of reactivity from hydrogen bonding, through non-classical carbocations and cracking, to olefin polymerization, oxidation, and metathesis. Van der Waals, electrostatic, and metallic bonding models also derive from quantum mechanical resonance. Finally, Pauli Principle-based orthogonality provides a way to electrostatically couple the QM and MM portions of a QM-MM model that will support arbitrarily large basis sets.

  7. An extensible interface for QM/MM molecular dynamics simulations with AMBER.

    PubMed

    Götz, Andreas W; Clark, Matthew A; Walker, Ross C

    2014-01-15

    We present an extensible interface between the AMBER molecular dynamics (MD) software package and electronic structure software packages for quantum mechanical (QM) and mixed QM and classical molecular mechanical (MM) MD simulations within both mechanical and electronic embedding schemes. With this interface, ab initio wave function theory and density functional theory methods, as available in the supported electronic structure software packages, become available for QM/MM MD simulations with AMBER. The interface has been written in a modular fashion that allows straight forward extensions to support additional QM software packages and can easily be ported to other MD software. Data exchange between the MD and QM software is implemented by means of files and system calls or the message passing interface standard. Based on extensive tests, default settings for the supported QM packages are provided such that energy is conserved for typical QM/MM MD simulations in the microcanonical ensemble. Results for the free energy of binding of calcium ions to aspartate in aqueous solution comparing semiempirical and density functional Hamiltonians are shown to demonstrate features of this interface.

  8. An extensible interface for QM/MM molecular dynamics simulations with AMBER

    PubMed Central

    Götz, Andreas W.; Clark, Matthew A.; Walker, Ross C.

    2014-01-01

    We present an extensible interface between the AMBER molecular dynamics (MD) software package and electronic structure software packages for quantum mechanical (QM) and mixed QM and classical molecular mechanical (MM) MD simulations within both mechanical and electronic embedding schemes. With this interface, ab initio wave function theory and density functional theory methods, as available in the supported electronic structure software packages, become available for QM/MM MD simulations with AMBER. The interface has been written in a modular fashion that allows straight forward extensions to support additional QM software packages and can easily be ported to other MD software. Data exchange between the MD and QM software is implemented by means of files and system calls or the message passing interface standard. Based on extensive tests, default settings for the supported QM packages are provided such that energy is conserved for typical QM/MM MD simulations in the microcanonical ensemble. Results for the free energy of binding of calcium ions to aspartate in aqueous solution comparing semiempirical and density functional Hamiltonians are shown to demonstrate features of this interface. PMID:24122798

  9. Qualification Motor no. 8 (QM-8), volume 1

    NASA Technical Reports Server (NTRS)

    Garecht, D. M.

    1989-01-01

    All inspection and instrumentation data indicate that the QM-8 static test firing conducted 20 January 1989 was successful. Ambient temperature at T-0 was 28 F. With two flights successfully accomplished, this final test in the redesigned solid rocket motor (RSRM) program certified that the design meets motor performance requirements under extreme cold conditions. This test was a prerequisite to the third flight. The entire test article was cold conditioned at 20 to 25 F for approximately 31 days to assure a maximum propellant mean bulk temperature (PMBT) of 40 F, making it the lowest PMBT in the history of the program. This extreme condition also presented the opportunity to certify critical components at low temperatures. Certification of field joint and igniter heaters, adhesive bondline integrity, flex bearing performance, flight instrumentation performance, RSRM seal performance, and LSC and nozzle plug performance was accomplished. Prior to motor ignition, the field joints were maintained between 75 to 130 F, the igniter-to-case joint was maintained between 75 to 123 F, and the case-to-nozzle joint was maintained between 75 to 120 F. QM-8 was tested with induced side loads to simulate the strut loads experienced during ignition and maximum aerodynamic loading conditions. The ability of the safe and arm device to change position from safe-to-arm and arm-to-safe was certified. Ballistics performance was certified at the lower limits. Values were within specification requirements. Nozzle performance was nominal with typical erosion. The use of Fiberite carbon-cloth phenolic was certified. The water deluge system, CO2 quench, and other test equipment performed as planned during all required test operations.

  10. Tumor suppressor QM-like gene from disk abalone (Haliotis discus discus): molecular characterization and transcriptional analysis upon immune challenge.

    PubMed

    Oh, Chulhong; De Zoysa, Mahanama; Nikapitiya, Chamilani; Whang, Ilson; Kim, Yu Cheol; Kang, Do-Hyung; Heo, Soo-jin; Choi, Young-Ung; Choi, Cheol Young; Lee, Jae-Seong; Lee, Jehee

    2010-09-01

    We describe molecular characterization and transcriptional analysis of the gene encoding tumor suppressor QM-like protein, AbQM, in the disk abalone Haliotis discus discus. The full-length cDNA (765-bp) of AbQM was found to consist of a 654-bp ORF coding for a 218 amino acid protein of a 25 kDa molecular mass with a 10.2 isoelectric point. Analysis of AbQM sequence revealed the presence of characteristic motifs, including the ribosomal protein L10 signature, SH3-binding motif and two antibiotic binding sites. Phylogenetic analysis confirmed that AbQM is closely related to other mollusk QM proteins, and altogether they form a mollusk QM protein sub-family which displays evolutionary conservation from yeast to human. Tissue-specific expression and transcriptional regulation of AbQM was analyzed by quantitative real-time PCR in response to bacterial (Vibrio alginolyticus and Vibrio parahemolyticus, Listeria monocytogenes) and viral (viral hemorrhagic septicemia virus, VHSV) challenge. AbQM transcripts were found to be expressed ubiquitously in all examined tissues in a constitutive manner, as similar expression levels were detected in hemocytes, mantle, digestive tract and muscle. Upon bacterial and VHSV challenge, AbQM showed significant up-regulation in gills, but not in hemocytes. Taken together, these findings suggest that AbQM in abalone-like mollusks can respond to and facilitate a defensive effect against pathogenic infection.

  11. Development and application of QM/MM methods to study the solvation effects and surfaces

    SciTech Connect

    Dibya, Pooja Arora

    2010-01-01

    Quantum mechanical (QM) calculations have the advantage of attaining high-level accuracy, however QM calculations become computationally inefficient as the size of the system grows. Solving complex molecular problems on large systems and ensembles by using quantum mechanics still poses a challenge in terms of the computational cost. Methods that are based on classical mechanics are an inexpensive alternative, but they lack accuracy. A good trade off between accuracy and efficiency is achieved by combining QM methods with molecular mechanics (MM) methods to use the robustness of the QM methods in terms of accuracy and the MM methods to minimize the computational cost. Two types of QM combined with MM (QM/MM) methods are the main focus of the present dissertation: the application and development of QM/MM methods for solvation studies and reactions on the Si(100) surface. The solvation studies were performed using a discreet solvation model that is largely based on first principles called the effective fragment potential method (EFP). The main idea of combining the EFP method with quantum mechanics is to accurately treat the solute-solvent and solvent-solvent interactions, such as electrostatic, polarization, dispersion and charge transfer, that are important in correctly calculating solvent effects on systems of interest. A second QM/MM method called SIMOMM (surface integrated molecular orbital molecular mechanics) is a hybrid QM/MM embedded cluster model that mimics the real surface.3 This method was employed to calculate the potential energy surfaces for reactions of atomic O on the Si(100) surface. The hybrid QM/MM method is a computationally inexpensive approach for studying reactions on larger surfaces in a reasonably accurate and efficient manner. This thesis is comprised of four chapters: Chapter 1 describes the general overview and motivation of the dissertation and gives a broad background of the computational methods that have been employed in this work

  12. Continuum-atomistic simulation of picosecond laser heating of copper with electron heat capacity from ab initio calculation

    NASA Astrophysics Data System (ADS)

    Ji, Pengfei; Zhang, Yuwen

    2016-03-01

    On the basis of ab initio quantum mechanics (QM) calculation, the obtained electron heat capacity is implemented into energy equation of electron subsystem in two temperature model (TTM). Upon laser irradiation on the copper film, energy transfer from the electron subsystem to the lattice subsystem is modeled by including the electron-phonon coupling factor in molecular dynamics (MD) and TTM coupled simulation. The results show temperature and thermal melting difference between the QM-MD-TTM integrated simulation and pure MD-TTM coupled simulation. The successful construction of the QM-MD-TTM integrated simulation provides a general way that is accessible to other metals in laser heating.

  13. Final report on APMP.QM-S5: Essential and toxic elements in seafood

    NASA Astrophysics Data System (ADS)

    Valiente, Liliana; Bennett, John W.; Caciano de Sena, Rodrigo; Kotzeva, Boriana; Massiff, Gabriela; Chao, Jingbo; Wang, Jun; Nasr, Randa; Labarraque, Guillaume; Kakoulidis, Elias; Lampi, Eugenia; Wai-mei Sin, Della; Mok, Chuen-shing; Wong, Siu-kay; Yip, Yiu-chung; Gopala Aggarwal, Shankar; Gupta, Prabhat K.; Zhu, Yanbei; Miyashita, Shin-ichi; Yim, Yong-Hyeon; Zakaria, Osman; Manzano, Judith Velina Lara; Shin, Richard; Horvat, Milena; Yafa, Charun

    2013-01-01

    The supplementary comparison APMP.QM-S5 was undertaken to demonstrate the capability of participating national metrology institutes (NMIs) and designated institutes (DIs) in measuring the contents of the incurred essential elements (iron and zinc) and toxic elements (total arsenic and cadmium) at µg/g levels in a test sample of dried shrimp by various analytical techniques. At the APMP TCQM Meeting held in Pattaya, Thailand in November 2010, Government Laboratory of the Government of the Hong Kong Special Administrative Region (GLHK) proposed this APMP supplementary comparison. The proposal was further discussed and agreed upon at the CCQM Inorganic Analysis Working Group Meeting held in Paris in April 2011. GLHK was the coordinating laboratory for the supplementary comparison. For enhancing the collaboration amongst specialized regional bodies in Asia-Pacific and to help build the laboratory capacity of NMIs/DIs from developing economies, the reference values of the supplementary comparison are used for evaluation of performance of participants of an APMP proficiency testing programme (APMP PT 11-01), an Asia-Pacific Laboratory Accreditation Cooperation proficiency testing programme (APLAC T082) and an Asia-Pacific Economic Co-operation proficiency testing programme (APEC PT), which were concurrently run using the same testing material as in APMP.QM-S5. The supplementary comparison serves to facilitate claims by participants on the Calibration and Measurement Capabilities (CMCs) as listed in Appendix C of the Key Comparison Database (KCDB) under the Mutual Recognition Arrangement of the International Committee for Weights and Measures (CIPM MRA). A total of 18 institutes registered for the supplementary comparison and all of them submitted their results. Most of the participants used microwave acid digestion methods for sample dissolution. For the instrumental determination, a variety of techniques like ICP-MS, ICP-OES, INAA and AAS were employed by the

  14. Influence of milling on the adsorption ability of eggshell waste.

    PubMed

    Baláž, Matej; Ficeriová, Jana; Briančin, Jaroslav

    2016-03-01

    Eggshell waste was successfully used for the removal of heavy metal ions from model solutions. The effect of ball milling on the structure and adsorption ability of eggshell (ES) and its membrane (ESM) was investigated, with the conclusion that milling is benefitial only for the ES. The adsorption experiments showed that the ESM is a selective adsorbent, as the adsorption ability toward different ions decreased in the following order: Ag(I) > Cd(II) > Zn(II). The obtained Qm values for Ag(I) adsorption on the ESM and ES were 52.9 and 55.7 mg g(-1), respectively. The potential industrial application of ES was also demonstrated by successful removal of Ag(I) from the technological waste. PMID:26741552

  15. Efficient approach to obtain free energy gradient using QM/MM MD simulation

    SciTech Connect

    Asada, Toshio; Koseki, Shiro; Ando, Kanta

    2015-12-31

    The efficient computational approach denoted as charge and atom dipole response kernel (CDRK) model to consider polarization effects of the quantum mechanical (QM) region is described using the charge response and the atom dipole response kernels for free energy gradient (FEG) calculations in the quantum mechanical/molecular mechanical (QM/MM) method. CDRK model can reasonably reproduce energies and also energy gradients of QM and MM atoms obtained by expensive QM/MM calculations in a drastically reduced computational time. This model is applied on the acylation reaction in hydrated trypsin-BPTI complex to optimize the reaction path on the free energy surface by means of FEG and the nudged elastic band (NEB) method.

  16. LICHEM: A QM/MM program for simulations with multipolar and polarizable force fields.

    PubMed

    Kratz, Eric G; Walker, Alice R; Lagardère, Louis; Lipparini, Filippo; Piquemal, Jean-Philip; Andrés Cisneros, G

    2016-04-30

    We introduce an initial implementation of the LICHEM software package. LICHEM can interface with Gaussian, PSI4, NWChem, TINKER, and TINKER-HP to enable QM/MM calculations using multipolar/polarizable force fields. LICHEM extracts forces and energies from unmodified QM and MM software packages to perform geometry optimizations, single-point energy calculations, or Monte Carlo simulations. When the QM and MM regions are connected by covalent bonds, the pseudo-bond approach is employed to smoothly transition between the QM region and the polarizable force field. A series of water clusters and small peptides have been employed to test our initial implementation. The results obtained from these test systems show the capabilities of the new software and highlight the importance of including explicit polarization. © 2016 Wiley Periodicals, Inc. PMID:26781073

  17. Adaptive Partitioning QM/MM Dynamics Simulations for Substrate Uptake, Product Release, and Solvent Exchange.

    PubMed

    Duster, A; Garza, C; Lin, H

    2016-01-01

    Combined quantum mechanics/molecular mechanics (QM/MM) plays an important role in multiscale simulations of biological systems including enzymes. The adaptive-partitioning (AP) schemes surpass the conventional QM/MM methods in that they allow the on-the-fly, smooth exchange of particles between QM and MM subsystems in molecular dynamics simulations, leading to a seamless and dynamic integration of the QM and MM realms. Originally developed for simulating ion solvation in bulk solutions, the AP schemes have recently been extended to the treatment of proteins, fostering applications in the simulations of enzymes. The present contribution provides a detailed account of the AP schemes. We delineate the background of the algorithms and their parallel implementation, as well as offer practical advice and examples for their applications in the simulations of biological systems. PMID:27498644

  18. A new smoothing function to introduce long-range electrostatic effects in QM/MM calculations

    SciTech Connect

    Fang, Dong; Duke, Robert E.; Andrés Cisneros, G.

    2015-07-28

    A new method to account for long range electrostatic contributions is proposed and implemented for quantum mechanics/molecular mechanics long range electrostatic correction (QM/MM-LREC) calculations. This method involves the use of the minimum image convention under periodic boundary conditions and a new smoothing function for energies and forces at the cutoff boundary for the Coulomb interactions. Compared to conventional QM/MM calculations without long-range electrostatic corrections, the new method effectively includes effects on the MM environment in the primary image from its replicas in the neighborhood. QM/MM-LREC offers three useful features including the avoidance of calculations in reciprocal space (k-space), with the concomitant avoidance of having to reproduce (analytically or approximately) the QM charge density in k-space, and the straightforward availability of analytical Hessians. The new method is tested and compared with results from smooth particle mesh Ewald (PME) for three systems including a box of neat water, a double proton transfer reaction, and the geometry optimization of the critical point structures for the rate limiting step of the DNA dealkylase AlkB. As with other smoothing or shifting functions, relatively large cutoffs are necessary to achieve comparable accuracy with PME. For the double-proton transfer reaction, the use of a 22 Å cutoff shows a close reaction energy profile and geometries of stationary structures with QM/MM-LREC compared to conventional QM/MM with no truncation. Geometry optimization of stationary structures for the hydrogen abstraction step by AlkB shows some differences between QM/MM-LREC and the conventional QM/MM. These differences underscore the necessity of the inclusion of the long-range electrostatic contribution.

  19. A new smoothing function to introduce long-range electrostatic effects in QM/MM calculations

    PubMed Central

    Fang, Dong; Duke, Robert E.; Cisneros, G. Andrés

    2015-01-01

    A new method to account for long range electrostatic contributions is proposed and implemented for quantum mechanics/molecular mechanics long range electrostatic correction (QM/MM-LREC) calculations. This method involves the use of the minimum image convention under periodic boundary conditions and a new smoothing function for energies and forces at the cutoff boundary for the Coulomb interactions. Compared to conventional QM/MM calculations without long-range electrostatic corrections, the new method effectively includes effects on the MM environment in the primary image from its replicas in the neighborhood. QM/MM-LREC offers three useful features including the avoidance of calculations in reciprocal space (k-space), with the concomitant avoidance of having to reproduce (analytically or approximately) the QM charge density in k-space, and the straightforward availability of analytical Hessians. The new method is tested and compared with results from smooth particle mesh Ewald (PME) for three systems including a box of neat water, a double proton transfer reaction, and the geometry optimization of the critical point structures for the rate limiting step of the DNA dealkylase AlkB. As with other smoothing or shifting functions, relatively large cutoffs are necessary to achieve comparable accuracy with PME. For the double-proton transfer reaction, the use of a 22 Å cutoff shows a close reaction energy profile and geometries of stationary structures with QM/MM-LREC compared to conventional QM/MM with no truncation. Geometry optimization of stationary structures for the hydrogen abstraction step by AlkB shows some differences between QM/MM-LREC and the conventional QM/MM. These differences underscore the necessity of the inclusion of the long-range electrostatic contribution. PMID:26233103

  20. A new smoothing function to introduce long-range electrostatic effects in QM/MM calculations

    NASA Astrophysics Data System (ADS)

    Fang, Dong; Duke, Robert E.; Cisneros, G. Andrés

    2015-07-01

    A new method to account for long range electrostatic contributions is proposed and implemented for quantum mechanics/molecular mechanics long range electrostatic correction (QM/MM-LREC) calculations. This method involves the use of the minimum image convention under periodic boundary conditions and a new smoothing function for energies and forces at the cutoff boundary for the Coulomb interactions. Compared to conventional QM/MM calculations without long-range electrostatic corrections, the new method effectively includes effects on the MM environment in the primary image from its replicas in the neighborhood. QM/MM-LREC offers three useful features including the avoidance of calculations in reciprocal space (k-space), with the concomitant avoidance of having to reproduce (analytically or approximately) the QM charge density in k-space, and the straightforward availability of analytical Hessians. The new method is tested and compared with results from smooth particle mesh Ewald (PME) for three systems including a box of neat water, a double proton transfer reaction, and the geometry optimization of the critical point structures for the rate limiting step of the DNA dealkylase AlkB. As with other smoothing or shifting functions, relatively large cutoffs are necessary to achieve comparable accuracy with PME. For the double-proton transfer reaction, the use of a 22 Å cutoff shows a close reaction energy profile and geometries of stationary structures with QM/MM-LREC compared to conventional QM/MM with no truncation. Geometry optimization of stationary structures for the hydrogen abstraction step by AlkB shows some differences between QM/MM-LREC and the conventional QM/MM. These differences underscore the necessity of the inclusion of the long-range electrostatic contribution.

  1. Construction of exchange repulsion in terms of the wave functions at QM/MM boundary region

    SciTech Connect

    Takahashi, Hideaki Umino, Satoru; Morita, Akihiro

    2015-08-28

    We developed a simple method to calculate exchange repulsion between a quantum mechanical (QM) solute and a molecular mechanical (MM) molecule in the QM/MM approach. In our method, the size parameter in the Buckingham type potential for the QM solute is directly determined in terms of the one-electron wave functions of the solute. The point of the method lies in the introduction of the exchange core function (ECF) defined as a Slater function which mimics the behavior of the exterior electron density at the QM/MM boundary region. In the present paper, the ECF was constructed in terms of the Becke-Roussel (BR) exchange hole function. It was demonstrated that the ECF yielded by the BR procedure can faithfully reproduce the radial behavior of the electron density of a QM solute. The size parameter of the solute as well as the exchange repulsion are, then, obtained using the overlap model without any fitting procedure. To examine the efficiency of the method, it was applied to calculation of the exchange repulsions for minimal QM/MM systems, hydrogen-bonded water dimer, and H{sub 3}O{sup +}–H{sub 2}O. We found that our approach is able to reproduce the potential energy curves for these systems showing reasonable agreements with those given by accurate full quantum chemical calculations.

  2. Toward Hamiltonian Adaptive QM/MM: Accurate Solvent Structures Using Many-Body Potentials.

    PubMed

    Boereboom, Jelle M; Potestio, Raffaello; Donadio, Davide; Bulo, Rosa E

    2016-08-01

    Adaptive quantum mechanical (QM)/molecular mechanical (MM) methods enable efficient molecular simulations of chemistry in solution. Reactive subregions are modeled with an accurate QM potential energy expression while the rest of the system is described in a more approximate manner (MM). As solvent molecules diffuse in and out of the reactive region, they are gradually included into (and excluded from) the QM expression. It would be desirable to model such a system with a single adaptive Hamiltonian, but thus far this has resulted in distorted structures at the boundary between the two regions. Solving this long outstanding problem will allow microcanonical adaptive QM/MM simulations that can be used to obtain vibrational spectra and dynamical properties. The difficulty lies in the complex QM potential energy expression, with a many-body expansion that contains higher order terms. Here, we outline a Hamiltonian adaptive multiscale scheme within the framework of many-body potentials. The adaptive expressions are entirely general, and complementary to all standard (nonadaptive) QM/MM embedding schemes available. We demonstrate the merit of our approach on a molecular system defined by two different MM potentials (MM/MM'). For the long-range interactions a numerical scheme is used (particle mesh Ewald), which yields energy expressions that are many-body in nature. Our Hamiltonian approach is the first to provide both energy conservation and the correct solvent structure everywhere in this system. PMID:27332140

  3. The study of non-linear kinetics and adsorption isotherm models for Acid Red 18 from aqueous solutions by magnetite nanoparticles and magnetite nanoparticles modified by sodium alginate.

    PubMed

    Berizi, Zohre; Hashemi, Seyed Yaser; Hadi, Mahdi; Azari, Ali; Mahvi, Amir Hosein

    2016-01-01

    Azo dyes are widely used in various industries. These substances produce toxic byproducts in aquatic environments in addition to their mutagenic and carcinogenic potential effects. In this study, the effect of magnetite nanoparticles and magnetite nanoparticles modified by sodium alginate in batch systems and nonlinear kinetic and adsorption isotherm models were investigated. Magnetite nanoparticles were synthesized by chemical co-precipitation method and then modified and used as adsorbent to adsorb Acid Red 18. After determining the optimum pH and adsorbent dose, non-equilibrium models for kinetic adsorption were tested with concentrations (25-100 mg/L) and at eight different periods of time (1-15 min) and the pseudo-first-order and pseudo-second-order non-linear models were used to describe the results. For adsorption isotherm, a contact time of 120 min was studied in different concentrations (25-100 mg/L) and the residual concentration of Acid Red 18 was obtained. The results are described by non-linear Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The optimum amounts of pH for magnetite nanoparticles and for modified ones were 3 and 5, respectively, the efficiencies were 0.75 and 0.2 g/L, respectively. According to the results sodium alginate has a high performance in adsorption of Acid Red 18. Adjusted correlation coefficients and chi-square test showed that Freundlich isotherm and then Langmuir isotherm can well describe the experimental results. In Freundlich, the value of (Kf) was 3.231 (L/g) for magnetite nanoparticles and 21.615 (L/g) for modified adsorbent. In Langmuir, the value of (qm) was 16.259 (mg/g) for magnetite nanoparticles and 73.464 (mg/g) for modified adsorbent. Comparing the Langmuir maximum calculated adsorption capacity indicated that modified adsorbent can adsorb the pollutants 6.5 times more than the other one.

  4. The study of non-linear kinetics and adsorption isotherm models for Acid Red 18 from aqueous solutions by magnetite nanoparticles and magnetite nanoparticles modified by sodium alginate.

    PubMed

    Berizi, Zohre; Hashemi, Seyed Yaser; Hadi, Mahdi; Azari, Ali; Mahvi, Amir Hosein

    2016-01-01

    Azo dyes are widely used in various industries. These substances produce toxic byproducts in aquatic environments in addition to their mutagenic and carcinogenic potential effects. In this study, the effect of magnetite nanoparticles and magnetite nanoparticles modified by sodium alginate in batch systems and nonlinear kinetic and adsorption isotherm models were investigated. Magnetite nanoparticles were synthesized by chemical co-precipitation method and then modified and used as adsorbent to adsorb Acid Red 18. After determining the optimum pH and adsorbent dose, non-equilibrium models for kinetic adsorption were tested with concentrations (25-100 mg/L) and at eight different periods of time (1-15 min) and the pseudo-first-order and pseudo-second-order non-linear models were used to describe the results. For adsorption isotherm, a contact time of 120 min was studied in different concentrations (25-100 mg/L) and the residual concentration of Acid Red 18 was obtained. The results are described by non-linear Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The optimum amounts of pH for magnetite nanoparticles and for modified ones were 3 and 5, respectively, the efficiencies were 0.75 and 0.2 g/L, respectively. According to the results sodium alginate has a high performance in adsorption of Acid Red 18. Adjusted correlation coefficients and chi-square test showed that Freundlich isotherm and then Langmuir isotherm can well describe the experimental results. In Freundlich, the value of (Kf) was 3.231 (L/g) for magnetite nanoparticles and 21.615 (L/g) for modified adsorbent. In Langmuir, the value of (qm) was 16.259 (mg/g) for magnetite nanoparticles and 73.464 (mg/g) for modified adsorbent. Comparing the Langmuir maximum calculated adsorption capacity indicated that modified adsorbent can adsorb the pollutants 6.5 times more than the other one. PMID:27642843

  5. PREFACE: EmQM13: Emergent Quantum Mechanics 2013

    NASA Astrophysics Data System (ADS)

    2014-04-01

    These proceedings comprise the invited lectures of the second international symposium on Emergent Quantum Mechanics (EmQM13), which was held at the premises of the Austrian Academy of Sciences in Vienna, Austria, 3-6 October 2013. The symposium was held at the ''Theatersaal'' of the Academy of Sciences, and was devoted to the open exploration of emergent quantum mechanics, a possible ''deeper level theory'' that interconnects three fields of knowledge: emergence, the quantum, and information. Could there appear a revised image of physical reality from recognizing new links between emergence, the quantum, and information? Could a novel synthesis pave the way towards a 21st century, ''superclassical'' physics? The symposium provided a forum for discussing (i) important obstacles which need to be overcome as well as (ii) promising developments and research opportunities on the way towards emergent quantum mechanics. Contributions were invited that presented current advances in both standard as well as unconventional approaches to quantum mechanics. The EmQM13 symposium was co-organized by Gerhard Grössing (Austrian Institute for Nonlinear Studies (AINS), Vienna), and by Jan Walleczek (Fetzer Franklin Fund, USA, and Phenoscience Laboratories, Berlin). After a very successful first conference on the same topic in 2011, the new partnership between AINS and the Fetzer Franklin Fund in producing the EmQM13 symposium was able to further expand interest in the promise of emergent quantum mechanics. The symposium consisted of two parts, an opening evening addressing the general public, and the scientific program of the conference proper. The opening evening took place at the Great Ceremonial Hall (Grosser Festsaal) of the Austrian Academy of Sciences, and it presented talks and a panel discussion on ''The Future of Quantum Mechanics'' with three distinguished speakers: Stephen Adler (Princeton), Gerard 't Hooft (Utrecht) and Masanao Ozawa (Nagoya). The articles contained in

  6. Size-fractionation and characterization of landfill leachate and the improvement of Cu2+ adsorption capacity in soil and aged refuse.

    PubMed

    Lou, Ziyang; Chai, Xiaoli; Niu, Dongjie; Ou, Yuanyang; Zhao, Youcai

    2009-01-01

    Leachate was collected from an anaerobic lagoon at Shanghai Laogang refuse landfill, the largest landfill in China, and the sample was separated into six fractions using micro-filtration membranes, followed by ultra-filtration membranes. Several parameters of the samples were measured, including chemical oxygen demand (COD), total organic carbon (TOC), total solids (TS), pH, total phosphate (TP), total nitrogen (TN), fixed solids (FS), NH4+, orthophosphate, color, turbidity, and conductivity. These parameters were then quantitatively correlated with the molecular weight cutoff of the membrane used. Organic matter in the dissolved fraction (MW<1kDa) predominated in the leachate, accounting for 65% of TOC. Thermal infrared spectroscopy was used to characterize the filter residues. Asymmetric and symmetric stretching of methyl and methylene groups, and of functional groups containing nitrogen and oxygen atoms, were observed. In addition, the ability of two different samples to adsorb heavy metals was tested. Cu2+ was chosen as the representative heavy metal in this study, and the samples were soil; aged refuse, which had spent 8 years in a conventional sanitary landfill; and samples of soil and aged refuse treated for 48h with leachate in the ratio of 5g of sample per 50ml of leachate. Cu2+ uptake by the raw soil was approximately 4.60microg/g, while uptake by the leachate-contacted soil and leachate-contacted aged refuse were 5.66 and 5.11microg/g, respectively. These results show that the organic matter in the leachate enhanced the capacity of aqueous solutions to adsorb Cu2+.

  7. Size-fractionation and characterization of landfill leachate and the improvement of Cu{sup 2+} adsorption capacity in soil and aged refuse

    SciTech Connect

    Lou Ziyang; Chai Xiaoli; Niu Dongjie; Ou Yuanyang; Zhao Youcai

    2009-01-15

    Leachate was collected from an anaerobic lagoon at Shanghai Laogang refuse landfill, the largest landfill in China, and the sample was separated into six fractions using micro-filtration membranes, followed by ultra-filtration membranes. Several parameters of the samples were measured, including chemical oxygen demand (COD), total organic carbon (TOC), total solids (TS), pH, total phosphate (TP), total nitrogen (TN), fixed solids (FS), NH{sub 4}{sup +}, orthophosphate, color, turbidity, and conductivity. These parameters were then quantitatively correlated with the molecular weight cutoff of the membrane used. Organic matter in the dissolved fraction (MW < 1 kDa) predominated in the leachate, accounting for 65% of TOC. Thermal infrared spectroscopy was used to characterize the filter residues. Asymmetric and symmetric stretching of methyl and methylene groups, and of functional groups containing nitrogen and oxygen atoms, were observed. In addition, the ability of two different samples to adsorb heavy metals was tested. Cu{sup 2+} was chosen as the representative heavy metal in this study, and the samples were soil; aged refuse, which had spent 8 years in a conventional sanitary landfill; and samples of soil and aged refuse treated for 48 h with leachate in the ratio of 5 g of sample per 50 ml of leachate. Cu{sup 2+} uptake by the raw soil was {approx}4.60 {mu}g/g, while uptake by the leachate-contacted soil and leachate-contacted aged refuse were 5.66 and 5.11 {mu}g/g, respectively. These results show that the organic matter in the leachate enhanced the capacity of aqueous solutions to adsorb Cu{sup 2+}.

  8. Effect of protein environment within cytochrome P450cam evaluated using a polarizable-embedding QM/MM method.

    PubMed

    Thellamurege, Nandun M; Hirao, Hajime

    2014-02-27

    Metalloenzymes accommodate cofactors and substrates in their active sites, thereby exerting powerful catalytic effects. Understanding the key elements of the mechanism via which such binding is accomplished using a number of atoms in a protein is a fundamental challenge. To address this issue computationally, here we used mechanical-embedding (ME), electronic-embedding (EE), and polarizable-embedding (PE) hybrid quantum mechanics and molecular mechanics (QM/MM) methods and performed an energy decomposition analysis (EDA) of the nonbonding protein environmental effect in the "compound I" intermediate state of cytochrome P450cam. The B3LYP and AMBER99/QP302 methods were used to deal with the QM and MM subsystems, respectively, and the nonbonding interaction energy between these subsystems was decomposed into electrostatic, van der Waals, and polarization contributions. The PE-QM/MM calculation was performed using polarizable force fields that were capable of describing induced dipoles within the MM subsystem, which arose in response to the electric field generated by QM electron density, QM nuclei, and MM point charges. The present QM/MM EDA revealed that the electrostatic term constituted the largest stabilizing interaction between the QM and MM subsystems. When proper adjustment was made for the point charges of the MM atoms located at the QM-MM boundary, EE-QM/MM and PE-QM/MM calculations yielded similar QM electron density distributions, indicating that the MM polarization effect does not have a significant influence on the extent of QM polarization in this particular enzyme system. PMID:24484442

  9. High-Efficiency Microiterative Optimization in QM/MM Simulations of Large Flexible Systems.

    PubMed

    Zhang, Yan; Xie, Peng; He, Xiaohu; Han, Keli

    2016-09-13

    We present here a double-optimizations-of-buffer-region (DOBR) microiterative scheme for high-efficiency energy minimizations of large, flexible systems in combined quantum-mechanical/molecular-mechanical (QM/MM) calculations. In the DOBR scheme, an entire system is divided into three regions: the core, buffer, and outer regions. The core region includes QM atoms and the MM atoms within a cutoff distance R1 to the QM atoms (denoted by MM1 atoms), and the buffer region consists of MM atoms within another cutoff distance R2 to MM1 atoms. Each DOBR microcycle involves two steps: First, QM atoms are assigned electrostatic-potential (ESP) charges, and the buffer and outer regions are optimized at the MM level with the core region kept frozen. Second, the core and buffer regions are optimized at the QM/MM level using the electrostatic embedding with the outer region kept frozen. The two steps are repeated until two optimizations converge at one structure. The DOBR scheme was tested in the optimizations of nucleobases solvated in water spheres of 30 Å radius, where the initial geometries were extracted from the trajectories of classical molecular dynamics simulations, and the cutoff distances R1 and R2 were set to 5.0 and 4.0 Å, respectively. For comparisons, the optimizations were also carried out by a "standard" scheme without microiteration and by the two-region microiterative (TRM) method. We found that the averaged number of QM calculations for the DOBR scheme is only ∼1% of that of the standard scheme and ∼6% of the TRM approach. The promising results indicate that the DOBR scheme could significantly increase the efficiency of geometry optimizations for large, flexible systems in QM/MM calculations. PMID:27505170

  10. The adaptive buffered force QM/MM method in the CP2K and AMBER software packages.

    PubMed

    Mones, Letif; Jones, Andrew; Götz, Andreas W; Laino, Teodoro; Walker, Ross C; Leimkuhler, Ben; Csányi, Gábor; Bernstein, Noam

    2015-04-01

    The implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER are presented. The implementations build on the existing QM/MM functionality in each code, extending it to allow for redefinition of the QM and MM regions during the simulation and reducing QM-MM interface errors by discarding forces near the boundary according to the buffered force-mixing approach. New adaptive thermostats, needed by force-mixing methods, are also implemented. Different variants of the method are benchmarked by simulating the structure of bulk water, water autoprotolysis in the presence of zinc and dimethyl-phosphate hydrolysis using various semiempirical Hamiltonians and density functional theory as the QM model. It is shown that with suitable parameters, based on force convergence tests, the AdBF QM/MM scheme can provide an accurate approximation of the structure in the dynamical QM region matching the corresponding fully QM simulations, as well as reproducing the correct energetics in all cases. Adaptive unbuffered force-mixing and adaptive conventional QM/MM methods also provide reasonable results for some systems, but are more likely to suffer from instabilities and inaccuracies.

  11. The adaptive buffered force QM/MM method in the CP2K and AMBER software packages

    PubMed Central

    Mones, Letif; Jones, Andrew; Götz, Andreas W; Laino, Teodoro; Walker, Ross C; Leimkuhler, Ben; Csányi, Gábor; Bernstein, Noam

    2015-01-01

    The implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER are presented. The implementations build on the existing QM/MM functionality in each code, extending it to allow for redefinition of the QM and MM regions during the simulation and reducing QM-MM interface errors by discarding forces near the boundary according to the buffered force-mixing approach. New adaptive thermostats, needed by force-mixing methods, are also implemented. Different variants of the method are benchmarked by simulating the structure of bulk water, water autoprotolysis in the presence of zinc and dimethyl-phosphate hydrolysis using various semiempirical Hamiltonians and density functional theory as the QM model. It is shown that with suitable parameters, based on force convergence tests, the AdBF QM/MM scheme can provide an accurate approximation of the structure in the dynamical QM region matching the corresponding fully QM simulations, as well as reproducing the correct energetics in all cases. Adaptive unbuffered force-mixing and adaptive conventional QM/MM methods also provide reasonable results for some systems, but are more likely to suffer from instabilities and inaccuracies. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:25649827

  12. Application of a BOSS-Gaussian interface for QM/MM simulations of Henry and methyl transfer reactions.

    PubMed

    Vilseck, Jonah Z; Kostal, Jakub; Tirado-Rives, Julian; Jorgensen, William L

    2015-10-15

    Hybrid quantum mechanics and molecular mechanics (QM/MM) computer simulations have become an indispensable tool for studying chemical and biological phenomena for systems too large to treat with QM alone. For several decades, semiempirical QM methods have been used in QM/MM simulations. However, with increased computational resources, the introduction of ab initio and density function methods into on-the-fly QM/MM simulations is being increasingly preferred. This adaptation can be accomplished with a program interface that tethers independent QM and MM software packages. This report introduces such an interface for the BOSS and Gaussian programs, featuring modification of BOSS to request QM energies and partial atomic charges from Gaussian. A customizable C-shell linker script facilitates the interprogram communication. The BOSS-Gaussian interface also provides convenient access to Charge Model 5 (CM5) partial atomic charges for multiple purposes including QM/MM studies of reactions. In this report, the BOSS-Gaussian interface is applied to a nitroaldol (Henry) reaction and two methyl transfer reactions in aqueous solution. Improved agreement with experiment is found by determining free-energy surfaces with MP2/CM5 QM/MM simulations than previously reported investigations using semiempirical methods.

  13. TINKTEP: A fully self-consistent, mutually polarizable QM/MM approach based on the AMOEBA force field

    NASA Astrophysics Data System (ADS)

    Dziedzic, Jacek; Mao, Yuezhi; Shao, Yihan; Ponder, Jay; Head-Gordon, Teresa; Head-Gordon, Martin; Skylaris, Chris-Kriton

    2016-09-01

    We present a novel quantum mechanical/molecular mechanics (QM/MM) approach in which a quantum subsystem is coupled to a classical subsystem described by the AMOEBA polarizable force field. Our approach permits mutual polarization between the QM and MM subsystems, effected through multipolar electrostatics. Self-consistency is achieved for both the QM and MM subsystems through a total energy minimization scheme. We provide an expression for the Hamiltonian of the coupled QM/MM system, which we minimize using gradient methods. The QM subsystem is described by the onetep linear-scaling DFT approach, which makes use of strictly localized orbitals expressed in a set of periodic sinc basis functions equivalent to plane waves. The MM subsystem is described by the multipolar, polarizable force field AMOEBA, as implemented in tinker. Distributed multipole analysis is used to obtain, on the fly, a classical representation of the QM subsystem in terms of atom-centered multipoles. This auxiliary representation is used for all polarization interactions between QM and MM, allowing us to treat them on the same footing as in AMOEBA. We validate our method in tests of solute-solvent interaction energies, for neutral and charged molecules, demonstrating the simultaneous optimization of the quantum and classical degrees of freedom. Encouragingly, we find that the inclusion of explicit polarization in the MM part of QM/MM improves the agreement with fully QM calculations.

  14. Study the adsorption of sulfates by high cross-linked polystyrene divinylbenzene anion-exchange resin

    NASA Astrophysics Data System (ADS)

    Fathy, Mahmoud; Moghny, Th. Abdel; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.

    2014-11-01

    In response to rising concerns about the effect of sulfate on water quality, human health, and agriculture, many jurisdictions around the world are imposing tighter regulations for sulfate discharge. This is driving the need for environmental compliance in industries like mining, metal processing, pulp and paper, sewage treatment, and chemical manufacturing. The sulfate removal from synthetic water by high cross-linked polystyrene divinylbenzene resin was studied at batch experiments in this study. The effect of pH, contact time, sulfates concentration, and adsorbent dose on the sulfate sequestration was investigated. The optimum conditions were studied on Saline water as a case study. The results showed that with increasing of the absorbent amount; contact time, and pH improve the efficiency of sulfate removal. The maximum sulfates uptake was obtained in pH and contact time 3.0 and 120 min, respectively. Also, with increasing initial concentration of sulfates in water, the efficiency of sulfate removal decreased. The obtained results in this study were matched with Freundlich isotherm and pseudo-second-order kinetic. The maximum adsorption capacity (Qm) and constant rate were found 0.318 (mg/g) and 0.21 (mg/g.min), respectively. This study also showed that in the optimum conditions, the sulfate removal efficiency from Saline water by 0.1 mg/L sulfates was 65.64 %. Eventually, high cross-linked polystyrene divinylbenzene resin is recommended as a suitable and low cost absorbent to sulfate removal from aqueous solutions.

  15. Adsorption of chlorpyrifos, penconazole and metalaxyl from aqueous solution by modified clays.

    PubMed

    Suciu, Nicoleta A; Capri, Ettore

    2009-08-01

    Sorption of three pesticides (chlorpyrifos, metalaxyl and penconazole) has been measured on a commercial clay montmorillonite and on the same mineral modified with either of two cationic-surfactant micelles. Both micelle-clay complexes, commercial names Cloisite 20A and Cloisite 30B, showed a good capacity to sorb all three pesticides from water, whereas their sorption on the natural montmorillonite was not described by an isotherm. Modelling sorption on both micelle-clay complexes showed that the Freundlich sorption constant (K(F)) was higher for chlorpyrifos on Cloisite 20A (K(F) = 7.76) than on Cloisite 30B (K(F) = 5.91), whereas the sorption of metalaxyl was stronger on Cloisite 30B (K(F) = 1.07) than on Cloisite 20A (K(F) = 0.57). Moreover the micelle-clay complex Cloisite 20A also showed a good affinity for penconazole, the maximum quantity adsorbed (q(m)) of 6.33 mg g(-1) being 45% more than that on Cloisite 30B. Single-batch adsorption of each pesticide onto both micelle-clay complexes was studied using the Freundlich isotherm for chlorpyrifos and metalaxyl and the Langmuir isotherm for penconazole. The Cloisite 20A micelle-clay complex was predicted to require 23% less adsorbent to treat certain volumes of wastewater containing 30 mg L(-1) chlorpyrifos, 43% more to treat metalaxyl similarly and 57% less to treat penconazole compared with Cloisite 30B. PMID:20183058

  16. Polymer adsorption

    NASA Astrophysics Data System (ADS)

    Joanny, Jean-Francois

    2008-03-01

    The aim of this talk is to review Pierre-Gilles deGennes' work on polymer adsorption and the impact that it has now in our understanding of this problem. We will first present the self-consistent mean-field theory and its applications to adsorption and depletion. De Gennes most important contribution is probably the derivation of the self-similar power law density profile for adsorbed polymer layers that we will present next, emphasizing the differences between the tail sections and the loop sections of the adsorbed polymers. We will then discuss the kinetics of polymer adsorption and the penetration of a new polymer chain in an adsobed layer that DeGennes described very elegantly in analogy with a quantum tunneling problem. Finally, we will discuss the role of polymer adsorption for colloid stabilization.

  17. Periodic boundary conditions for QM/MM calculations: Ewald summation for extended Gaussian basis sets

    SciTech Connect

    Holden, Zachary C.; Richard, Ryan M.; Herbert, John M.

    2013-12-28

    An implementation of Ewald summation for use in mixed quantum mechanics/molecular mechanics (QM/MM) calculations is presented, which builds upon previous work by others that was limited to semi-empirical electronic structure for the QM region. Unlike previous work, our implementation describes the wave function's periodic images using “ChElPG” atomic charges, which are determined by fitting to the QM electrostatic potential evaluated on a real-space grid. This implementation is stable even for large Gaussian basis sets with diffuse exponents, and is thus appropriate when the QM region is described by a correlated wave function. Derivatives of the ChElPG charges with respect to the QM density matrix are a potentially serious bottleneck in this approach, so we introduce a ChElPG algorithm based on atom-centered Lebedev grids. The ChElPG charges thus obtained exhibit good rotational invariance even for sparse grids, enabling significant cost savings. Detailed analysis of the optimal choice of user-selected Ewald parameters, as well as timing breakdowns, is presented.

  18. A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water.

    PubMed

    Wang, Lee-Ping; Van Voorhis, Troy

    2012-02-14

    We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E0. The QM/MM model uses density functional theory (DFT) to model the solute and a polarizable molecular mechanics (MM) force field to describe the solvent. The linear response approximation is applied to estimate E0 from the thermally averaged electron attachment/detachment energies computed in the oxidized and reduced states. Using the QM/MM model, we calculated one-electron E0 values for several aqueous transition-metal complexes and found substantially improved agreement with experiment compared to values obtained from implicit solvent models. A detailed breakdown of the physical effects in the QM/MM model indicates that hydrogen-bonding effects are mainly responsible for the differences in computed values of E0 between the QM/MM and implicit models. Our results highlight the importance of including solute-solvent hydrogen-bonding effects in the theoretical modeling of redox processes.

  19. Simple Link Atom Saccharide Hybrid (SLASH) Treatment for Glycosidic Bonds at the QM/MM Boundary.

    PubMed

    Crous, Werner; Field, Martin J; Naidoo, Kevin J

    2014-04-01

    We investigated link atom approaches for treating the polar C-O bond with particular reference to the glycosidic bond found in complex carbohydrates. We show that cutting this bond after the oxygen in the QM region and saturating the QM system with a hydrogen link atom leads to greater conformational and configurational accuracy at the boundary compared with cutting the bond before oxygen and saturating the QM system with a halogen link atom to represent the oxygen. Furthermore, we find that balancing the MM atom charges and redistributing the boundary atom charges at the QM/MM boundary minimizes the effect of the link atom, both energetically and structurally. This is illustrated via a series of calculations on a set of carbohydrate and carbohydrate-like model compounds. Finally, we confirm the validity of our model by performing molecular dynamics simulations for a typical disaccharide model compound in water. Our postsimulation conformational and configurational analyses show that the oxygen-to-water hydrogen pair distribution functions and the Φ,Ψ distributions at the glycosidic boundary between the quantum and classical regions compare favorably with results obtained from complete QM and complete MM treatments of the saccharide.

  20. Phosphate adsorption on lanthanum loaded biochar.

    PubMed

    Wang, Zhanghong; Shen, Dekui; Shen, Fei; Li, Tianyu

    2016-05-01

    To attain a low-cost and high-efficient phosphate adsorbent, lanthanum (La) loaded biochar (La-BC) prepared by a chemical precipitation method was developed. La-BC and its pristine biochar (CK-BC) were comparatively characterized using zeta potential, BET surface area, scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). The adsorption ability and the mechanisms during adsorption process for the La-BC samples were also investigated. La loaded on the surface of biochar can be termed as La-composites (such as LaOOH, LaONO3 and La(OH)3), leading to the decrease of negative charge and surface area of biochar. La-BC exhibited the high adsorption capacity to phosphate compared to CK-BC. Adsorption isotherm and adsorption kinetic studies showed that the Langmuir isotherm and second order model could well describe the adsorption process of La-BC, indicating that the adsorption was dominated by a homogeneous and chemical process. The calculated maximum adsorption capacity was as high as 46.37 mg g(-1) (computed in P). Thermodynamic analysis revealed that the adsorption was spontaneous and endothermic. SEM, XRD, XPS and FT-IR analysis suggested that the multi-adsorption mechanisms including precipitation, ligand exchange and complexation interactions can be evidenced during the phosphate adsorption process by La-composites in La-BC. PMID:26871732

  1. Optimization of indigo production by a newly isolated Pseudomonas sp. QM.

    PubMed

    Qu, Yuanyuan; Ma, Qiao; Zhang, Xuwang; Zhou, Hao; Li, Xinliang; Zhou, Jiti

    2012-12-01

    Optimization of indigo production process from indole using a newly isolated phenol-degrading bacterial strain was performed by Plackett-Burman design and response surface methodology. The strain designated as QM was identified as Pseudomonas sp. according to 16S rDNA analysis. Spectrum analysis of indole biotransformation products revealed the presence of indigo and a by-product indirubin. To improve indigo yield, Plackett-Burman design was used to select significant factors from 8 viriables. Then response surface methodology based on a 2(3) central composite design was used to further optimize the transformation process. Under the optimal conditons, strain QM can produce 27.20 mg/l indigo after 24 h cultivation at 30 °C, which was 151.3% higher than that from the initial conversion condition. The results indicated that Pseudomonas sp. QM should be a potential candidate for indigo industial production. PMID:22359270

  2. New QM/MM implementation of the DFTB3 method in the gromacs package.

    PubMed

    Kubař, Tomáš; Welke, Kai; Groenhof, Gerrit

    2015-10-01

    The approximate density-functional tight-binding theory method DFTB3 has been implemented in the quantum mechanics/molecular mechanics (QM/MM) framework of the Gromacs molecular simulation package. We show that the efficient smooth particle-mesh Ewald implementation of Gromacs extends to the calculation of QM/MM electrostatic interactions. Further, we make use of the various free-energy functionalities provided by Gromacs and the PLUMED plugin. We exploit the versatility and performance of the current framework in three typical applications of QM/MM methods to solve biophysical problems: (i) ultrafast proton transfer in malonaldehyde, (ii) conformation of the alanine dipeptide, and (iii) electron-induced repair of a DNA lesion. Also discussed is the further development of the framework, regarding mostly the options for parallelization. PMID:26238364

  3. [Adsorption and Desorption Characteristics of Endosulfan in Purple Soil].

    PubMed

    Zhao, Yan; Zheng, Guo-can; Zhu, Heng; Zhang, Jin-zhong; Zhu, Xiu-ying; Hu, Shu-chun; Wu, Ya-lin

    2015-09-01

    In order to reveal the residual process of endosulfan in purple soil and protect soil ecological environment, the adsorption and desorption characteristics of endosulfan in purple soil were investigated, and effects of temperature, adsorbent amount, and initial pH of adsorption solution on the adsorption capacity were also examined by static adsorption and desorption experiments. The results showed that the adsorption kinetic process could be well described by the second-order kinetic equation with the initial rate constants of α-, β-endosulfan as 0. 157 and 0. 115 mg.(g.min)-1, respectively. The adsorption thermodynamic process could be well described by the Langmuir isotherm with the maximum adsorption capacities of α-, β-endosulfan as 0. 257 mg . g -1 and 0. 155 mg . g -1, respectively. The adsorption process of endosulfan in purple soil may be an exothermic physicochemical process, and is dominated by physical adsorption. Under the experimental conditions examined in this study, the initial pH of adsorption solution had a relative great influence on the adsorption capacity, whereas the temperature and adsorbent amount had no significant influence. The desorption experiments found that the maximum desorption capacities of α-, β-endosulfan adsorbed in purple soil were 0. 029 mg . g -1 and 0. 017 mg . g -1 at 6 and 4 h, and accounted for 10. 5% and 16. 1% in the maximum adsorption capacities, respectively. PMID:26717711

  4. [Adsorption and Desorption Characteristics of Endosulfan in Purple Soil].

    PubMed

    Zhao, Yan; Zheng, Guo-can; Zhu, Heng; Zhang, Jin-zhong; Zhu, Xiu-ying; Hu, Shu-chun; Wu, Ya-lin

    2015-09-01

    In order to reveal the residual process of endosulfan in purple soil and protect soil ecological environment, the adsorption and desorption characteristics of endosulfan in purple soil were investigated, and effects of temperature, adsorbent amount, and initial pH of adsorption solution on the adsorption capacity were also examined by static adsorption and desorption experiments. The results showed that the adsorption kinetic process could be well described by the second-order kinetic equation with the initial rate constants of α-, β-endosulfan as 0. 157 and 0. 115 mg.(g.min)-1, respectively. The adsorption thermodynamic process could be well described by the Langmuir isotherm with the maximum adsorption capacities of α-, β-endosulfan as 0. 257 mg . g -1 and 0. 155 mg . g -1, respectively. The adsorption process of endosulfan in purple soil may be an exothermic physicochemical process, and is dominated by physical adsorption. Under the experimental conditions examined in this study, the initial pH of adsorption solution had a relative great influence on the adsorption capacity, whereas the temperature and adsorbent amount had no significant influence. The desorption experiments found that the maximum desorption capacities of α-, β-endosulfan adsorbed in purple soil were 0. 029 mg . g -1 and 0. 017 mg . g -1 at 6 and 4 h, and accounted for 10. 5% and 16. 1% in the maximum adsorption capacities, respectively.

  5. Methodological aspects of QM/MM calculations: A case study on matrix metalloproteinase-2.

    PubMed

    Vasilevskaya, Tatiana; Khrenova, Maria G; Nemukhin, Alexander V; Thiel, Walter

    2016-07-15

    We address methodological issues in quantum mechanics/molecular mechanics (QM/MM) calculations on a zinc-dependent enzyme. We focus on the first stage of peptide bond cleavage by matrix metalloproteinase-2 (MMP-2), that is, the nucleophilic attack of the zinc-coordinating water molecule on the carbonyl carbon atom of the scissile fragment of the substrate. This step is accompanied by significant charge redistribution around the zinc cation, bond cleavage, and bond formation. We vary the size and initial geometry of the model system as well as the computational protocol to demonstrate the influence of these choices on the results obtained. We present QM/MM potential energy profiles for a set of snapshots randomly selected from QM/MM-based molecular dynamics simulations and analyze the differences in the computed profiles in structural terms. Since the substrate in MMP-2 is located on the protein surface, we investigate the influence of the thickness of the water layer around the enzyme on the QM/MM energy profile. Thin water layers (0-2 Å) give unrealistic results because of structural reorganizations in the active-site region at the protein surface. A 12 Å water layer appears to be sufficient to capture the effect of the solvent; the corresponding QM/MM energy profile is very close to that obtained from QM/MM/SMBP calculations using the solvent macromolecular boundary potential (SMBP). We apply the optimized computational protocol to explain the origin of the different catalytic activity of the Glu116Asp mutant: the energy barrier for the first step is higher, which is rationalized on structural grounds. © 2016 Wiley Periodicals, Inc. PMID:27140531

  6. Self-consistent QM/MM methodologies for structural refinement of photosystem II and other macromolecules of biological interest

    SciTech Connect

    Batista, Enrique R; Sproviero, Eduardo M; Newcomer, Michael; Gascon, Jose A; Batista, Victor S

    2008-01-01

    The combination of quantum mechanics and molecular mechanics (QM/MM) is one of the most promising approaches to study the structure, function, and properties of proteins and nucleic acids. However, there some instances in which the limitations of either the MM (lack of a proper electronic description) or QM (limited to a few number of atoms) methods prevent a proper description of the system. To address this issue, we review here our approach to fine-tune the structure of biological systems using post-QM/MM refinements. These protocols are based on spectroscopy data, and/or partitioning of the system to extend the QM description to a larger region of a protein. We illustrate these methodologies through applications to several biomolecules, which were pre-optimized at the QM/MM level and then further refined using postQM/MM refinement methodologies: mod(QM/MM), which refines the atomic charges of the residues included in the MM region accounting for polarization effects; mod(QM/MM)-opt that partition the MM region in smaller parts and optimizes each part in an iterative. self-consistent way, and the Polarized-Extended X-Ray Absorption Fine Structure (P-EXAFS) fitting procedure, which fine-tune the atomic coordinates to reproduce experimental polarized EXAFS spectra. The first two techniques were applied to the guanine quadruplex. while the P-EXAFS refinement was applied to the oxygen evolving complex of photosystem II.

  7. Application of a BOSS – Gaussian Interface for QM/MM Simulations of Henry and Methyl Transfer Reactions

    PubMed Central

    Vilseck, Jonah Z.; Kostal, Jakub; Tirado-Rives, Julian; Jorgensen, William L.

    2015-01-01

    Hybrid quantum mechanics and molecular mechanics (QM/MM) computer simulations have become an indispensable tool for studying chemical and biological phenomena for systems too large to treat with quantum mechanics alone. For several decades, semi-empirical QM methods have been used in QM/MM simulations. However, with increased computational resources, the introduction of ab initio and density function methods into on-the-fly QM/MM simulations is being increasingly preferred. This adaptation can be accomplished with a program interface that tethers independent QM and MM software packages. This report introduces such an interface for the BOSS and Gaussian programs, featuring modification of BOSS to request QM energies and partial atomic charges from Gaussian. A customizable C-shell linker script facilitates the inter-program communication. The BOSS–Gaussian interface also provides convenient access to Charge Model 5 (CM5) partial atomic charges for multiple purposes including QM/MM studies of reactions. In this report, the BOSS–Gaussian interface is applied to a nitroaldol (Henry) reaction and two methyl transfer reactions in aqueous solution. Improved agreement with experiment is found by determining free-energy surfaces with MP2/CM5 QM/MM simulations than previously reported investigations employing semiempirical methods. PMID:26311531

  8. Convergence of QM/MM free-energy perturbations based on molecular-mechanics or semiempirical simulations.

    PubMed

    Heimdal, Jimmy; Ryde, Ulf

    2012-09-28

    Lately, there has been great interest in performing free-energy perturbation (FEP) at the combined quantum mechanics and molecular mechanics (QM/MM) level, e.g. for enzyme reactions. Such calculations require extensive sampling of phase space, which typically is prohibitive with density-functional theory or ab initio methods. Therefore, such calculations have mostly been performed with semiempirical QM (SQM) methods, or by using a thermodynamic cycle involving sampling at the MM level and perturbations between the MM and QM/MM levels of theory. However, the latter perturbations typically have convergence problems, unless the QM system is kept fixed during the simulations, because the MM and QM/MM descriptions of the internal degrees of freedom inside the QM system are too dissimilar. We have studied whether the convergence of the MM → QM/MM perturbation can be improved by using a thoroughly parameterised force field or by using SQM/MM methods. As a test case we use the first half-reaction of haloalkane dehalogenase and the QM calculations are performed with the PBE, B3LYP, and TPSSH density-functional methods. We show that the convergence can be improved with a tailored force field, but only locally around the parameterised state. Simulations based on SQM/MM methods using the MNDO, AM1, PM3, RM1, PDDG-MNDO, and PDDG-PM3 Hamiltonians have slightly better convergence properties, but very long simulations are still needed (~10 ns) and convergence is obtained only if electrostatic interactions between the QM system and the surroundings are ignored. This casts some doubts on the common practice to base QM/MM FEPs on semiempirical simulations without any reweighting of the trajectories.

  9. Convergence of QM/MM free-energy perturbations based on molecular-mechanics or semiempirical simulations.

    PubMed

    Heimdal, Jimmy; Ryde, Ulf

    2012-09-28

    Lately, there has been great interest in performing free-energy perturbation (FEP) at the combined quantum mechanics and molecular mechanics (QM/MM) level, e.g. for enzyme reactions. Such calculations require extensive sampling of phase space, which typically is prohibitive with density-functional theory or ab initio methods. Therefore, such calculations have mostly been performed with semiempirical QM (SQM) methods, or by using a thermodynamic cycle involving sampling at the MM level and perturbations between the MM and QM/MM levels of theory. However, the latter perturbations typically have convergence problems, unless the QM system is kept fixed during the simulations, because the MM and QM/MM descriptions of the internal degrees of freedom inside the QM system are too dissimilar. We have studied whether the convergence of the MM → QM/MM perturbation can be improved by using a thoroughly parameterised force field or by using SQM/MM methods. As a test case we use the first half-reaction of haloalkane dehalogenase and the QM calculations are performed with the PBE, B3LYP, and TPSSH density-functional methods. We show that the convergence can be improved with a tailored force field, but only locally around the parameterised state. Simulations based on SQM/MM methods using the MNDO, AM1, PM3, RM1, PDDG-MNDO, and PDDG-PM3 Hamiltonians have slightly better convergence properties, but very long simulations are still needed (~10 ns) and convergence is obtained only if electrostatic interactions between the QM system and the surroundings are ignored. This casts some doubts on the common practice to base QM/MM FEPs on semiempirical simulations without any reweighting of the trajectories. PMID:22797613

  10. Combined quantum mechanics/molecular mechanics (QM/MM) methods in computational enzymology.

    PubMed

    van der Kamp, Marc W; Mulholland, Adrian J

    2013-04-23

    Computational enzymology is a rapidly maturing field that is increasingly integral to understanding mechanisms of enzyme-catalyzed reactions and their practical applications. Combined quantum mechanics/molecular mechanics (QM/MM) methods are important in this field. By treating the reacting species with a quantum mechanical method (i.e., a method that calculates the electronic structure of the active site) and including the enzyme environment with simpler molecular mechanical methods, enzyme reactions can be modeled. Here, we review QM/MM methods and their application to enzyme-catalyzed reactions to investigate fundamental and practical problems in enzymology. A range of QM/MM methods is available, from cheaper and more approximate methods, which can be used for molecular dynamics simulations, to highly accurate electronic structure methods. We discuss how modeling of reactions using such methods can provide detailed insight into enzyme mechanisms and illustrate this by reviewing some recent applications. We outline some practical considerations for such simulations. Further, we highlight applications that show how QM/MM methods can contribute to the practical development and application of enzymology, e.g., in the interpretation and prediction of the effects of mutagenesis and in drug and catalyst design.

  11. Generalized Observables, Bell's Inequalities and Mixtures in the ESR Model for QM

    NASA Astrophysics Data System (ADS)

    Garola, Claudio; Sozzo, Sandro

    2011-03-01

    The extended semantic realism ( ESR) model proposes a new theoretical perspective which embodies the mathematical formalism of standard (Hilbert space) quantum mechanics (QM) into a noncontextual framework, reinterpreting quantum probabilities as conditional instead of absolute. We provide in this review an overall view on the present status of our research on this topic. We attain in a new, shortened way a mathematical representation of the generalized observables introduced by the ESR model and a generalization of the projection postulate of elementary QM. Basing on these results we prove that the Bell-Clauser-Horne-Shimony-Holt (BCHSH) inequality, a modified BCHSH inequality and quantum predictions hold together in the ESR model because they refer to different parts of the picture of the physical world supplied by the model. Then we show that a new mathematical representation of mixtures must be introduced in the ESR model which does not coincide with the standard representation in QM and avoids some deep problems that arise from the representation of mixtures provided by QM. Finally we get a nontrivial generalization of the Lüders postulate, which is justified in a special case by introducing a reasonable physical assumption on the evolution of the compound system made up of the measured system and the measuring apparatus.

  12. Quantum and Molecular Mechanical (QM/MM) Monte Carlo Techniques for Modeling Condensed-Phase Reactions

    PubMed Central

    Jorgensen, Wiliiam L.

    2014-01-01

    A recent review (Acc. Chem. Res. 2010, 43:142–151) examined our use and development of a combined quantum and molecular mechanical (QM/MM) technique for modelling organic and enzymatic reactions. Advances included the PDDG/PM3 semiempirical QM (SQM) method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo simulations, and a polynomial quadrature method for rapidly treating proton-transfer reactions. The current article serves as a follow up on our progress. Highlights include new reactions, alternative SQM methods, a polarizable OPLS force field, and novel solvent environments, e.g., “on water” and room temperature ionic liquids. The methodology is strikingly accurate across a wide range of condensed-phase and antibody-catalyzed reactions including substitution, decarboxylation, elimination, isomerization, and pericyclic classes. Comparisons are made to systems treated with continuum-based solvents and ab initio or density functional theory (DFT) methods. Overall, the QM/MM methodology provides detailed characterization of reaction paths, proper configurational sampling, several advantages over implicit solvent models, and a reasonable computational cost. PMID:25431625

  13. Inhibitor Ranking through QM Based Chelation Calculations for Virtual Screening of HIV-1 RNase H Inhibition

    PubMed Central

    Poongavanam, Vasanthanathan; Steinmann, Casper; Kongsted, Jacob

    2014-01-01

    Quantum mechanical (QM) calculations have been used to predict the binding affinity of a set of ligands towards HIV-1 RT associated RNase H (RNH). The QM based chelation calculations show improved binding affinity prediction for the inhibitors compared to using an empirical scoring function. Furthermore, full protein fragment molecular orbital (FMO) calculations were conducted and subsequently analysed for individual residue stabilization/destabilization energy contributions to the overall binding affinity in order to better understand the true and false predictions. After a successful assessment of the methods based on the use of a training set of molecules, QM based chelation calculations were used as filter in virtual screening of compounds in the ZINC database. By this, we find, compared to regular docking, QM based chelation calculations to significantly reduce the large number of false positives. Thus, the computational models tested in this study could be useful as high throughput filters for searching HIV-1 RNase H active-site molecules in the virtual screening process. PMID:24897431

  14. Photocopy of drawing (original drawing of Q.M. Gas & Oil ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Photocopy of drawing (original drawing of Q.M. Gas & Oil House in possession of MacDill Air Force Base, Civil Engineering, Tampa, Florida; 1940 architectural drawings by Construction Division, Office of the Quartermaster General) ELEVATIONS AND DETAILS - MacDill Air Force Base, Quartermaster Gas & Oil House, 8103 Hanger Loop Drive, Tampa, Hillsborough County, FL

  15. QM/MM modeling of benzene hydroxylation in human cytochrome P450 2C9.

    PubMed

    Bathelt, Christine M; Mulholland, Adrian J; Harvey, Jeremy N

    2008-12-18

    The mechanism of benzene hydroxylation was investigated in the realistic enzyme environment of the human CYP 2C9 by using quantum mechanical/molecular mechanical (QM/MM) calculations of the whole reaction profile using the B3LYP method to describe the QM region. The calculated QM/MM barriers for addition of the active species Compound I to benzene are consistent with experimental rate constants for benzene metabolism in CYP 2E1. In contrast to gas-phase model calculations, our results suggest that competing side-on and face-on geometries of arene addition may both occur in the case of aromatic ring oxidation in cytochrome P450s. QM/MM profiles for three different rearrangement pathways of the initially formed sigma-adduct, leading to formation of epoxide, ketone, and an N-protonated porphyrin species, were calculated. Our results suggest that epoxide and ketone products form with comparable ease in the face-on pathway, whereas epoxide formation is preferred in the side-on pathway. Additionally, rearrangement to the N-protonated porphyrin species was found to be competitive with side-on epoxide formation. This suggests that overall, the competition between formation of epoxide and phenol final products in P450 oxidation of aromatic substrates is quite finely balanced. PMID:18754597

  16. Photocopy of drawing (original drawing of Q.M. Warehouse in possession ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Photocopy of drawing (original drawing of Q.M. Warehouse in possession of MacDill Air Force Base, Civil Engineering, Tampa, Florida; 1940 architectural drawings by Construction Division, Office of the Quartermaster General) PLANS, ELEVATIONS, SECTIONS, AND ELECTRICAL DETAILS - MacDill Air Force Base, Quartermaster Warehouse, 7605 Hillsborough Loop Drive, Tampa, Hillsborough County, FL

  17. FAST TRACK COMMUNICATION: A globally diagonalizable α2-dynamo operator, SUSY QM and the Dirac equation

    NASA Astrophysics Data System (ADS)

    Günther, Uwe; Samsonov, Boris F.; Stefani, Frank

    2007-02-01

    A new class of semi-analytically solvable MHD α2-dynamos is found based on a global diagonalization of the matrix part of the dynamo differential operator. Close parallels to SUSY QM are used to relate these models to the Dirac equation and to extract non-numerical information about the dynamo spectrum.

  18. Quantum and Molecular Mechanical (QM/MM) Monte Carlo Techniques for Modeling Condensed-Phase Reactions.

    PubMed

    Acevedo, Orlando; Jorgensen, Wiliiam L

    2014-09-01

    A recent review (Acc. Chem. Res. 2010, 43:142-151) examined our use and development of a combined quantum and molecular mechanical (QM/MM) technique for modelling organic and enzymatic reactions. Advances included the PDDG/PM3 semiempirical QM (SQM) method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo simulations, and a polynomial quadrature method for rapidly treating proton-transfer reactions. The current article serves as a follow up on our progress. Highlights include new reactions, alternative SQM methods, a polarizable OPLS force field, and novel solvent environments, e.g., "on water" and room temperature ionic liquids. The methodology is strikingly accurate across a wide range of condensed-phase and antibody-catalyzed reactions including substitution, decarboxylation, elimination, isomerization, and pericyclic classes. Comparisons are made to systems treated with continuum-based solvents and ab initio or density functional theory (DFT) methods. Overall, the QM/MM methodology provides detailed characterization of reaction paths, proper configurational sampling, several advantages over implicit solvent models, and a reasonable computational cost. PMID:25431625

  19. Born-Oppenheimer Ab Initio QM/MM Molecular Dynamics Simulations of Enzyme Reactions.

    PubMed

    Zhou, Y; Wang, S; Li, Y; Zhang, Y

    2016-01-01

    There are two key requirements for reliably simulating enzyme reactions: one is a reasonably accurate potential energy surface to describe the bond-forming/breaking process as well as to adequately model the heterogeneous enzyme environment; the other is to perform extensive sampling since an enzyme system consists of at least thousands of atoms and its energy landscape is very complex. One attractive approach to meet both daunting tasks is Born-Oppenheimer ab initio QM/MM molecular dynamics (aiQM/MM-MD) simulation with umbrella sampling. In this chapter, we describe our recently developed pseudobond Q-Chem-Amber interface, which employs a combined electrostatic-mechanical embedding scheme with periodic boundary condition and the particle mesh Ewald method for long-range electrostatics interactions. In our implementation, Q-Chem and the sander module of Amber are combined at the source code level without using system calls, and all necessary data communications between QM and MM calculations are achieved via computer memory. We demonstrate the applicability of this pseudobond Q-Chem-Amber interface by presenting two examples, one reaction in aqueous solution and one enzyme reaction. Finally, we describe our established aiQM/MM-MD enzyme simulation protocol, which has been successfully applied to study more than a dozen enzymes. PMID:27498636

  20. Final report of APMP.QM-S6: clenbuterol in porcine meat

    NASA Astrophysics Data System (ADS)

    Sin, D. W.-M.; Ho, C.; Yip, Y.-C.

    2016-01-01

    At the CCQM Organic Analysis Working Group (OAWG) Meeting held in April 2012 and the APMP TCQM Meeting held in November 2012, an APMP supplementary comparison (APMP.QM-S6) on the determination of clenbuterol in porcine meat was supported by the OAWG and APMP TCQM. This comparison was organized by the Government Laboratory, Hong Kong. In order to accommodate a wider participation, a pilot study (APMP.QM-P22) was run in parallel to APMP.QM-S6. This study provided the means for assessing the measurement capabilities for determination of low-polarity measurands in a procedure that requires extraction, clean-up, analytical separation, and selective detection in a food matrix. A total of 7 institutes registered for the supplementary comparison and 6 of them submitted their results. 4 results were included for SCRV calculation. All participating laboratories applied Isotope Dilution Liquid Chromatography-Tandem Mass Spectrometry (ID-LCMS/MS) technique with clenbuterol-d9 as internal standard spiked for quantitation in this programme. KEY WORDS FOR SEARCH APMP.QM-S6 and Clenbuterol Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  1. Physical adsorption strength in open systems.

    PubMed

    Knippenberg, M Todd; Stuart, Steven J; Cooper, Alan C; Pez, G P; Cheng, Hansong

    2006-11-23

    For a physical adsorption system, the distances of adsorbates from the surface of a substrate can vary significantly, depending on particle loading and interatomic interactions. Although the total adsorption energy is quantified easily, the normalized, per-particle adsorption energies are more ambiguous if some of these particles are far away from the surface and are interacting only weakly with the substrate. A simple analytical procedure is proposed to characterize the distance dependence of the physisorption strength and effective adsorption capacity. As an example, the method is utilized to describe H2 physisorption in a finite bundle of single-walled carbon nanotubes. PMID:17107125

  2. Charge-dependent many-body exchange and dispersion interactions in combined QM/MM simulations

    NASA Astrophysics Data System (ADS)

    Kuechler, Erich R.; Giese, Timothy J.; York, Darrin M.

    2015-12-01

    Accurate modeling of the molecular environment is critical in condensed phase simulations of chemical reactions. Conventional quantum mechanical/molecular mechanical (QM/MM) simulations traditionally model non-electrostatic non-bonded interactions through an empirical Lennard-Jones (LJ) potential which, in violation of intuitive chemical principles, is bereft of any explicit coupling to an atom's local electronic structure. This oversight results in a model whereby short-ranged exchange-repulsion and long-ranged dispersion interactions are invariant to changes in the local atomic charge, leading to accuracy limitations for chemical reactions where significant atomic charge transfer can occur along the reaction coordinate. The present work presents a variational, charge-dependent exchange-repulsion and dispersion model, referred to as the charge-dependent exchange and dispersion (QXD) model, for hybrid QM/MM simulations. Analytic expressions for the energy and gradients are provided, as well as a description of the integration of the model into existing QM/MM frameworks, allowing QXD to replace traditional LJ interactions in simulations of reactive condensed phase systems. After initial validation against QM data, the method is demonstrated by capturing the solvation free energies of a series of small, chlorine-containing compounds that have varying charge on the chlorine atom. The model is further tested on the SN2 attack of a chloride anion on methylchloride. Results suggest that the QXD model, unlike the traditional LJ model, is able to simultaneously obtain accurate solvation free energies for a range of compounds while at the same time closely reproducing the experimental reaction free energy barrier. The QXD interaction model allows explicit coupling of atomic charge with many-body exchange and dispersion interactions that are related to atomic size and provides a more accurate and robust representation of non-electrostatic non-bonded QM/MM interactions.

  3. Charge-dependent many-body exchange and dispersion interactions in combined QM/MM simulations.

    PubMed

    Kuechler, Erich R; Giese, Timothy J; York, Darrin M

    2015-12-21

    Accurate modeling of the molecular environment is critical in condensed phase simulations of chemical reactions. Conventional quantum mechanical/molecular mechanical (QM/MM) simulations traditionally model non-electrostatic non-bonded interactions through an empirical Lennard-Jones (LJ) potential which, in violation of intuitive chemical principles, is bereft of any explicit coupling to an atom's local electronic structure. This oversight results in a model whereby short-ranged exchange-repulsion and long-ranged dispersion interactions are invariant to changes in the local atomic charge, leading to accuracy limitations for chemical reactions where significant atomic charge transfer can occur along the reaction coordinate. The present work presents a variational, charge-dependent exchange-repulsion and dispersion model, referred to as the charge-dependent exchange and dispersion (QXD) model, for hybrid QM/MM simulations. Analytic expressions for the energy and gradients are provided, as well as a description of the integration of the model into existing QM/MM frameworks, allowing QXD to replace traditional LJ interactions in simulations of reactive condensed phase systems. After initial validation against QM data, the method is demonstrated by capturing the solvation free energies of a series of small, chlorine-containing compounds that have varying charge on the chlorine atom. The model is further tested on the SN2 attack of a chloride anion on methylchloride. Results suggest that the QXD model, unlike the traditional LJ model, is able to simultaneously obtain accurate solvation free energies for a range of compounds while at the same time closely reproducing the experimental reaction free energy barrier. The QXD interaction model allows explicit coupling of atomic charge with many-body exchange and dispersion interactions that are related to atomic size and provides a more accurate and robust representation of non-electrostatic non-bonded QM/MM interactions.

  4. Charge-dependent many-body exchange and dispersion interactions in combined QM/MM simulations.

    PubMed

    Kuechler, Erich R; Giese, Timothy J; York, Darrin M

    2015-12-21

    Accurate modeling of the molecular environment is critical in condensed phase simulations of chemical reactions. Conventional quantum mechanical/molecular mechanical (QM/MM) simulations traditionally model non-electrostatic non-bonded interactions through an empirical Lennard-Jones (LJ) potential which, in violation of intuitive chemical principles, is bereft of any explicit coupling to an atom's local electronic structure. This oversight results in a model whereby short-ranged exchange-repulsion and long-ranged dispersion interactions are invariant to changes in the local atomic charge, leading to accuracy limitations for chemical reactions where significant atomic charge transfer can occur along the reaction coordinate. The present work presents a variational, charge-dependent exchange-repulsion and dispersion model, referred to as the charge-dependent exchange and dispersion (QXD) model, for hybrid QM/MM simulations. Analytic expressions for the energy and gradients are provided, as well as a description of the integration of the model into existing QM/MM frameworks, allowing QXD to replace traditional LJ interactions in simulations of reactive condensed phase systems. After initial validation against QM data, the method is demonstrated by capturing the solvation free energies of a series of small, chlorine-containing compounds that have varying charge on the chlorine atom. The model is further tested on the SN2 attack of a chloride anion on methylchloride. Results suggest that the QXD model, unlike the traditional LJ model, is able to simultaneously obtain accurate solvation free energies for a range of compounds while at the same time closely reproducing the experimental reaction free energy barrier. The QXD interaction model allows explicit coupling of atomic charge with many-body exchange and dispersion interactions that are related to atomic size and provides a more accurate and robust representation of non-electrostatic non-bonded QM/MM interactions. PMID

  5. Charge-dependent many-body exchange and dispersion interactions in combined QM/MM simulations

    SciTech Connect

    Kuechler, Erich R.; Giese, Timothy J.; York, Darrin M.

    2015-12-21

    Accurate modeling of the molecular environment is critical in condensed phase simulations of chemical reactions. Conventional quantum mechanical/molecular mechanical (QM/MM) simulations traditionally model non-electrostatic non-bonded interactions through an empirical Lennard-Jones (LJ) potential which, in violation of intuitive chemical principles, is bereft of any explicit coupling to an atom’s local electronic structure. This oversight results in a model whereby short-ranged exchange-repulsion and long-ranged dispersion interactions are invariant to changes in the local atomic charge, leading to accuracy limitations for chemical reactions where significant atomic charge transfer can occur along the reaction coordinate. The present work presents a variational, charge-dependent exchange-repulsion and dispersion model, referred to as the charge-dependent exchange and dispersion (QXD) model, for hybrid QM/MM simulations. Analytic expressions for the energy and gradients are provided, as well as a description of the integration of the model into existing QM/MM frameworks, allowing QXD to replace traditional LJ interactions in simulations of reactive condensed phase systems. After initial validation against QM data, the method is demonstrated by capturing the solvation free energies of a series of small, chlorine-containing compounds that have varying charge on the chlorine atom. The model is further tested on the S{sub N}2 attack of a chloride anion on methylchloride. Results suggest that the QXD model, unlike the traditional LJ model, is able to simultaneously obtain accurate solvation free energies for a range of compounds while at the same time closely reproducing the experimental reaction free energy barrier. The QXD interaction model allows explicit coupling of atomic charge with many-body exchange and dispersion interactions that are related to atomic size and provides a more accurate and robust representation of non-electrostatic non-bonded QM

  6. Protein NMR chemical shift calculations based on the automated fragmentation QM/MM approach.

    PubMed

    He, Xiao; Wang, Bing; Merz, Kenneth M

    2009-07-30

    An automated fragmentation quantum mechanics/molecular mechanics (AF-QM/MM) approach has been developed to routinely calculate ab initio protein NMR chemical shielding constants. The AF-QM/MM method is linear-scaling and trivially parallel. A general fragmentation scheme is employed to generate each residue-centric region which is treated by quantum mechanics, and the environmental electrostatic field is described with molecular mechanics. The AF-QM/MM method shows good agreement with standard self-consistent field (SCF) calculations of the NMR chemical shieldings for the mini-protein Trp cage. The root-mean-square errors (RMSEs) for 1H, 13C, and 15N NMR chemical shieldings are equal to or less than 0.09, 0.32, and 0.78 ppm, respectively, for all Hartree-Fock (HF) and density functional theory (DFT) calculations reported in this work. The environmental electrostatic potential is necessary to accurately reproduce the NMR chemical shieldings using the AF-QM/MM approach. The point-charge models provided by AMBER, AM1/CM2, PM3/CM1, and PM3/CM2 all effectively model the electrostatic field. The latter three point-charge models are generated via semiempirical linear-scaling SCF calculations of the entire protein system. The correlations between experimental 1H NMR chemical shifts and theoretical predictions are >0.95 for AF-QM/MM calculations using B3LYP with the 6-31G**, 6-311G**, and 6-311++G** basis sets. Our study, not unexpectedly, finds that conformational changes within a protein structure play an important role in the accurate prediction of experimental NMR chemical shifts from theory.

  7. Tomato QM-Like Protein Protects Saccharomyces cerevisiae Cells against Oxidative Stress by Regulating Intracellular Proline Levels

    PubMed Central

    Chen, Changbin; Wanduragala, Srimevan; Becker, Donald F.; Dickman, Martin B.

    2006-01-01

    Exogenous proline can protect cells of Saccharomyces cerevisiae from oxidative stress. We altered intracellular proline levels by overexpressing the proline dehydrogenase gene (PUT1) of S. cerevisiae. Put1p performs the first enzymatic step of proline degradation in S. cerevisiae. Overexpression of Put1p results in low proline levels and hypersensitivity to oxidants, such as hydrogen peroxide and paraquat. A put1-disrupted yeast mutant deficient in Put1p activity has increased protection from oxidative stress and increased proline levels. Following a conditional life/death screen in yeast, we identified a tomato (Lycopersicon esculentum) gene encoding a QM-like protein (tQM) and found that stable expression of tQM in the Put1p-overexpressing strain conferred protection against oxidative damage from H2O2, paraquat, and heat. This protection was correlated with reactive oxygen species (ROS) reduction and increased proline accumulation. A yeast two-hybrid system assay was used to show that tQM physically interacts with Put1p in yeast, suggesting that tQM is directly involved in modulating proline levels. tQM also can rescue yeast from the lethality mediated by the mammalian proapoptotic protein Bax, through the inhibition of ROS generation. Our results suggest that tQM is a component of various stress response pathways and may function in proline-mediated stress tolerance in plants. PMID:16751508

  8. The MOD-QM/MM Method: Applications to Studies of Photosystem II and DNA G-Quadruplexes.

    PubMed

    Askerka, M; Ho, J; Batista, E R; Gascón, J A; Batista, V S

    2016-01-01

    Quantum mechanics/molecular mechanics (QM/MM) hybrid methods are currently the most powerful computational tools for studies of structure/function relations and catalytic sites embedded in macrobiomolecules (eg, proteins and nucleic acids). QM/MM methodologies are highly efficient since they implement quantum chemistry methods for modeling only the portion of the system involving bond-breaking/forming processes (QM layer), as influenced by the surrounding molecular environment described in terms of molecular mechanics force fields (MM layer). Some of the limitations of QM/MM methods when polarization effects are not explicitly considered include the approximate treatment of electrostatic interactions between QM and MM layers. Here, we review recent advances in the development of computational protocols that allow for rigorous modeling of electrostatic interactions in biomacromolecules and structural refinement, beyond the common limitations of QM/MM hybrid methods. We focus on photosystem II (PSII) with emphasis on the description of the oxygen-evolving complex (OEC) and its high-resolution extended X-ray absorption fine structure spectra (EXAFS) in conjunction with Monte Carlo structural refinement. Furthermore, we review QM/MM structural refinement studies of DNA G4 quadruplexes with embedded monovalent cations and direct comparisons to NMR data. PMID:27498648

  9. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  10. CRYOGENIC ADSORPTION OF HYDROGEN ISOTOPES OVER NANO-STRUCTURED MATERIALS

    SciTech Connect

    Xiao, S.; Heung, L.

    2010-10-07

    Porous materials such as zeolites, activated carbon, silica gels, alumina and a number of industrial catalysts are compared and ranked for hydrogen and deuterium adsorption at liquid nitrogen temperature. All samples show higher D{sub 2} adsorption than that of H{sub 2}, in which a HY sample has the greatest isotopic effect while 13X has the highest hydrogen uptake capacity. Material's moisture content has significant impact to its hydrogen uptake. A material without adequate drying could result in complete loss of its adsorption capacity. Even though some materials present higher H{sub 2} adsorption capacity at full pressure, their adsorption at low vapor pressure may not be as good as others. Adsorption capacity in a dynamic system is much less than in a static system. A sharp desorption is also expected in case of temperature upset.

  11. Toward Accurate Modelling of Enzymatic Reactions: All Electron Quantum Chemical Analysis combined with QM/MM Calculation of Chorismate Mutase

    SciTech Connect

    Ishida, Toyokazu

    2008-09-17

    To further understand the catalytic role of the protein environment in the enzymatic process, the author has analyzed the reaction mechanism of the Claisen rearrangement of Bacillus subtilis chorismate mutase (BsCM). By introducing a new computational strategy that combines all-electron QM calculations with ab initio QM/MM modelings, it was possible to simulate the molecular interactions between the substrate and the protein environment. The electrostatic nature of the transition state stabilization was characterized by performing all-electron QM calculations based on the fragment molecular orbital technique for the entire enzyme.

  12. Superior adsorption of pharmaceutical molecules by highly porous BN nanosheets.

    PubMed

    Liu, Dan; Lei, Weiwei; Qin, Si; Klika, Karel D; Chen, Ying

    2016-01-01

    Highly porous boron nitride nanosheets (BNNSs) were tested as a re-usable adsorbent for the removal of pharmaceuticals from aqueous solution. The BNNSs exhibit both unprecedentedly high adsorption capacities and excellent recyclability while maintaining their high adsorption capacity by a simple regeneration process. These advantages render BNNSs a promising material for water remediation applications. PMID:26618906

  13. Adsorption of phenolic compound by aged-refuse.

    PubMed

    Xiaoli, Chai; Youcai, Zhao

    2006-09-01

    The adsorption of phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol by aged-refuse has been studied. Adsorption isotherms have been determined for phenol, 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol and the data fits well to the Freundlich equation. The chlorinated phenols are absorbed more strongly than the phenol and the adsorption capacity has an oblivious relationship with the numbers and the position of chlorine subsistent. The experiment data suggests that both the partition function and the chemical adsorption involve in the adsorption process. Pseudo-first-order and pseudo-second-order model were applied to investigate the kinetics of the adsorption and the results show that it fit the pseudo-second-order model. More than one step involves in the adsorption process and the overall rate of the adsorption process appears to be controlled by the chemical reaction. The thermodynamic analysis indicates that the adsorption is spontaneous and endothermic.

  14. Choosing a density functional for modeling adsorptive hydrogen storage: reference quantum mechanical calculations and a comparison of dispersion-corrected density functionals.

    PubMed

    Kocman, Mikuláš; Jurečka, Petr; Dubecký, Matúš; Otyepka, Michal; Cho, Yeonchoo; Kim, Kwang S

    2015-03-01

    Hydrogen storage in carbonaceous materials and their derivatives is currently a widely investigated topic. The rational design of novel adsorptive materials is often attempted with the help of computational chemistry tools, in particular density functional theory (DFT). However, different exchange-correlation functionals provide a very wide range of hydrogen binding energies. The aim of this article is to offer high level QM reference data based on coupled-cluster singles and doubles calculations with perturbative triple excitations, CCSD(T), and a complete basis set limit estimate that can be used to assess the accuracy of various DFT-based predictions. For one complex, the CCSD(T) result is verified against diffusion quantum Monte Carlo calculations. Reference binding curves are calculated for two model compounds representing weak and strong hydrogen adsorption: coronene (-4.7 kJ mol(-1) per H2), and coronene modified with boron and lithium (-14.3 kJ mol(-1)). The reference data are compared to results obtained with widely used density functionals including pure DFT, M06, DFT-D3, PBE-TS, PBE + MBD, optB88-vdW, vdW-DF, vdW-DF2 and VV10. We find that whereas DFT-D3 shows excellent results for weak hydrogen adsorption on coronene, most of the less empirical density based dispersion functionals except VV10 overestimate this interaction. On the other hand, some of the less empirical density based dispersion functionals better describe stronger binding in the more polar coroB2Li22H2 complex which is one of realistic models for high-capacity hydrogen storage materials. Our results may serve as a guide for choosing suitable DFT methods for quickly evaluating hydrogen binding potential and as a reference for assessing the accuracy of the previously published DFT results.

  15. Ab initio quantum chemical and mixed quantum mechanics/molecular mechanics (QM/MM) methods for studying enzymatic catalysis.

    PubMed

    Friesner, Richard A; Guallar, Victor

    2005-01-01

    We describe large scale ab initio quantum chemical and mixed quantum mechanics/molecular mechanics (QM/MM) methods for studying enzymatic reactions. First, technical aspects of the methodology are reviewed, including the hybrid density functional theory (DFT) methods that are typically employed for the QM aspect of the calculations, and various approaches to defining the interface between the QM and MM regions in QM/MM approaches. The modeling of the enzymatic catalytic cycle for three examples--methane monooxygenase, cytochrome P450, and triose phosphate isomerase--are discussed in some depth, followed by a brief summary of other systems that have been investigated by ab initio methods over the past several years. Finally, a discussion of the qualitative and quantitative conclusions concerning enzymatic catalysis that are available from modern ab initio approaches is presented, followed by a conclusion briefly summarizing future prospects.

  16. Calculating hyperfine couplings in large ionic crystals containing hundreds of QM atoms: subsystem DFT is the key.

    PubMed

    Kevorkyants, Ruslan; Wang, Xiqiao; Close, David M; Pavanello, Michele

    2013-11-14

    We present an application of the linear scaling frozen density embedding (FDE) formulation of subsystem DFT to the calculation of isotropic hyperfine coupling constants (hfcc's) of atoms belonging to a guanine radical cation embedded in a guanine hydrochloride monohydrate crystal. The model systems range from an isolated guanine to a 15,000 atom QM/MM cluster where the QM region is comprised of 36 protonated guanine cations, 36 chlorine anions, and 42 water molecules. Our calculations show that the embedding effects of the surrounding crystal cannot be reproduced by small model systems nor by a pure QM/MM procedure. Instead, a large QM region is needed to fully capture the complicated nature of the embedding effects in this system. The unprecedented system size for a relativistic all-electron isotropic hfcc calculation can be approached in this work because the local nature of the electronic structure of the organic crystals considered is fully captured by the FDE approach.

  17. PUPIL: A Software Integration System for Multi-Scale QM/MM-MD Simulations and Its Application to Biomolecular Systems.

    PubMed

    Torras, Juan; Roberts, Benjamin P; Seabra, Gustavo M; Trickey, Samuel B

    2015-01-01

    PUPIL (Program for User Package Interfacing and Linking) implements a distinctive multi-scale approach to hybrid quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations. Originally developed to interface different external programs for multi-scale simulation with applications in the materials sciences, PUPIL is finding increasing use in the study of complex biological systems. Advanced MD techniques from the external packages can be applied readily to a hybrid QM/MM treatment in which the forces and energy for the QM region can be computed by any of the QM methods available in any of the other external packages. Here, we give a survey of PUPIL design philosophy, main features, and key implementation decisions, with an orientation to biomolecular simulation. We discuss recently implemented features which enable highly realistic simulations of complex biological systems which have more than one active site that must be treated concurrently. Examples are given.

  18. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test

    SciTech Connect

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-15

    Highlights: • Equilibrium test was attempted to evaluate adsorption characteristics of siloxane. • L2 had higher removal efficiency in carbon compared to noncarbon adsorbents. • Total adsorption capacity of siloxane was 300 mg/g by coal activated carbon. • Adsorption characteristics rely on size of siloxane molecule and adsorbent pore. • Conversion of siloxane was caused by adsorption of noncarbon adsorbents. - Abstract: Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

  19. Protein Adsorption in Three Dimensions

    PubMed Central

    Vogler, Erwin A.

    2011-01-01

    Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

  20. QSAR and QM/MM approaches applied to drug metabolism prediction.

    PubMed

    Braga, R C; Andrade, C H

    2012-06-01

    In modern drug discovery process, ADME/Tox properties should be determined as early as possible in the test cascade to allow a timely assessment of their property profiles. To help medicinal chemists in designing new compounds with improved pharmacokinetics, the knowledge of the soft spot position or the site of metabolism (SOM) is needed. In recent years, large number of in silico approaches for metabolism prediction have been developed and reported. Among these methods, QSAR models and combined quantum mechanics/molecular mechanics (QM/MM) methods for predicting drug metabolism have undergone significant advances. This review provides a perspective of the utility of QSAR and QM/MM approaches on drug metabolism prediction, highlighting the present challenges, limitations, and future perspectives in medicinal chemistry.

  1. Induced fit docking, and the use of QM/MM methods in docking.

    PubMed

    Xu, Mengang; Lill, Markus A

    2013-09-01

    Docking methods are popular computational techniques in drug discovery to identify new active molecules that bind to a given biological target. Although widely used, the predictive reliability of docking methods is often limited by the inability to accurately and efficiently model protein flexibility and quantify binding strength. We highlight several emerging concepts that address those methodological issues including a discussion on the incorporation of QM/MM methodologies in the scoring process.

  2. Recent advances in QM/MM free energy calculations using reference potentials☆

    PubMed Central

    Duarte, Fernanda; Amrein, Beat A.; Blaha-Nelson, David; Kamerlin, Shina C.L.

    2015-01-01

    Background Recent years have seen enormous progress in the development of methods for modeling (bio)molecular systems. This has allowed for the simulation of ever larger and more complex systems. However, as such complexity increases, the requirements needed for these models to be accurate and physically meaningful become more and more difficult to fulfill. The use of simplified models to describe complex biological systems has long been shown to be an effective way to overcome some of the limitations associated with this computational cost in a rational way. Scope of review Hybrid QM/MM approaches have rapidly become one of the most popular computational tools for studying chemical reactivity in biomolecular systems. However, the high cost involved in performing high-level QM calculations has limited the applicability of these approaches when calculating free energies of chemical processes. In this review, we present some of the advances in using reference potentials and mean field approximations to accelerate high-level QM/MM calculations. We present illustrative applications of these approaches and discuss challenges and future perspectives for the field. Major conclusions The use of physically-based simplifications has shown to effectively reduce the cost of high-level QM/MM calculations. In particular, lower-level reference potentials enable one to reduce the cost of expensive free energy calculations, thus expanding the scope of problems that can be addressed. General significance As was already demonstrated 40 years ago, the usage of simplified models still allows one to obtain cutting edge results with substantially reduced computational cost. This article is part of a Special Issue entitled Recent developments of molecular dynamics. PMID:25038480

  3. QM/MM Analysis of Cellulase Active Sites and Actions of the Enzymes on Substrates

    SciTech Connect

    Saharay, Moumita; Guo, Hao-Bo; Smith, Jeremy C; Guo, Hong

    2010-01-01

    Biodegradation of cellulosic biomass requires the actions of three types of secreted enzymes; endoglucanase (EC 3.2.1.4), cellobiohydrolase or exoglucanase (EC 3.2.1.91), and -glucosidase (EC 4.2.1.21). These enzymes act synergistically to hydrolyse the -1,4 bonds of cellulose and converts it into simple sugar. Hydrolysis of the glycosidic bond can occur either by net retention or by inversion of anomeric configuration at the anomeric center. QM/MM simulations are useful tools to study the energetics of the reactions and analyze the active-site structures at different states of the catalysis, including the formation of unstable transition states. Here, a brief description of previous work on glycoside hydrolases is first given. The results of the QM/MM potential energy and free energy simulations corresponding to glycosylation and deglycosylation processes are then provided for two retaining endoglucanases, Cel12A and Cel5A. The active-site structural features are analyzed based on the QM/MM results. The role of different residues and hydrogen bonding interactions during the catalysis and the importance of the sugar ring distortion are discussed for these two enzymes.

  4. QuanPol: a full spectrum and seamless QM/MM program.

    PubMed

    Thellamurege, Nandun M; Si, Dejun; Cui, Fengchao; Zhu, Hongbo; Lai, Rui; Li, Hui

    2013-12-15

    The quantum chemistry polarizable force field program (QuanPol) is implemented to perform combined quantum mechanical and molecular mechanical (QM/MM) calculations with induced dipole polarizable force fields and induced surface charge continuum solvation models. The QM methods include Hartree-Fock method, density functional theory method (DFT), generalized valence bond theory method, multiconfiguration self-consistent field method, Møller-Plesset perturbation theory method, and time-dependent DFT method. The induced dipoles of the MM atoms and the induced surface charges of the continuum solvation model are self-consistently and variationally determined together with the QM wavefunction. The MM force field methods can be user specified, or a standard force field such as MMFF94, Chemistry at Harvard Molecular Mechanics (CHARMM), Assisted Model Building with Energy Refinement (AMBER), and Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). Analytic gradients for all of these methods are implemented so geometry optimization and molecular dynamics (MD) simulation can be performed. MD free energy perturbation and umbrella sampling methods are also implemented.

  5. Novel sandwich structure adsorptive membranes for removal of 4-nitrotoluene from water.

    PubMed

    Guo, Yuexin; Jia, Zhiqian

    2016-11-01

    Novel sandwich PES-SPES/PS-PDVB/PTFE adsorptive membranes were prepared by a filtration/immersion precipitation method and employed for the removal of 4-nitrotoluene from water. The static adsorption thermodynamics, kinetics, dynamic adsorption/desorption and membrane reusability were investigated. The results showed that the Freundlich model describes the adsorption isotherm satisfactorily. With increased PS-PDVB content, the maximum static adsorption capacity, partition coefficient, apparent adsorption rate constant, and dynamic adsorption capacity all significantly increased. The sandwich membranes showed much higher removal efficiency and adsorption capacity than those of mixed matrix membranes. With respect to dynamics adsorption/desorption, the sandwich membranes exhibited excellent reusability, with a removal efficiency greater than 95% even after five recycles. PMID:27322899

  6. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    PubMed

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

  7. COMPETITIVE ADSORPTION OF VOCS AND BOM: THE ROLE OF MOLECULAR OXYGEN

    EPA Science Inventory

    In this study, the presence of background organic matter (BOM) was seen to reduce the adsorptive capacity of carbon for chloroform, chlorobenzene, and dibromochloropropane. Adsorption of these compounds was further reduced under oxic conditions. This additional reduction in cap...

  8. Fluorocarbon Adsorption in Hierarchical Porous Frameworks

    SciTech Connect

    Motkuri, Radha K.; Annapureddy, Harsha V.; Vijayakumar, M.; Schaef, Herbert T.; Martin, P F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-09

    The adsorption behavior of a series of fluorocarbon derivatives was examined on a set of microporous metal organic framework (MOF) sorbents and another set of hierarchical mesoporous MOFs. The microporous M-DOBDC (M = Ni, Co) showed a saturation uptake capacity for R12 of over 4 mmol/g at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous MOF MIL-101 showed an exceptionally high uptake capacity reaching over 14 mmol/g at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption were found to generally correlate with the polarizability of the refrigerant with R12 > R22 > R13 > R14 > methane. These results suggest the possibility of exploiting MOFs for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling and refrigeration applications.

  9. Phosphate adsorption on aluminum-coordinated functionalized macroporous–mesoporous silica: Surface structure and adsorption behavior

    SciTech Connect

    Huang, Weiya; Li, Dan; Zhu, Yi; Xu, Kai; Li, Jianqiang; Han, Boping; Zhang, Yuanming

    2013-12-15

    Graphical abstract: - Highlights: • Al-coordinated functionalized macroporous–mesoporous silica for phosphate removal. • It had the maximum adsorption capacity of 23.59 mg P/g. • Over 95% of the final adsorption capacity reached in the first 1 min. - Abstract: In this study, Al(III)-coordinated diamino-functionalized macroporous–mesoporous silica was synthesized and characterized by X-ray diffraction, N{sub 2} adsorption–desorption, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy. Because of well-defined and interconnecting macroporous–mesoporous networks, the resulting adsorbent (MM-SBA) exhibited a significantly better phosphate adsorption performance and faster removal rate, as compared with the mesoporous adsorbent (M-SBA). Based on the Freundlich and Langmuir models, the phosphate adsorption capacity and the maximum adsorption capacity of MM-SBA were 7.99 mg P/g and 23.59 mg P/g, respectively. In the kinetic study of MM-SBA, over 95% of its final adsorption capacity reached in the first 1 min; whereas that of M-SBA was less than 79%.

  10. Kinetic and thermodynamic studies of sulforaphane adsorption on macroporous resin.

    PubMed

    Yuanfeng, Wu; Lei, Zhang; Jianwei, Mao; Shiwang, Liu; Jun, Huang; Yuru, You; Lehe, Mei

    2016-08-15

    The adsorption equilibrium, kinetic and thermodynamic of sulforaphane (SF) adsorption onto macroporous resin in aqueous phase were studied. The SP850 resin was screened as the appropriate resin for SF purification. From the equilibrium studies, the Redlich-Peterson model was found to be the best for description of the adsorption behavior of SF onto SP850 resin, followed by the Freundlich model and the Langmuir model. Batch equilibrium experiments demonstrated that, in the examined temperature range, the equilibrium adsorption capacity of SP850 resin decreased with increasing adsorption temperature. Thermodynamics studies indicated that the adsorption of SF was a physical, exothermic, and spontaneous process. The adsorption kinetics revealed that the pseudo-second-order kinetic model was suitable to characterize the kinetics of adsorption of SF onto SP850. Finally, the intra-particle diffusion model demonstrated that SF diffused quickly into macropores, and that diffusion slowed down in the meso- and micropores. PMID:27391585

  11. Adsorption of thorium from aqueous solutions by perlite.

    PubMed

    Talip, Z; Eral, M; Hiçsönmez, U

    2009-02-01

    The use of expanded perlite for the adsorption of thorium from aqueous solution by batch technique is presented. The effects of particle size, pH of the solution, initial thorium concentration, shaking time, V/m ratio and temperature were determined. It was found that the adsorption capacity increases by the increase in the pH of the suspensions. The rate of thorium adsorption on expanded perlite was observed to be fast in the first hour of the reaction time. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models and the adsorption experiments conducted at 30 +/- 1 degrees C showed that the adsorption isotherms correlated well with the Langmuir model. From the adsorption data, thermodynamic parameters such as DeltaG(o), DeltaH(o) and DeltaS(o) were calculated as a function of temperature.

  12. Competitive adsorption of heavy metals onto sesame straw biochar in aqueous solutions.

    PubMed

    Park, Jong-Hwan; Ok, Yong Sik; Kim, Seong-Heon; Cho, Ju-Sik; Heo, Jong-Soo; Delaune, Ronald D; Seo, Dong-Cheol

    2016-01-01

    Objective of this research was to evaluate adsorption of heavy metals in mono and multimetal forms onto sesame straw biochar (SSB). Competitive sorption of metals by SSB has never been reported previously. The maximum adsorption capacities (mgg(-1)) of metals by SSB were in the order of Pb (102)≫Cd (86)≫Cr (65)>Cu (55)≫Zn (34) in the monometal adsorption isotherm and Pb (88)≫Cu (40)≫Cr (21)>Zn (7)⩾Cd (5) in the multimetal adsorption isotherm. Based on data obtained from the distribution coefficients, Freundlich and Langmuir adsorption models, and three-dimensional simulation, multimetal adsorption behaviors differed from monometal adsorption due to competition. Especially, during multimetal adsorption, Cd was easily exchanged and substituted by other metals. Further competitive adsorption studies are necessary in order to accurately estimate the heavy metal adsorption capacity of biochar in natural environments.

  13. Investigation into the Use of the Concept Laser QM System as an In-Situ Research and Evaluation Tool

    NASA Technical Reports Server (NTRS)

    Bagg, Stacey

    2014-01-01

    The NASA Marshall Space Flight Center (MSFC) is using a Concept Laser Fusing (Cusing) M2 powder bed additive manufacturing system for the build of space flight prototypes and hardware. NASA MSFC is collecting and analyzing data from the M2 QM Meltpool and QM Coating systems for builds. This data is intended to aide in understanding of the powder-bed additive manufacturing process, and in the development of a thermal model for the process. The QM systems are marketed by Concept Laser GmbH as in-situ quality management modules. The QM Meltpool system uses both a high-speed near-IR camera and a photodiode to monitor the melt pool generated by the laser. The software determines from the camera images the size of the melt pool. The camera also measures the integrated intensity of the IR radiation, and the photodiode gives an intensity value based on the brightness of the melt pool. The QM coating system uses a high resolution optical camera to image the surface after each layer has been formed. The objective of this investigation was to determine the adequacy of the QM Meltpool system as a research instrument for in-situ measurement of melt pool size and temperature and its applicability to NASA's objectives in (1) Developing a process thermal model and (2) Quantifying feedback measurements with the intent of meeting quality requirements or specifications. Note that Concept Laser markets the system only as capable of giving an indication of changes between builds, not as an in-situ research and evaluation tool. A secondary objective of the investigation is to determine the adequacy of the QM Coating system as an in-situ layer-wise geometry and layer quality evaluation tool.

  14. Adsorption behavior of alpha -cypermethrin on cork and activated carbon.

    PubMed

    Domingues, Valentina F; Priolo, Giuseppe; Alves, Arminda C; Cabral, Miguel F; Delerue-Matos, Cristina

    2007-08-01

    Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.

  15. [Fluoride adsorption form drinking water by granular lanthanum alginate].

    PubMed

    Huo, Ya-Kun; Ding, Wen-Ming; Huang, Xia

    2010-11-01

    Granular lanthanum alginate was prepared by dripping solved sodium alginate into lanthanum chloride solution. After washed and dried, sorbent with 1-1.5 mm diameter, 25% (mass fraction) La content was made and applied for fluoride removal from drinking test. Adsorption performance such as adsorption rate, adsorption isotherm, pH and disturbing ions effects were tested in batch adsorption. The changes of adsorbent surface and the solution composition before and after adsorption were also studied. Results showed that the adsorption rate was fast, fluoride concentration trend to stable after 2h reaction, and the adsorption rate fit for pseudo second order equation. The adsorption was significantly affected by pH and some disturbing ions, optimum pH = 4, phosphate and carbonate reduced adsorption. Adsorption isotherm fitted Langmuir equation well; the max adsorption capacity was 197.2 mg x g(-1). SEM photographs of sorbent before and after adsorption showed significantly different surface morphology; EDX composition analysis of sorbent surface and solution concentration changes before and after adsorption showed that ion exchange take placed between solution F- and sorbent surface Cl- and OH-.

  16. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.

    PubMed

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-01

    Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

  17. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.

    PubMed

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-01

    Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane. PMID:23684695

  18. The CHARMM-TURBOMOLE interface for efficient and accurate QM/MM molecular dynamics, free energies, and excited state properties.

    PubMed

    Riahi, Saleh; Rowley, Christopher N

    2014-10-30

    The quantum mechanical (QM)/molecular mechanical (MM) interface between Chemistry at HARvard Molecular Mechanics (CHARMM) and TURBOMOLE is described. CHARMM provides an extensive set of simulation algorithms, like molecular dynamics (MD) and free energy perturbation, and support for mature nonpolarizable and Drude polarizable force fields. TURBOMOLE provides fast QM calculations using density functional theory or wave function methods and excited state properties. CHARMM-TURBOMOLE is well-suited for extended QM/MM MD simulations using first principles methods with large (triple-ζ) basis sets. We demonstrate these capabilities with a QM/MM simulation of Mg(2+) (aq), where the MM outer sphere water molecules are represented using the SWM4-NDP Drude polarizable force field and the ion and inner coordination sphere are represented using QM PBE, PBE0, and MP2 methods. The relative solvation free energies of Mg(2+) and Zn(2+) were calculated using thermodynamic integration. We also demonstrate the features for excited state properties. We calculate the time-averaged solution absorption spectrum of indole, the emission spectrum of the indole 1La excited state, and the electronic circular dichroism spectrum of an oxacepham.

  19. Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path–Force Matching QM/MM Method

    PubMed Central

    Zhou, Y.; Ojeda-May, P.; Nagaraju, M.; Pu, J.

    2016-01-01

    Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path–force matching (RP–FM) has been developed. In RP–FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP–FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

  20. Clinical Decision Support-based Quality Measurement (CDS-QM) Framework: Prototype Implementation, Evaluation, and Future Directions

    PubMed Central

    Kukhareva, Polina V; Kawamoto, Kensaku; Shields, David E; Barfuss, Darryl T; Halley, Anne M; Tippetts, Tyler J; Warner, Phillip B; Bray, Bruce E; Staes, Catherine J

    2014-01-01

    Electronic quality measurement (QM) and clinical decision support (CDS) are closely related but are typically implemented independently, resulting in significant duplication of effort. While it seems intuitive that technical approaches could be re-used across these two related use cases, such reuse is seldom reported in the literature, especially for standards-based approaches. Therefore, we evaluated the feasibility of using a standards-based CDS framework aligned with anticipated EHR certification criteria to implement electronic QM. The CDS-QM framework was used to automate a complex national quality measure (SCIP-VTE-2) at an academic healthcare system which had previously relied on time-consuming manual chart abstractions. Compared with 305 manually-reviewed reference cases, the recall of automated measurement was 100%. The precision was 96.3% (CI:92.6%-98.5%) for ascertaining the denominator and 96.2% (CI:92.3%-98.4%) for the numerator. We therefore validated that a standards-based CDS-QM framework can successfully enable automated QM, and we identified benefits and challenges with this approach. PMID:25954389

  1. Toward Determining ATPase Mechanism in ABC Transporters: Development of the Reaction Path-Force Matching QM/MM Method.

    PubMed

    Zhou, Y; Ojeda-May, P; Nagaraju, M; Pu, J

    2016-01-01

    Adenosine triphosphate (ATP)-binding cassette (ABC) transporters are ubiquitous ATP-dependent membrane proteins involved in translocations of a wide variety of substrates across cellular membranes. To understand the chemomechanical coupling mechanism as well as functional asymmetry in these systems, a quantitative description of how ABC transporters hydrolyze ATP is needed. Complementary to experimental approaches, computer simulations based on combined quantum mechanical and molecular mechanical (QM/MM) potentials have provided new insights into the catalytic mechanism in ABC transporters. Quantitatively reliable determination of the free energy requirement for enzymatic ATP hydrolysis, however, requires substantial statistical sampling on QM/MM potential. A case study shows that brute force sampling of ab initio QM/MM (AI/MM) potential energy surfaces is computationally impractical for enzyme simulations of ABC transporters. On the other hand, existing semiempirical QM/MM (SE/MM) methods, although affordable for free energy sampling, are unreliable for studying ATP hydrolysis. To close this gap, a multiscale QM/MM approach named reaction path-force matching (RP-FM) has been developed. In RP-FM, specific reaction parameters for a selected SE method are optimized against AI reference data along reaction paths by employing the force matching technique. The feasibility of the method is demonstrated for a proton transfer reaction in the gas phase and in solution. The RP-FM method may offer a general tool for simulating complex enzyme systems such as ABC transporters. PMID:27498639

  2. Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies.

    PubMed

    Sodt, Alexander J; Mei, Ye; König, Gerhard; Tao, Peng; Steele, Ryan P; Brooks, Bernard R; Shao, Yihan

    2015-03-01

    In combined quantum mechanical/molecular mechanical (QM/MM) free energy calculations, it is often advantageous to have a frozen geometry for the quantum mechanical (QM) region. For such multiple-environment single-system (MESS) cases, two schemes are proposed here for estimating the polarization energy: the first scheme, termed MESS-E, involves a Roothaan step extrapolation of the self-consistent field (SCF) energy; whereas the other scheme, termed MESS-H, employs a Newton-Raphson correction using an approximate inverse electronic Hessian of the QM region (which is constructed only once). Both schemes are extremely efficient, because the expensive Fock updates and SCF iterations in standard QM/MM calculations are completely avoided at each configuration. They produce reasonably accurate QM/MM polarization energies: MESS-E can predict the polarization energy within 0.25 kcal/mol in terms of the mean signed error for two of our test cases, solvated methanol and solvated β-alanine, using the M06-2X or ωB97X-D functionals; MESS-H can reproduce the polarization energy within 0.2 kcal/mol for these two cases and for the oxyluciferin-luciferase complex, if the approximate inverse electronic Hessians are constructed with sufficient accuracy.

  3. Refined models of New Delhi metallo-beta-lactamase-1 with inhibitors: an QM/MM modeling study.

    PubMed

    Wang, Yeng-Tseng; Cheng, Tian-Lu

    2016-10-01

    New Delhi metallo-beta-lactamase 1 (NDM-1) has been identified as a potential target for the treatment of multi-drug resistance bacterial infections. We used molecular docking, normal MD, SIE, QM/MM MD simulations, QM/MM GBSA binding free energy, and QM/MM GBSA alanine-scanning mutagenesis techniques to investigate interactions of the NDM-1 with 11 inhibitors (Tigecycline, BAL30072, D-captopril, Penicillin G, Ampicillin, Carbenicillin, Cephalexin, Cefaclor, Nitrocefin, Meropenem, and Imipenem). From our normal MD and QM/MM simulations, the correlation coefficients between the predicted binding free energies and experimental values are .88 and .93, respectively. Then simulations, which combined QM/MM/GBSA and alanine-scanning mutagenesis techniques, were performed and our results show that two residues (Lys211 and His250) have the strongest impact on the binding affinities of the 11 NDM-1/inhibitors. Therefore, our approach theoretically suggests that the two residues (Lys211 and His250) are responsible for the selectivity of NDM-1 associated inhibitors. PMID:26488313

  4. A Comparison of Transfer Hamiltonian vs. DFT Methods in QM/CM Multi-Scale Modeling

    NASA Astrophysics Data System (ADS)

    Mallik, Aditi; Runge, Keith; Cheng, Hai-Ping; Dufty, James

    2004-11-01

    A method for a consistent embedding of a quantum (QM) domain in its classical (CM) environment has been developed for application in QM/CM simulations for multi-scale modeling. A benchmark system is considered: a silica nanorod in which a part of the rod is treated quantum mechanically and the rest is treated classically. This system is chosen because a full ab initio quantum data can be obtained for the entire rod to assess the quality of the proposed embedding technique. However, even at the quantum level each possible choice for the ab initio method entails approximations used to optimize the accuracy and speed of the calculations. Each approximation has its own advantages and limitations, but the embedding scheme should be insensitive to these. In order to test how robust our proposed embedding scheme is, we have chosen two different methods for the underlying quantum mechanical description. The first method used is the Transfer Hamiltonian (TH) Neglect of Diatomic Differential Overlap (NDDO) (Bartlett, 2003). The TH method uses a semi empirical Hamiltonian that has been parameterized to yield coupled cluster quality forces, thereby taking electron correlations into account like post-Hartree Fock methods. The second method used is the Born-Oppenheimer local spin density (Barnett and Landman, 1993) within density functional theory (DFT) and generalized gradient approximation (GGA). We use the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional. Here, the embedding method and resulting QM/CM composite rods using the two different ab initio methods are compared for the silica nanorod. It is found that the two quantum rods have noticeable differences, although the embedding method for the equilibrium composite rods is faithful to the underlying quantum method in each case. Nonequilibrium elastic properties are discussed briefly.

  5. The ESR model: A proposal for a noncontextual and local Hilbert space extension of QM

    NASA Astrophysics Data System (ADS)

    Garola, C.; Sozzo, S.

    2009-04-01

    The extended semantic realism (ESR) model proposes a new theoretical perspective that embodies the mathematical formalism of standard (Hilbert space) quantum mechanics (QM) in a noncontextual framework, reinterpreting quantum probabilities as conditional instead of absolute. We provide here a Hilbert space representation of the generalized observables introduced by the ESR model. By using this representation, we supply a straightforward generalization of the projection postulate and justify it in the case of discrete generalized observables by introducing a reasonable physical assumption on the evolution of the compound system made up of the (microscopic) measured system and the (macroscopic) measuring apparatus.

  6. GPU Accelerated Implementation of Density Functional Theory for Hybrid QM/MM Simulations.

    PubMed

    Nitsche, Matías A; Ferreria, Manuel; Mocskos, Esteban E; González Lebrero, Mariano C

    2014-03-11

    The hybrid simulation tools (QM/MM) evolved into a fundamental methodology for studying chemical reactivity in complex environments. This paper presents an implementation of electronic structure calculations based on density functional theory. This development is optimized for performing hybrid molecular dynamics simulations by making use of graphic processors (GPU) for the most computationally demanding parts (exchange-correlation terms). The proposed implementation is able to take advantage of modern GPUs achieving acceleration in relevant portions between 20 to 30 times faster than the CPU version. The presented code was extensively tested, both in terms of numerical quality and performance over systems of different size and composition. PMID:26580175

  7. A comparison of three adsorption equations and sensitivity study of parameter uncertainty effects on adsorption refrigeration thermal performance estimation

    NASA Astrophysics Data System (ADS)

    Zhao, Yongling; Hu, Eric; Blazewicz, Antoni

    2012-02-01

    This paper presents isosteric-based adsorption equilibrium tests of three activated carbon samples with methanol as an adsorbate. Experimental data was fitted into Langmuir equation, Freundlich equation and Dubinin-Astakov (D-A) equation, respectively. The fitted adsorption equations were compared in terms of agreement with experimental data. Moreover, equation format's impacts on calculation of the coefficient of performance (COP) and refrigeration capacity of an adsorption refrigeration system was analyzed. In addition, the sensitivity of each parameter in each adsorption equation format to the estimation of cycle's COP and refrigeration capacity was investigated. It was found that the D-A equation is the best form for presenting the adsorptive property of a carbon-methanol working pair. The D-A equation is recommended for estimating thermal performance of an adsorption refrigeration system because simulation results obtained using the D-A equation are less sensitive to errors of experimentally determined D-A equation's parameters.

  8. New insight into the biological treatment by activated sludge: the role of adsorption process.

    PubMed

    Zhang, Xiaochun; Li, Xinrun; Zhang, Qingrui; Peng, Qiuming; Zhang, Wen; Gao, Faming

    2014-02-01

    The objective of this study was to evaluate the effect of adsorption on the biological treatment process of wastewater. In the absence of substrate in the water, activated sludge developed well in the first hour, indicating that the growth of microorganism was not directly related to substrate concentration and the dissolved organic matter in the water assays were performed, no organic matter was detected out, revealing that there was no desorption in the activated sludge adsorption process. Activated sludge batch growth experiments in the presence of different adsorption capacities indicated that specific growth rate increased as specific adsorption capacity increased. The experiment on the relationship of adsorption capacity and substrate concentration or sludge concentration was also carried out. Specific adsorption capacity increased as sludge load increased, presenting linear correlation. The experiment results showed that adsorption should be taken into account in the study of the biological treatment process of wastewater.

  9. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  10. Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene

    SciTech Connect

    Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin; Xia, Yanzhi; Xia, Linhua; Wang, Zonghua; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-08-15

    Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m{sup 2}/g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.

  11. Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers.

    PubMed

    Sun, Yue; Li, Xiao-Tao; Xu, Chao; Chen, Jin-Long; Li, Ai-Min; Zhang, Quan-Xing

    2005-01-01

    Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

  12. Adsorption coefficients for TNT on soil and clay minerals

    NASA Astrophysics Data System (ADS)

    Rivera, Rosángela; Pabón, Julissa; Pérez, Omarie; Muñoz, Miguel A.; Mina, Nairmen

    2007-04-01

    To understand the fate and transport mechanisms of TNT from buried landmines is it essential to determine the adsorption process of TNT on soil and clay minerals. In this research, soil samples from horizons Ap and A from Jobos Series at Isabela, Puerto Rico were studied. The clay fractions were separated from the other soil components by centrifugation. Using the hydrometer method the particle size distribution for the soil horizons was obtained. Physical and chemical characterization studies such as cation exchange capacity (CEC), surface area, percent of organic matter and pH were performed for the soil and clay samples. A complete mineralogical characterization of clay fractions using X-ray diffraction analysis reveals the presence of kaolinite, goethite, hematite, gibbsite and quartz. In order to obtain adsorption coefficients (K d values) for the TNT-soil and TNT-clay interactions high performance liquid chromatography (HPLC) was used. The adsorption process for TNT-soil was described by the Langmuir model. A higher adsorption was observed in the Ap horizon. The Freundlich model described the adsorption process for TNT-clay interactions. The affinity and relative adsorption capacity of the clay for TNT were higher in the A horizon. These results suggest that adsorption by soil organic matter predominates over adsorption on clay minerals when significant soil organic matter content is present. It was found that, properties like cation exchange capacity and surface area are important factors in the adsorption of clayey soils.

  13. Defluoridation of drinking water using adsorption processes.

    PubMed

    Loganathan, Paripurnanda; Vigneswaran, Saravanamuthu; Kandasamy, Jaya; Naidu, Ravi

    2013-03-15

    Excessive intake of fluoride (F), mainly through drinking water, is a serious health hazard affecting humans worldwide. There are several methods used for the defluoridation of drinking water, of which adsorption processes are generally considered attractive because of their effectiveness, convenience, ease of operation, simplicity of design, and for economic and environmental reasons. In this paper, we present a comprehensive and a critical literature review on various adsorbents used for defluoridation, their relative effectiveness, mechanisms and thermodynamics of adsorption, and suggestions are made on choice of adsorbents for various circumstances. Effects of pH, temperature, kinetics and co-existing anions on F adsorption are also reviewed. Because the adsorption is very weak in extremely low or high pHs, depending on the adsorbent, acids or alkalis are used to desorb F and regenerate the adsorbents. However, adsorption capacity generally decreases with repeated use of the regenerated adsorbent. Future research needs to explore highly efficient, low cost adsorbents that can be easily regenerated for reuse over several cycles of operations without significant loss of adsorptive capacity and which have good hydraulic conductivity to prevent filter clogging during the fixed-bed treatment process.

  14. EFFECT OF GAC CHARACTERISTICS ON ADSORPTION OF ORGANIC POLLUTANTS

    EPA Science Inventory

    The impact of the characteristics of granular activated carbon (GAC) on adsorption capacity and on the potential for polymerization of phenolic compounds on the surface of GAC in the presence of molecular oxygen is evaluated in this study. Adsorption isotherm data were collected...

  15. Combined quantum mechanics/molecular mechanics (QM/MM) simulations for protein-ligand complexes: free energies of binding of water molecules in influenza neuraminidase.

    PubMed

    Woods, Christopher J; Shaw, Katherine E; Mulholland, Adrian J

    2015-01-22

    The applicability of combined quantum mechanics/molecular mechanics (QM/MM) methods for the calculation of absolute binding free energies of conserved water molecules in protein/ligand complexes is demonstrated. Here, we apply QM/MM Monte Carlo simulations to investigate binding of water molecules to influenza neuraminidase. We investigate five different complexes, including those with the drugs oseltamivir and peramivir. We investigate water molecules in two different environments, one more hydrophobic and one hydrophilic. We calculate the free-energy change for perturbation of a QM to MM representation of the bound water molecule. The calculations are performed at the BLYP/aVDZ (QM) and TIP4P (MM) levels of theory, which we have previously demonstrated to be consistent with one another for QM/MM modeling. The results show that the QM to MM perturbation is significant in both environments (greater than 1 kcal mol(-1)) and larger in the more hydrophilic site. Comparison with the same perturbation in bulk water shows that this makes a contribution to binding. The results quantify how electronic polarization differences in different environments affect binding affinity and also demonstrate that extensive, converged QM/MM free-energy simulations, with good levels of QM theory, are now practical for protein/ligand complexes.

  16. A Mixed Quantum Mechanics/Molecular Mechanics (qm/mm) Method for Large-Scale Modeling of Chemistry in Protein Environments

    SciTech Connect

    Murphy, Robert B.; Philipp, Dean M.; Friesner, Richard A.

    2000-07-13

    A QM/MM method, using our previously developed frozen orbital QM/MM interface methodology, is presented as a general, accurate, and computationally efficient model for studying chemical problems in a protein environment. The method, its parameterization, and a preliminary application to modeling cytochrome P-450 chemistry are presented.

  17. CPMD/GULP QM/MM interface for modeling periodic solids: Implementation and its application in the study of Y-zeolite supported Rhn clusters.

    PubMed

    Sahoo, Sudhir K; Nair, Nisanth N

    2016-07-01

    We report here the development of hybrid quantum mechanics/molecular mechanics (QM/MM) interface between the plane-wave density functional theory based CPMD code and the empirical force-field based GULP code for modeling periodic solids and surfaces. The hybrid QM/MM interface is based on the electrostatic coupling between QM and MM regions. The interface is designed for carrying out full relaxation of all the QM and MM atoms during geometry optimizations and molecular dynamics simulations, including the boundary atoms. Both Born-Oppenheimer and Car-Parrinello molecular dynamics schemes are enabled for the QM part during the QM/MM calculations. This interface has the advantage of parallelization of both the programs such that the QM and MM force evaluations can be carried out in parallel to model large systems. The interface program is first validated for total energy conservation and parallel scaling performance is benchmarked. Oxygen vacancy in α-cristobalite is then studied in detail and the results are compared with a fully QM calculation and experimental data. Subsequently, we use our implementation to investigate the structure of rhodium cluster (Rhn ; n = 2 to 6) formed from Rh(C2 H4 )2 complex adsorbed within a cavity of Y-zeolite in a reducible atmosphere of H2 gas. © 2016 Wiley Periodicals, Inc. PMID:27092962

  18. Study of Adsorption of Copper Species onto Multiwall Carbon Nanotubes

    EPA Science Inventory

    Functionalized CNTs have improved adsorptive capacities over pristine CNTs. These can be used for sensors, membranes, filters and matrix composite enhancements made possible because of their nano-size.

  19. Structural characterization of carbohydrate attached to the glycoprotein cellulase enzymes of Trichoderma reesei QM 9414

    SciTech Connect

    de Chasteigner du Mee, C.P.R.

    1984-01-01

    Cellobiohydrolases I(D) and II were purified by ion exchange chromatography from an extracellular culture filtrate of Tricoderma reesei QM 9414. Neutral sugar composition of each was determined by gas-liquid chromatographic analysis of the peracetylated alditol and aldononitrile acetate derivatives of sugars released by either reductive US -elimination or acid hydrolysis. The alkaline borohydride-released carbohydrate was analyzed by high-pressure liquid chromatography (HPLC). The HPLC data demonstrated that each molecule of cellobiohydrolase I(D) contained 5.9% carbohydrate and that cellobiohydrolase II contained 18.9% carbohydrate. The purified oligosaccharides were shown by methylation analysis to contain (1-2) and (1-6) glycosidic linkages and the position of the 6-substituted residues was confirmed by acetolysis. The sequence and anomeric nature of the sugar residues in each oligosaccharide was determined by sequential glycosidase digestion, and all the residues were found to be -linked. Proton decoupled TC-NMR analysis suggested that for cellobiohydrolase I(D), each oligosaccharide was attached to a threonyl residue on the polypeptide and for cellobiohydrolase II, each oligosaccharide was attached to threonyl and seryl residues on the polypeptides. Coupled TC-NMR and H-NMR data to define the structures of the oligosaccharides attached to the enzyme were determined and are reported. Thus, work with the cellobiohydrolases and the endoglucanases indicated that the predominant cellulase enzymes secreted by T. reesei QM 9414 are each glycosylated with similar oligosaccharides.

  20. Intermediates in dioxygen activation by methane monooxygenase: A QM/MM study

    PubMed Central

    Rinaldo, David; Philipp, Dean M.; Lippard, Stephen J.; Friesner, Richard A.

    2008-01-01

    Protein effects in the activation of dioxygen by methane monooxygenase (MMO) were investigated by using combined QM/MM and broken-symmetry Density Functional Theory (DFT) methods. The effects of a novel empirical scheme recently developed by our group on the relative DFT energies of the various intermediates in the catalytic cycle are investigated. Inclusion of the protein leads to much better agreement between the experimental and computed geometric structures for the reduced form (MMOHred). Analysis of the electronic structure of MMOHred reveals that the two iron atoms have distinct environments. Different coordination geometries tested for the MMOHperoxo intermediate reveal that, in the protein environment, the μ-η2,η2 structure is more stable than the others. Our analysis also shows that the protein helps to drive reactants towards products along the reaction path. Furthermore, these results demonstrate the importance of including the protein environment in our models and the usefulness of the QM/MM approach for accurate modeling of enzymatic reactions. A discrepancy remains in our calculation of the Fe-Fe distance in our model of HQ as compared to EXAFS data obtained several years ago, for which we currently do not have an explanation. PMID:17326634

  1. FT-Raman and QM/MM study of the interaction between histamine and DNA

    NASA Astrophysics Data System (ADS)

    Ruiz-Chica, A. J.; Soriano, A.; Tuñón, I.; Sánchez-Jiménez, F. M.; Silla, E.; Ramírez, F. J.

    2006-05-01

    The interaction between histamine and highly polymerized calf-thymus DNA has been investigated using FT-Raman spectroscopy and the hybrid QM/MM (quantum mechanics/molecular mechanics) methodology. Raman spectra of solutions containing histamine and calf-thymus DNA, at different molar ratios, were recorded. Solutions were prepared at physiological settings of pH and ionic strength, using both natural and heavy water as the solvent. The analysis of the spectral changes on the DNA Raman spectra when adding different concentrations of histamine allowed us to identify the reactive sites of DNA and histamine, which were used to built two minor groove and one intercalated binding models. They were further used as starting points of the QM/MM theoretical study. However, minimal energy points were only reached for the two minor groove models. For each optimized structure, we calculated analytical force constants of histamine molecule in order to perform the vibrational dynamics. Normal mode descriptions allowed us to compare calculated wavenumbers for DNA-interacting histamine to those measured in the Raman spectra of DNA-histamine solutions.

  2. QM/MM Protocol for Direct Molecular Dynamics of Chemical Reactions in Solution: The Water-Accelerated Diels-Alder Reaction.

    PubMed

    Yang, Zhongyue; Doubleday, Charles; Houk, K N

    2015-12-01

    We describe a solvent-perturbed transition state (SPTS) sampling scheme for simulating chemical reaction dynamics in condensed phase. The method, adapted from Truhlar and Gao's ensemble-averaged variational transition state theory, includes the effect of instantaneous solvent configuration on the potential energy surface of the reacting system (RS) and allows initial conditions for the RS to be sampled quasiclassically by TS normal mode sampling. We use a QM/MM model with direct dynamics, in which QM forces of the RS are computed at each trajectory point. The SPTS scheme is applied to the acceleration of the Diels-Alder reaction of cyclopentadiene (CP) + methyl vinyl ketone (MVK) in water. We explored the effect of the number of SPTS and of solvent box size on the distribution of bond lengths in the TS. Statistical sampling of the sampling was achieved when distribution of forming bond lengths converged. We describe the region enclosing the partial bond lengths as the transition zone. Transition zones in the gas phase, SMD implicit solvent, QM/MM, and QM/MM+QM (3 water molecules treated by QM) vary according to the ability of the medium to stabilize zwitterionic structures. Mean time gaps between formation of C-C bonds vary from 11 fs for gas phase to 25 fs for QM/MM+QM. Mean H-bond lengths to O(carbonyl) in QM/MM+QM are 0.14 Å smaller at the TS than in MVK reactant, and the mean O(carbonyl)-H(water)-O(water) angle of H-bonds at the TS is 10° larger than in MVK reactant.

  3. Characterization of biochars derived from agriculture wastes and their adsorptive removal of atrazine from aqueous solution: A comparative study.

    PubMed

    Liu, Na; Charrua, Alberto Bento; Weng, Chih-Huang; Yuan, Xiaoling; Ding, Feng

    2015-12-01

    The physicochemical properties of biochars produced from soybeans (SBB), corn stalks (CSB), rice stalks (RSB), poultry manure (PMB), cattle manure (CMB), and pig manure (PgMB) and their adsorption characteristics of atrazine were investigated. The adsorption capacity increased with the increase of temperature and initial atrazine concentration. More atrazine was removed from basic solutions than acidic solutions, due to the effects of adsorption and hydrolysis. The Freundlich isotherm adsorption parameters indicated that the adsorption capacity decreased in the order SBB>RSB>CMB>CSB>PMB>PgMB, which is associated to the pore volume of biochars. The total pore volume and biochar pH were concluded to play important roles in determining the adsorption capacity, and they may have contributed to physical adsorption mechanisms dominating the overall adsorption process (the low activation energy for all of the biochars). Modified Freundlich and intraparticle diffusion models were used to describe the kinetics of the adsorption process.

  4. Protein adsorption to multi-component glasses

    NASA Astrophysics Data System (ADS)

    Hall, Matthew Micah

    2003-07-01

    The adsorption of human serum albumin (HSA) to sodium silicate, soda lime silicate (SLS), and sodium aluminosilicate (SAS) glass microspheres was investigated using sodiumdodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) in conjunction with a colloidal silver stain for visualization. The 30 Na2O·70 SiO2 composition could not be evaluated due to an apparent chemical interference that occurred during silver staining. This inhibitory effect was attributed to the extensive corrosion that occurred during the protein elution and caused an elevation in the pH of the solution. The remaining glass compositions were sufficiently durable for further study. The HSA adsorption capacity of SLS glass microspheres containing 70 and 80 mol% SiO2 increased as CaO was substituted for Na2O. An abrupt decrease in the HSA adsorption capacity was observed for SLS glasses containing 60 mol% SiO2. A similar trend was observed for the SAS glass microspheres, although the SAS glasses adsorbed less HSA than the SLS glasses containing equivalent molar percentages of SiO2. The initial increase in HSA adsorption capacity for SLS and SAS glasses containing 70 and 80 MOM SiO2 was attributed to the introduction of positive charges into the glass surfaces via Ca2+ and Al3+ cations. The decrease in HSA adsorption capacity for SLS and SAS glasses containing 60 mol% SiO2 may be due to an enhanced affinity between the glasses and HSA, resulting in a "flattened" conformation that limits the total accessible area for adsorption.

  5. Progresses in Ab Initio QM/MM Free Energy Simulations of Electrostatic Energies in Proteins: Accelerated QM/MM Studies of pKa, Redox Reactions and Solvation Free Energies

    SciTech Connect

    Kamerlin, Shina C. L.; Haranczyk, Maciej; Warshel, Arieh

    2009-03-01

    Hybrid quantum mechanical / molecular mechanical (QM/MM) approaches have been used to provide a general scheme for chemical reactions in proteins. However, such approaches still present a major challenge to computational chemists, not only because of the need for very large computer time in order to evaluate the QM energy but also because of the need for propercomputational sampling. This review focuses on the sampling issue in QM/MM evaluations of electrostatic energies in proteins. We chose this example since electrostatic energies play a major role in controlling the function of proteins and are key to the structure-function correlation of biological molecules. Thus, the correct treatment of electrostatics is essential for the accurate simulation of biological systems. Although we will be presenting here different types of QM/MM calculations of electrostatic energies (and related properties), our focus will be on pKa calculations. This reflects the fact that pKa of ionizable groups in proteins provide one of the most direct benchmarks for the accuracy of electrostatic models of macromolecules. While pKa calculations by semimacroscopic models have given reasonable results in many cases, existing attempts to perform pKa calculations using QM/MM-FEP have led to large discrepancies between calculated and experimental values. In this work, we accelerate our QM/MM calculations using an updated mean charge distribution and a classical reference potential. We examine both a surface residue (Asp3) of the bovine pancreatic trypsin inhibitor, as well as a residue buried in a hydrophobic pocket (Lys102) of the T4-lysozyme mutant. We demonstrate that by using this approach, we are able to reproduce the relevant sidechain pKas with an accuracy of 3 kcal/mol. This is well within the 7 kcal/mol energy difference observed in studies of enzymatic catalysis, and is thus sufficient accuracy to determine the main contributions to the catalytic energies of enzymes. We also provide an

  6. Centrifugal Adsorption Cartridge System

    NASA Technical Reports Server (NTRS)

    Gonda, Steve R.; Tsao, Yow-Min D.; Lee, Wenshan

    2004-01-01

    The centrifugal adsorption cartridge system (CACS) is an apparatus that recovers one or more bioproduct(s) from a dilute aqueous solution or suspension flowing from a bioreactor. The CACS can be used both on Earth in unit gravity and in space in low gravity. The CACS can be connected downstream from the bioreactor; alternatively, it can be connected into a flow loop that includes the bioreactor so that the liquid can be recycled. A centrifugal adsorption cartridge in the CACS (see figure) includes two concentric cylinders with a spiral ramp between them. The volume between the inner and outer cylinders, and between the turns of the spiral ramp is packed with an adsorbent material. The inner cylinder is a sieve tube covered with a gas-permeable, hydrophobic membrane. During operation, the liquid effluent from the bioreactor is introduced at one end of the spiral ramp, which then constrains the liquid to flow along the spiral path through the adsorbent material. The spiral ramp also makes the flow more nearly uniform than it would otherwise be, and it minimizes any channeling other than that of the spiral flow itself. The adsorbent material is formulated to selectively capture the bioproduct(s) of interest. The bioproduct(s) can then be stored in bound form in the cartridge or else eluted from the cartridge. The centrifugal effect of the spiral flow is utilized to remove gas bubbles from the liquid. The centrifugal effect forces the bubbles radially inward, toward and through the membrane of the inner cylinder. The gas-permeable, hydrophobic membrane allows the bubbles to enter the inner cylinder while keeping the liquid out. The bubbles that thus enter the cylinder are vented to the atmosphere. The spacing between the ramps determines rate of flow along the spiral, and thereby affects the air-bubble-removal efficiency. The spacing between the ramps also determines the length of the fluid path through the cartridge adsorbent, and thus affects the bioproduct

  7. Heavy metal adsorption changes of EAF steel slag after phosphorus adsorption.

    PubMed

    Song, Guanling; Cao, Lijing; Chen, Xiao; Hou, Wenhua; Wang, Qunhui

    2012-01-01

    A kind of electric arc furnace (EAF) steel slag was phosphated, and its isothermal and dynamic adsorptions of copper, cadmium, and lead ions were measured to determine if heavy metal adsorption changes after phosphorus adsorption. The surface area increased greatly after the slag was phosphated. Isothermal adsorption experiments showed that the theoretical Q(max) of the EAF steel slag on Cu(2+), Cd(2+), and Pb(2+) improved 59, 50, and 89% respectively after it was phosphated. Dynamic adsorption results showed that the greatest adsorption capacities of unit volume of Cu(2+), Cd(2+), and Pb(2+) were 2.2, 1.8, and 1.8 times that of the column packed with original EAF steel slag when the column was packed with phosphate EAF steel slag at the same heavy metal ion concentration. The breakthrough time, the exhaustion time and elution efficiency of the column also increased when the column was packed with phosphated EAF steel slag compared with that packed with original EAF steel slag. Phosphorus adsorption could further improve the heavy metal ion adsorption of the EAF steel slag.

  8. Industrial water treatment, by adsorption, using organized mesoporous materials

    NASA Astrophysics Data System (ADS)

    Koubaissy, Bachar; Toufaily, Joumana; Kafrouny, Lina; Joly, Guy; Magnoux, Patrick; Hamieh, Tayssir

    In this work, pure silica SBA-15 was synthesized by a sol-gel method and in-situ functionalized by a series of organosilane. These mesoporous materials are used to absorb polluants from wastewater. We studied the influence of functional groups on adsorption of phenol drifts. The carboxylic acid groups and substituted chlorine on phenol have been studied. There is a sharp increase of adsorption (more than double compared to phenol) which is very encouraging. Furthermore we note that the percentage of grafted ligands also plays an important role in adsorption. Finally, the adsorption capacity also depends on the nature and percentage of ligands present.

  9. Removal of carbonyl sulfide using activated carbon adsorption.

    PubMed

    Sattler, Melanie L; Rosenberk, Ranjith Samuel

    2006-02-01

    Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.

  10. Assessing the Adsorption Properties of Shales

    NASA Astrophysics Data System (ADS)

    Pini, R.

    2014-12-01

    Fine-grained rocks, such as shales, contain a significant amount of nanopores that can significantly contribute to their storage capacity through the mechanism of adsorption. The current ability to extract natural gas that is adsorbed in the rock's matrix is limited and current technology focuses primarily on the free gas in the fractures, thus leading to very low recovery efficiencies. Shales constitute also a great portion of so-called caprocks above potential CO2 sequestration sites; hereby, the adsorption process may limit the CO2 mobility within the cap-rock, thus minimizing leakage phenomena. Whether it is a reservoir or a caprock, understanding and quantifying the mechanisms of adsorption in these natural materials is key to improve the engineering design of subsurface operations. Results will be presented from a laboratory study that combines conventional techniques for the measurement of adsorption isotherms with novel methods that allows for the imaging of adsorption using x-rays. Various nanoporous materials are considered, thus including rocks, such as shales and coals, pure clay minerals and engineered adsorbents with well-defined nanopore structures, such as zeolites. Supercritical CO2 adsorption isotherms have been measured with a Rubotherm Magnetic Suspension balance by covering the pressure range 0.1-20~MPa. A medical x-ray CT scanner has been used to identify three-dimensional patterns of the adsorption properties of a packed-bed of adsorbent, thus enabling to assess the spatial variability of the adsorption isotherm. The data are analyzed by using thermodynamically rigorous measures of adsorption and a graphical method is applied for their interpretation. The density of the adsorbed phase is estimated and compared to data reported in the literature; the latter is key to disclose gas-reserves and/or potential storage capacity estimates. When evaluated against classic adsorbent materials, the adsorption mechanism in shales is further complicated by

  11. Enterovirus 71 adsorption on metal ion-composite chitosan beads.

    PubMed

    Lin, Ya-Ching; Lin, Shu-Ting; Chen, Cheng-Yi; Wu, Sheng-Chi

    2012-01-01

    In this study, we developed composite chitosan beads combining various metal ions, including Ni(2+), Cu(2+), Zn(2+), and Fe(2+), for direct adsorption of enterovirus 71 (EV71). The metal-ion species had significant effects on the adsorption capacity of beads. Among these metal ion-composite chitosan beads, Ni(2+)-chitosan beads exhibited the best adsorption capacity of EV71. Using a concentration of 0.01-M Ni(2+) was found to best provide for bead formation and EV71 adsorption. The adsorption of EV71 for Ni(2+)-chitosan beads at neutral or alkaline pH was favored. Under a competitive condition with albumin proteins, Ni(2+)-chitosan beads exhibited significant capacity of EV71 adsorption in culture media. The adsorption of EV71 on the Ni(2+)-chitosan beads was attributed to the strong binding between Ni(2+) ions chelated to the surface amino acid of EV71 capsids and Ni(2+) ions chelated on the chitosan materials. Moreover, the adsorbed EV71 retained its antigenicity and infectivity after desorption. The Ni(2+)-chitosan beads exhibit a promising application to EV71 adsorption and removal.

  12. Study of Methylene Blue adsorption on keratin nanofibrous membranes.

    PubMed

    Aluigi, A; Rombaldoni, F; Tonetti, C; Jannoke, L

    2014-03-15

    In this work, keratin nanofibrous membranes (mean diameter of about 220nm) were prepared by electrospinning and tested as adsorbents for Methylene Blue through batch adsorption tests. The adsorption capacity of the membranes was evaluated as a function of initial dye concentration, pH, adsorbent dosage, time and temperature. The adsorption capacity increased with increasing the initial dye concentration and pH, while it decreased with increasing the adsorbent dosage and temperature, indicating an exothermic process. The adsorption results indicated that the Langmuir isotherm fitted the experimental data better than the Freundlich and Temkin isotherm models. A mean free energy evaluated through the Dubinin-Radushkevich model of about 16kJmol(-1), indicated a chemisorption process which occurred by ion exchange. The kinetic data were found to fit the pseudo-second-order model better than the pseudo-first-order model. The obtained results suggest that keratin nanofibrous membranes could be promising candidates as dye adsorption filters.

  13. Use of statistical design of experiments to evaluate the sorption capacity of 7-amine-4-azaheptylsilica and 10-amine- 4-azadecylsilica for Cu(II), Pb(II), and Fe(III) adsorption.

    PubMed

    Passos, Camila G; Ribaski, Fernanda S; Simon, Nathália M; dos Santos, Araci A; Vaghetti, Júlio C P; Benvenutti, Edilson V; Lima, Eder Cláudio

    2006-10-15

    7-Amine-4-azaheptylsilica (AAH Si) and 10-amine-4-azadecylsilica (AAD Si) were prepared and used for removal of Cu(II), Pb(II), and Fe(III) from aqueous solutions. Full 2(3) factorial designs with two pseudo-central points were carried out in order to achieve the best conditions of the batch adsorption procedure for metallic ion uptake by the adsorbents. To continue the optimizations, central composite surface design was also employed. These two independent statistical designs of experiments lead to the following conditions: m=30.0 mg of adsorbent; pH 6.0 for Cu(II) and Pb(II), pH 4.0 for Fe(III); t of contact 180 min to guarantee equilibration at higher adsorbate concentration. After optimization of the conditions, isotherms of the metallic ions adsorbed on the AAH Si and AAD Si adsorbents were obtained, which were fitted to nonlinear Langmuir and Freundlich isotherm models.

  14. Adsorption behavior of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on boehmite.

    PubMed

    Wang, Fei; Liu, Chengshuai; Shih, Kaimin

    2012-11-01

    Understanding the interaction of perfluorochemicals, persistent pollutants with known human health effects, with mineral compounds in surface water and groundwater environments is essential to determining their fate and transport. Kinetic experiments showed that adsorption equilibrium can be achieved within 48 h and the boehmite (AlOOH) surface is receptive to perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite as 0.877 μg m(-2) and 0.633 μg m(-2), respectively. Compared to the adsorption capacity on γ-alumina, the abundant hydroxyl groups on boehmite surfaces resulted in the 2-3 times higher adsorption of PFOS and PFOA. Increasing solution pH led to a moderate decrease in PFOS and PFOA adsorption, owing to an increase in ligand exchange reactions and the decrease of electrostatic interactions. The presence of NaCl and CaCl(2) in solution demonstrated negative effects for PFOS and PFOA adsorption on boehmite surfaces, with potential mechanisms being electrical double layer compression, competitive adsorption of chloride, and the Ca(2+) bridging effect between perfluorochemicals. PMID:22897837

  15. Fluorescence of PRODAN in Water: a Computational QM/MM MD Study

    SciTech Connect

    Pederzoli, Marek; Sobek, Lukas; Brabec, Jiri; Kowalski, Karol; Cwiklik, Lukasz; Pittner, Jiri

    2014-03-28

    Fluorescent properties of PRODAN (6-propionyl-2-dimethylaminonaphthalene) in water were studied by means of excited state molecular dynamics simulations employing a combined quantum mechanical and molecular mechanical approach with the time-dependent density functional theory (TD-DFT QM/MM MD). The state of the art coupled cluster method was used to benchmark density functional theory calculations. The influence of the water environment on PRODAN emission was investigated by employing several computational schemes with varying description of the solvent. The issue of the molecular geometry of the excited state PRODAN molecule in water was addressed. The experimental emission spectrum was reproduced for the planar excited state conformer of PRODAN in the extended environment of 300 explicit water molecules. The planar conformer was shown to be predominantly responsible for fluorescence. The twisted isomer is strongly stabilized in water, but rapidly evolve towards a conical intersection, and hence the twisted conformer is fluorescently inactive.

  16. Final report on AFRIMETS.QM-K27: Determination of ethanol in aqueous matrix

    NASA Astrophysics Data System (ADS)

    Archer, Marcellé; Fernandes-Whaley, Maria; Visser, Ria; de Vos, Jayne; Prins, Sara; Rosso, Adriana; Ruiz de Arechavaleta, Mariana; Tahoun, Ibrahim; Kakoulides, Elias; Luvonga, Caleb; Muriira, Geoffrey; Naujalis, Evaldas; Zakaria, Osman Bin; Buzoianu, Mirella; Bebic, Jelena; Achour Mounir, Ben; Thanh, Ngo Huy

    2013-01-01

    From within AFRIMETS, the Regional Metrology Organization (RMO) for Africa, the RMO Key Comparison AFRIMETS.QM-K27 was coordinated by the National Metrology Institute of South Africa (NMISA) in 2011. Ten Metrology Institutes participated, comprising three AFRIMETS, two APMP, four EURAMET and one SIM participant. Participants were required to determine the forensic level concentration of two aqueous ethanol solutions that were gravimetrically prepared by the NMISA. Concentrations were expected to lie in the range of 0.1 mg/g to 5.0 mg/g. The accurate determination of ethanol content in aqueous medium is critical for regulatory forensic and trade purposes. The CCQM Organic Analysis Working Group has carried out several key comparisons (CCQM-K27 series) on the determination of ethanol in wine and aqueous matrices. Developing NMIs now had the opportunity to link to the earlier CCQM-K27 studies through the AFRIMETS.QM-K27 study. Gas chromatography coupled to flame ionisation or mass spectrometric detection was applied by eight of the participants, while three participants (including NMISA) applied titrimetry for the ethanol assay. The assigned reference value of the aqueous ethanol solutions was used to link AFRIMETS.QM-K27 to the CCQM-K27 key comparison reference value. The assigned reference values for AFRIMETS.QM-K27 Level 1 and Level 2 were (0.3249 ± 0.0021) mg/g (k = 2) and (4.6649 ± 0.0152) mg/g (k = 2), respectively. The reference values were determined using the purity-corrected gravimetric preparation values, while the standard uncertainty incorporated the gravimetric preparation and titrimetric homogeneity uncertainties. From previous CCQM-K27 studies, the expected spread (%CV) of higher order measurements of ethanol in aqueous medium is about 0.85% relative. In this study the CV for Level 1 is about 12% (10% with two outliers removed) and for Level 2 about 4%. Three of the ten laboratories submitted results within 1.5% of the gravimetric reference value for

  17. Local and global refinement of electronic and structural properties of proteins via QM/MM

    NASA Astrophysics Data System (ADS)

    Gascon, Jose

    2007-03-01

    This talk presents a new method to incorporate polarization effects in the electrostatic potential of proteins and enzymes, with potential application to even larger biological systems such as ribosomes. Polarization effects are incorporated via an iterative self-consistent point-charge model of the protein electrostatic potential. The method, which scales linearly with the size of the protein, achieves quantitative agreement with full QM calculations in the description of electrostatic potentials of small polypeptides where polarization effects are significant, showing a remarkable improvement relative to the corresponding electrostatic potentials obtained with popular MM force fields. The capabilities of the method will be demonstrated in several applications, including calculations of the electrostatic potential in the potassium channel protein and the description of protein-protein association.

  18. A study of QM/Langevin-MD simulation for oxygen-evolving center of photosystem II

    SciTech Connect

    Uchida, Waka; Kimura, Yoshiro; Wakabayashi, Masamitsu; Hatakeyama, Makoto; Ogata, Koji; Nakamura, Shinichiro; Yokojima, Satoshi

    2013-12-10

    We have performed three QM/Langevin-MD simulations for oxygen-evolving complex (OEC) and surrounding residues, which are different configurations of the oxidation numbers on Mn atoms in the Mn{sub 4}O{sub 5}Ca cluster. By analyzing these trajectories, we have observed sensitivity of the change to the configuration of Mn oxidation state on O atoms of carboxyl on three amino acids, Glu354, Ala344, and Glu333. The distances from Mn to O atoms in residues contacting with the Mn{sub 4}O{sub 5}Ca cluster were analyzed for the three trajectories. We found the good correlation of the distances among the simulations. However, the distances with Glu354, Ala344, and Glu333 have not shown the correlation. These residues can be sensitive index of the changes of Mn oxidation numbers.

  19. Use of QM/DMD as a Multiscale Approach to Modeling Metalloenzymes.

    PubMed

    Gallup, N M; Alexandrova, A N

    2016-01-01

    Enzymes are complex biomolecules capable of performing unique catalysis under physiological conditions at neutral temperature and pH. However, the architecture of enzymatic catalysis is often a combination of the quantum influence of the immediate active site, as well as the electrostatic and configurational influences of amino acids surrounding the active site. As a result of this cooperation between baseline chemical reactivity and electrostatic assistance, it has become important to model enzymes using multiscale methods that take advantage of treating the active site with quantum mechanical methods, while approximately treating the surrounding protein using cheaper, classically driven force-field molecular mechanics methods. Here we describe the use of a multiscale engine which utilizes a combination of density functional theory with discrete molecular dynamics (dubbed QM/DMD) to aid in the characterization of metalloenzymes. PMID:27498643

  20. Prospects of Applying Enhanced Semi-Empirical QM Methods for 2101 Virtual Drug Design.

    PubMed

    Yilmazer, Nusret Duygu; Korth, Martin

    2016-01-01

    The last five years have seen a renaissance of semiempirical quantum mechanical (SQM) methods in the field of virtual drug design, largely due to the increased accuracy of so-called enhanced SQM approaches. These methods make use of additional terms for treating dispersion (D) and hydrogen bond (H) interactions with an accuracy comparable to dispersion-corrected density functional theory (DFT-D). DFT-D in turn was shown to provide an accuracy comparable to the most sophisticated QM approaches when it comes to non-covalent intermolecular forces, which usually dominate the protein/ligand interactions that are central to virtual drug design. Enhanced SQM methods thus offer a very promising way to improve upon the current state of the art in the field of virtual drug design. PMID:27183985

  1. Adsorption of reovirus by minerals and soils.

    PubMed Central

    Moore, R S; Taylor, D H; Reddy, M M; Sturman, L S

    1982-01-01

    Adsorption of [35S]methionine-labeled reovirus by 30 dry soils, minerals, and finely ground rocks suspended in synthetic freshwater at pH 7 was investigated to determine the conditions necessary for optimum virus removal during land application of wastewaters. All of the minerals and soils studied were excellent adsorbents of reovirus, with greater than 99% of the virus adsorbed after 1 h at 4 degrees C. Thereafter, virus remaining in suspension was significantly inactivated, and within 24 h a three to five log10 reduction in titer occurred. The presence of divalent cations, i.e., Ca2+ and Mg2+, in synthetic freshwater enhanced removal, whereas soluble organic matter decreased the amount of virus adsorbed in secondary effluent. The amount of virus adsorbed by these substrates was inversely correlated with the amount of organic matter, capacity to adsorb cationic polyelectrolyte, and electrophoretic mobility. Adsorption increased with increasing available surface area, as suspended infectivity was reduced further by the more finely divided substrates. However, the organic content of the soils reduced the level of infectious virus adsorbed below that expected from surface area measurements alone. The inverse correlation between virus adsorption and substrate capacity for cationic polyelectrolyte indicates that the adsorption of infectious reovirus particles is predominately a charged colloidal particle-charged surface interaction. Thus, adsorption of polyelectrolyte may be useful in predicting the fate of viruses during land application of sewage effluents and sludges. PMID:7149717

  2. Comparative evaluation of adsorption kinetics of diclofenac and isoproturon by activated carbon.

    PubMed

    Torrellas, Silvia A; Rodriguez, Araceli R; Escudero, Gabriel O; Martín, José María G; Rodriguez, Juan G

    2015-01-01

    Adsorption mechanism of diclofenac and isoproturon onto activated carbon has been proposed using Langmuir and Freundlich isotherms. Adsorption capacity and optimum adsorption isotherms were predicted by nonlinear regression method. Different kinetic equations, pseudo-first-order, pseudo-second-order, intraparticle diffusion model and Bangham kinetic model, were applied to study the adsorption kinetics of emerging contaminants on activated carbon in two aqueous matrices. PMID:26301850

  3. Evaluation of the isosteric heat of adsorption at zero coverage for hydrogen on activated carbons

    NASA Astrophysics Data System (ADS)

    Dohnke, E.; Beckner, M.; Romanos, J.; Olsen, R.; Wexler, C.; Pfeifer, P.

    2011-03-01

    Activated carbons made from corn cob show promise as materials for high-capacity hydrogen storage. As part of our characterization of these materials, we are interested in learning how different production methods affect the adsorption energies. In this talk, we will show how hydrogen adsorption isotherms may be used to calculate these adsorption energies at zero coverage using Henry's law. We will additionally discuss differences between the binding energy and the isosteric heat of adsorption by applying this analysis at different temperatures.

  4. A polarizable QM/MM approach to the molecular dynamics of amide groups solvated in water.

    PubMed

    Schwörer, Magnus; Wichmann, Christoph; Tavan, Paul

    2016-03-21

    The infrared (IR) spectra of polypeptides are dominated by the so-called amide bands. Because they originate from the strongly polar and polarizable amide groups (AGs) making up the backbone, their spectral positions sensitively depend on the local electric fields. Aiming at accurate computations of these IR spectra by molecular dynamics (MD) simulations, which derive atomic forces from a hybrid quantum and molecular mechanics (QM/MM) Hamiltonian, here we consider the effects of solvation in bulk liquid water on the amide bands of the AG model compound N-methyl-acetamide (NMA). As QM approach to NMA we choose grid-based density functional theory (DFT). For the surrounding MM water, we develop, largely based on computations, a polarizable molecular mechanics (PMM) model potential called GP6P, which features six Gaussian electrostatic sources (one induced dipole, five static partial charge distributions) and, therefore, avoids spurious distortions of the DFT electron density in hybrid DFT/PMM simulations. Bulk liquid GP6P is shown to have favorable properties at the thermodynamic conditions of the parameterization and beyond. Lennard-Jones (LJ) parameters of the DFT fragment NMA are optimized by comparing radial distribution functions in the surrounding GP6P liquid with reference data obtained from a "first-principles" DFT-MD simulation. Finally, IR spectra of NMA in GP6P water are calculated from extended DFT/PMM-MD trajectories, in which the NMA is treated by three different DFT functionals (BP, BLYP, B3LYP). Method-specific frequency scaling factors are derived from DFT-MD simulations of isolated NMA. The DFT/PMM-MD simulations with GP6P and with the optimized LJ parameters then excellently predict the effects of aqueous solvation and deuteration observed in the IR spectra of NMA. As a result, the methods required to accurately compute such spectra by DFT/PMM-MD also for larger peptides in aqueous solution are now at hand.

  5. Thermodynamics calculation of protein-ligand interactions by QM/MM polarizable charge parameters.

    PubMed

    Wang, Jinan; Shao, Qiang; Cossins, Benjamin P; Shi, Jiye; Chen, Kaixian; Zhu, Weiliang

    2016-01-01

    The calculation of protein-ligand binding free energy (ΔG) is of great importance for virtual screening and drug design. Molecular dynamics (MD) simulation has been an attractive tool to investigate this scientific problem. However, the reliability of such approach is affected by many factors including electrostatic interaction calculation. Here, we present a practical protocol using quantum mechanics/molecular mechanics (QM/MM) calculations to generate polarizable QM protein charge (QMPC). The calculated QMPC of some atoms in binding pockets was obviously different from that calculated by AMBER ff03, which might significantly affect the calculated ΔG. To evaluate the effect, the MD simulations and MM/GBSA calculation with QMPC for 10 protein-ligand complexes, and the simulation results were then compared to those with the AMBER ff03 force field and experimental results. The correlation coefficient between the calculated ΔΔG using MM/GBSA under QMPC and the experimental data is .92, while that with AMBER ff03 force field is .47 for the complexes formed by streptavidin or its mutants and biotin. Moreover, the calculated ΔΔG with QMPC for the complexes formed by ERβ and five ligands is positively related to experimental result with correlation coefficient of .61, while that with AMBER ff03 charge is negatively related to experimental data with correlation coefficient of .42. The detailed analysis shows that the electrostatic polarization introduced by QMPC affects the electrostatic contribution to the binding affinity and thus, leads to better correlation with experimental data. Therefore, this approach should be useful to virtual screening and drug design.

  6. [Adsorption kinetics of reactive dyes on activated carbon fiber].

    PubMed

    Li, Ying; Yue, Qin-Yan; Gao, Bao-Yu; Yang, Jing; Zheng, Yan

    2007-11-01

    The adsorption capability of activated carbon fiber (ACF) to four reactive dyes (reactive brilliant red K-2BP, reactive turquoise blue KN-G, reactive golden yellow K-3RP, reactive black KN-B) in aqueous solution was studied, and adsorption mechanism was focused on from kinetics point of view. The results show that the equilibrium adsorbing capacity (q(e)) of each dye increases with the addition of initial concentration or temperature. On the same condition, the order of q(e) is: reactive brilliant red > reactive golden yellow > reactive black > reactive turquoise blue. The adsorption processes follow a pseudo second-order kinetic rate equation, and the steric structure, size and polarity of dyes are important influence factors to initial adsorption rate. The adsorption activation energy of each dye is low (16.42, 3.56, 5.21, 26.38 kJ x mol(-1) respectively), which indicates that it belongs to physics adsorption.

  7. Tetraethylenepentamine embedded zeolite A for carbon dioxide adsorption.

    PubMed

    Kim, Young-Ki; Mo, Yong-Hwan; Lee, Jun; You, Hyo-Sang; Yi, Chang-Keun; Park, Young Cheol; Park, Sang-Eon

    2013-04-01

    Tetraethylenepentamine (TEPA) embedded zeolite A crystals were synthesized by using TEPA and the preformed zeolite A precursor under the microwave irradiation. The presence of TEPA in zeolite A crystal was confirmed by TG analysis and FTIR, Raman spectra. The CO2 adsorptive behavior of TEPA embedded zeolite A samples was investigated by CO2 isotherms measured at 25 degrees C comparing with zeolite A. The optimum CO2 sorption capacity was found in the case of 7.5% TEPA embedded zeolite A, which showed 3.75 mmol g(-1) where as the zeolite A showed less CO2 adsorption capacity of 2.88 mmol g(-1). The adsorption capacity of TEPA embedded Zeolite A was sustained up to 90% during 4 cycles of temperature swing adsorption (TSA) from 40 degrees C to 140 degrees C, indicating that the TEPA embedded Zeolite A was found to be useful as one of the application to solid amine adsorbent for CO2.

  8. MOLECULAR OXYGEN AND THE ADSORPTION OF PHENOLS - EFFECT OF FUNCTIONAL GROUPS

    EPA Science Inventory

    This study reveals that the presence of molecular oxygen (oxic conditions) has a significant impact on the exhibited adsorptive capacity of granular activated carbon (GAC) for several phenolic compounds. The increase in the GAC adsorptive capacity under oxic conditions results f...

  9. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  10. Determination of binding capacity and adsorption enthalpy between Human Glutamate Receptor (GluR1) peptide fragments and kynurenic acid by surface plasmon resonance experiments. Part 2: Interaction of GluR1270-300 with KYNA.

    PubMed

    Csapó, E; Bogár, F; Juhász, Á; Sebők, D; Szolomájer, J; Tóth, G K; Majláth, Z; Vécsei, L; Dékány, I

    2015-09-01

    In the course of our previous work, the interactions of two peptide fragments (GluR1201-230 and GluR1231-259) of human glutamate receptor (GluR1201-300) polypeptide with kynurenic acid (KYNA) were investigated by surface plasmon resonance (SPR) spectroscopy. Besides quantitation of the interactions, the enthalpies of binding of KYNA on certain peptide fragment-modified gold surfaces were also reported. In the present work, a third peptide fragment (GluR1270-300) of the glutamate receptor was synthesized and its interaction with KYNA was investigated by an SPR technique. This 31-membered peptide was chemically bonded onto a gold-coated SPR chip via a cysteine residue. The peptide-functionalized biosensor chip was analyzed by atomic force microscopy (AFM) and theoretical calculations were performed on the structure and dimensions of the peptide on the gold surface. In order to determine the isosteric heat of adsorption of the binding of KYNA on the peptide-functionalized gold thin film, SPR experiments were carried out between +10°C and +40°C. The results on the GluR1270-300-KYNA system were compared with the previously published binding parameters of the interactions of GluR1201-230 and GluR1231-259 with KYNA. The binding abilities of KYNA with all three peptide fragments immobilized on the gold surface were estimated by a molecular docking procedure and the binding free energies of these AMPA receptor subunits with KYNA were determined.

  11. Microemulsion synthesis of hydroxyapatite nanomaterials and their adsorption behaviors for Cr3+ ions

    NASA Astrophysics Data System (ADS)

    Gao, Y. L.; Wang, X. S.; Cui, H. H.; Mu, M. M.; Huang, F. Z.

    2016-05-01

    Hydroxyapatite (HAP) nanoparticles with different morphologies, such as nanorods, nanospheres, and their mixtures were successfully synthesized by microemulsion method with soluble additive. Their adsorption capacity for Cr3+ ion was investigated. Most of the Cr3+ were absorbed by HAP within 60 min. The adsorption capacity of the HAP nanospheres was the best, and the maximum Cr3+ removal ratio was 96.4%, revealing that the metal ions adsorption by HAP is dependent on the morphology of its particles.

  12. Adsorption of herbicides using activated carbons

    SciTech Connect

    Derbyshire, F.; Jagtoyan, M.; Lafferty, C.; Kimber, G.

    1996-10-01

    This work describes development of a series of novel activated carbon materials and their testing for possible water treatment applications by studying the adsorption of sodium pentachlorphenolate, PCP (a common herbicide/wood preservative). Although the application of activated carbons is an established technology for the treatment of public water supplies, there is a growing need for materials with higher selectivity and adsorptive capacities as well as high abrasion resistance. The materials that will be discussed include extruded wood-derived carbons with novel pore size distributions and high hardness, as well as activated carbon fiber composites. Comparisons will be made with commercial granular water treatment carbons.

  13. Effect of aging process on adsorption of diethyl phthalate in soils amended with bamboo biochar.

    PubMed

    Zhang, Xiaokai; Sarmah, Ajit K; Bolan, Nanthi S; He, Lizhi; Lin, Xiaoming; Che, Lei; Tang, Caixian; Wang, Hailong

    2016-01-01

    Biochar is a carbonaceous sorbent and can be used as a potential material to reduce the bioavailability of organic pollutants in contaminated soils. In the present study, the adsorption and desorption of diethyl phthalate (DEP) onto soils amended with bamboo biochar was investigated with a special focus on the effect of biochar application rates and aging conditions on the adsorption capacity of the soils. Biochar amendment significantly enhanced the soil adsorption of DEP that increased with increasing application rates of biochar. However, the adsorption capacity decreased by two aging processes (alternating wet and dry, and constantly moist). In the soil with low organic carbon (OC) content, the addition of 0.5% biochar (without aging) increased the adsorption by nearly 98 times compared to the control, and exhibited the highest adsorption capacity among all the treatments. In the soil with high OC content, the adsorption capacity in the treatment of 0.5% biochar without aging was 3.5 and 3 times greater than those of the treatments of biochar aged by alternating wet and dry, and constantly moist, respectively. Moreover, constantly moist resulted in a greater adsorption capacity than alternating wet and dry treatments regardless of biochar addition. This study revealed that biochar application enhanced soil sorption of DEP, however, the enhancement of the adsorption capacity was dependent on the soil organic carbon levels, and aging processes of biochar.

  14. Continuous fixed bed adsorption of Cu(II) by halloysite nanotube-alginate hybrid beads: an experimental and modelling study.

    PubMed

    Wang, Yanyan; Zhang, Xiang; Wang, Qiuru; Zhang, Bing; Liu, Jindun

    2014-01-01

    We used natural resources of halloysite nanotubes and alginate to prepare a novel porous adsorption material of organic-inorganic hybrid beads. The adsorption behaviour of Cu(II) onto the hybrid beads was examined by a continuous fixed bed column adsorption experiment. Meanwhile, the factors affecting the adsorption capacity such as bed height, influent concentration and flow rate were investigated. The adsorption capacity (Q0) reached 74.13 mg/g when the initial inlet concentration was 100 mg/L with a bed height of 12 cm and flow rate of 3 ml/min. The Thomas model and bed-depth service time fitted well with the experimental data. In the regeneration experiment, the hybrid beads retained high adsorption capacity after three adsorption-desorption cycles. Over the whole study, the new hybrid beads showed excellent adsorption and regeneration properties as well as favourable stability. PMID:25051464

  15. Adsorption Refrigeration System

    SciTech Connect

    Wang, Kai; Vineyard, Edward Allan

    2011-01-01

    Adsorption refrigeration is an environmentally friendly cooling technology which could be driven by recovered waste heat or low-grade heat such as solar energy. In comparison with absorption system, an adsorption system has no problems such as corrosion at high temperature and salt crystallization. In comparison with vapor compression refrigeration system, it has the advantages of simple control, no moving parts and less noise. This paper introduces the basic theory of adsorption cycle as well as the advanced adsorption cycles such as heat and mass recovery cycle, thermal wave cycle and convection thermal wave cycle. The types, characteristics, advantages and drawbacks of different adsorbents used in adsorption refrigeration systems are also summarized. This article will increase the awareness of this emerging cooling technology among the HVAC engineers and help them select appropriate adsorption systems in energy-efficient building design.

  16. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite.

    PubMed

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g · L(-1), in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics. PMID:26698573

  17. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite

    PubMed Central

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g·L-1, in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics. PMID:26698573

  18. Studies of gas adsorption in flexible Metal-Organic frameworks

    NASA Astrophysics Data System (ADS)

    Sircar, Sarmishtha

    Flexible Metal-Organic frameworks that exhibit a gate-opening (GO) adsorption mechanism have potential for gas separations and gas storage. The GO phenomenon occurs when molecular gates in the structure expand/contract in response to the activation/de-activation of a system variable e.g. temperature, pressure or gas. Sharp discontinuities in the isotherm leading to S-shapes and large adsorption-desorption hysteresis are typical of this phenomenon. This study investigates the kinetics and thermodynamics of the GO behavior by combining adsorption measurements and analytical modeling of adsorption kinetics and capacity as a function of adsorbate, GO pressure, and temperature. Basic understanding of GO mechanism will help harness GO-MOF's as adsorbents for gas separations and storage. Experiments were performed on two precharacterized MOFs with verified GO behavior. These are (1) Zn2(bpdc)2(bpee), which expands from a relative amorphous to crystalline structure and (2) Cu[(dhbc) 2(4,4f-bpy)]H2O, a mutually interdigitated 2-D structure (bpdc = biphenyldicarboxylate, bpee = 1,2]bipyridylethene; DMF = N,N-dimethyl formamide, dhbc= 2,5-dihydroxybenzoic acid, bpy=bipyridine). Both sub- and super-critical adsorption data were collected using three adsorption units: a standard low-pressure volumetric adsorption unit, a commercial high-pressure gravimetric analyzer and a custom-built high-pressure differential volumetric unit. Collected laboratory data were combined with published adsorption rate and isotherm data for analysis to broaden the range of data collection. The accuracy of the high-pressure differential unit was improved by over 300-fold by changing analytical methods of processing data to establish a reliable null correction. A pronounced effect of the allowed experimental time was found at cryogenic temperatures on (1). Tightening the stability criteria used by the adsorption equipment to determine equilibration increased the experimental time from the order of

  19. EVALUATING CAPACITIES OF GAC PRELOADED WITH NATURAL WATER

    EPA Science Inventory

    Adsorption studies are conducted to determine how preloading a natural groundwater onto GAC affects the adsorption of cis-1,2-dichloroexthene in small-scale and pilot-scale columns. Capacities are determined from batch-isotherm tests, microcolumns, and pilot columns, which are p...

  20. Impact of salinity and dispersed oil on adsorption of dissolved aromatic hydrocarbons by activated carbon and organoclay.

    PubMed

    Younker, Jessica M; Walsh, Margaret E

    2015-12-15

    Adsorption capacity of phenol and naphthalene by powdered activated carbon (PAC), a commercial organoclay (OC) and a lab synthesized organoclay (BTMA) was studied using batch adsorption experiments under variable feed water quality conditions including single- and multi- solute conditions, fresh water, saline water and oily-and-saline water. Increasing salinity levels was found to reduce adsorption capacity of OC, likely due to destabilization, aggregation and subsequent removal of organoclay from the water column, but did not negatively impact adsorption capacity of PAC or BTMA. Increased dispersed oil concentrations were found to reduce the surface area of all adsorbents. This decreased the adsorption capacity of PAC for both phenol and naphthalene, and reduced BTMA adsorption of phenol, but did not negatively affect naphthalene removals by either organoclay. The presence of naphthalene as a co-solute significantly reduced phenol adsorption by PAC, but had no impact on organoclay adsorption. These results indicated that adsorption by PAC occurred via a surface adsorption mechanism, while organoclay adsorption occurred by hydrophobic or pi electron interactions. In general, PAC was more sensitive to changes in water quality than either of the organoclays evaluated in this study. However, PAC exhibited a higher adsorption capacity for phenol and naphthalene compared to both organoclays even in adverse water quality conditions. PMID:26259095

  1. Effect of DOM Size on Organic Micropollutant Adsorption by GAC.

    PubMed

    Kennedy, Anthony M; Summers, R Scott

    2015-06-01

    Granular activated carbon (GAC) adsorption of the micropollutants 2-methylisoborneol (MIB) and warfarin (WFN) at ng/L levels was investigated in five waters with isolated natural dissolved organic matter (DOM) held at a constant dissolved organic carbon concentration. Each water was evaluated for competitive adsorption effects based on the pretreatment of ultrafiltration, coagulation, and additional background micropollutants. Using the breakthrough with unfractionated DOM as a baseline, on average, the water with lower molecular weight (MW) DOM decreased MIB and WFN adsorption capacity by 59%, whereas the water with higher MW DOM increased MIB and WFN adsorption capacity by 64%. All waters showed similar decreasing MIB and WFN adsorption capacity with increasing empty bed contact time (EBCT), with more dramatic effects seen for the more strongly adsorbing WFN. On average, MIB and WFN adsorption kinetics were two times slower in the water with higher MW DOM compared to the water with lower MW DOM, as described by the intraparticle pore diffusion tortuosity. Increased adsorption competition from 27 micropollutants other than MIB and WFN at environmentally relevant concentrations had little to no effect on MIB and WFN breakthrough behavior. Any competitive effect from background micropollutants became indiscernible at longer EBCTs. PMID:25955134

  2. Synthesis and CO₂ adsorption properties of molecularly imprinted adsorbents.

    PubMed

    Zhao, Yi; Shen, Yanmei; Bai, Lu; Hao, Rongjie; Dong, Liyan

    2012-02-01

    A series of molecularly imprinted adsorbents of CO(2) were developed by molecular self-assembly procedures, using ethanedioic acid, acrylamide, and ethylene glycol dimethacrylate as template, functional monomer, and cross-linker, respectively. Textural properties of these adsorbents were characterized by N(2) adsorption experiment, thermo-gravimetric analysis, and Fourier transform infrared spectroscopy. CO(2) adsorption capacities of adsorbents were investigated by thermo-gravimetric balance under 15% CO(2)/85% Ar atmosphere. Adsorption selectivity of CO(2) was studied by fixed-bed adsorption/desorption experiments. All the adsorbents displayed good thermal stability at 200 °C. Among them, MIP1b, with the higher amine content, exhibited the largest CO(2) capacity, which maintained steady after 50 adsorption-desorption cycles. Although MIP3 showed the highest specific surface, the CO(2) capacity was lower than that of MIP1b. CO(2) adsorption mechanism of molecularly imprinted adsorbents was determined to be physical sorption according to the adsorption enthalpies integrated from the DSC heatflow profiles. The calculated separation factors of CO(2) under 15% CO(2)/85% N(2) atmosphere were above 100 for all adsorbents.

  3. Cost-effective nanoporous Agar-Agar polymer/Nickel powder composite particle for effective bio-products adsorption by expanded bed chromatography.

    PubMed

    Asgari, Setareh; Jahanshahi, Mohsen; Rahimpour, Ahmad

    2014-09-26

    degree, viscosity of the liquid phase and the density of adsorbent. It was observed that the application of matrix with high density was proper for high operation, fluid velocity, since the addition of densifier improves the rigidity of the matrix. Three momentous factors, pH, ionic strength and initial concentration of BSA were analyzed. The best results showed that the adsorption equilibrium isotherms seems to follow a typical Langmuir isotherm and also the maximum adsorption capacity (qm) of BSA on RB4-Agar-Ni (64.01 mg/ml adsorbent) was higher than that on RB4-Streamline commercial adsorbent (about 54 mg.ml adsorbent). Additionally kinetic adsorption processes were characterized by the pseudo-first-order and pseudo-second-order kinetics equations. The experimental data followed the pseudo-first-order kinetic equation. Also the breakthrough curves were investigated. It was found that dynamic binding capacity (DBC) decreased with increasing the flow rate and the values of DBC decreased from 21.08 to 11.15 mg/ml adsorbent when the density of composite beads increased from 1.64 to 2.78 g/ml. All results indicate that the prepared composite is promising for efficient bioproduct adsorption with good hydrodynamic characteristics, high stability and it is suitable for expanded bed usage as a cost-effective adsorbent.

  4. Cost-effective nanoporous Agar-Agar polymer/Nickel powder composite particle for effective bio-products adsorption by expanded bed chromatography.

    PubMed

    Asgari, Setareh; Jahanshahi, Mohsen; Rahimpour, Ahmad

    2014-09-26

    degree, viscosity of the liquid phase and the density of adsorbent. It was observed that the application of matrix with high density was proper for high operation, fluid velocity, since the addition of densifier improves the rigidity of the matrix. Three momentous factors, pH, ionic strength and initial concentration of BSA were analyzed. The best results showed that the adsorption equilibrium isotherms seems to follow a typical Langmuir isotherm and also the maximum adsorption capacity (qm) of BSA on RB4-Agar-Ni (64.01 mg/ml adsorbent) was higher than that on RB4-Streamline commercial adsorbent (about 54 mg.ml adsorbent). Additionally kinetic adsorption processes were characterized by the pseudo-first-order and pseudo-second-order kinetics equations. The experimental data followed the pseudo-first-order kinetic equation. Also the breakthrough curves were investigated. It was found that dynamic binding capacity (DBC) decreased with increasing the flow rate and the values of DBC decreased from 21.08 to 11.15 mg/ml adsorbent when the density of composite beads increased from 1.64 to 2.78 g/ml. All results indicate that the prepared composite is promising for efficient bioproduct adsorption with good hydrodynamic characteristics, high stability and it is suitable for expanded bed usage as a cost-effective adsorbent. PMID:25152492

  5. Adsorption of mercury on laterite from Guizhou Province, China.

    PubMed

    Yu, Xiaohong; Zhu, Lijun; Guo, Baiwei; He, Shouyang

    2008-01-01

    The adsorption behaviors of Hg(II) on laterite from Guizhou Province, China, were studied and the adsorption mechanism was discussed. The results showed that different mineral compositons in the laterite will cause differences in the adsorption capacity of laterite to Hg(II). Illite and non-crystalloids are the main contributors to enhancing the adsorption capacity of laterite to Hg(II). The pH of the solution is an important factor affecting the adsorption of Hg(II) on laterite. The alkalescent environment (pH 7-9) is favorable to the adsorption of Hg(II). The amount of adsorbed Hg(II) increases with increasing pH. When the pH reaches a certain value, the amount of the adsorbed Hg(II) will reach the maximum level. The amount of adsorbed Hg(II) decreases with increasing pH. The optimal pHs of laterite and kaolinite are 9 and 8, respectively. The optimal initial concentrations of Hg(II) on laterite and kaolinite are 250 and 200 microg/ml, respectively. The adsorption isotherms were described by the Langmuir model. The adsorption of Hg(II) on laterite is a quick process while that of Hg(II) on kaolinite is a slow reaction. Laterite from Guizhou Province is a promising environmental material which can be used in the removal of Hg(II) from wastewater. PMID:19202872

  6. Mechanism of amitriptyline adsorption on Ca-montmorillonite (SAz-2).

    PubMed

    Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui; Kuo, Chung-Yih; Jean, Jiin-Shuh; Chen, Wan-Ru; Lv, Guocheng

    2014-07-30

    The uptake of amitriptyline (AMI) from aqueous environment by Ca-montmorillonite (SAz-2) was studied in a batch system under different physicochemical conditions. The adsorbent was characterized by X-ray diffraction and Fourier transform infrared (FTIR) analyses. The AMI adsorption on SAz-2 obeyed the Langmuir isotherm with a capacity of 330mg/g (1.05mmol/g) at pH 6-7. The adsorption kinetics was fast, almost reaching equilibrium in 2h, and followed a pseudo-second-order kinetic model. Desorption of exchangeable cations correlated with the AMI adsorption well, indicating that cation exchange was the major mechanism. X-ray diffraction patterns showing significant expansions of the d001 spacing and characteristic FTIR band shifts toward higher frequencies after AMI adsorption onto SAz-2 indicated that the adsorbed AMI molecules were intercalated into the interlayers of the mineral. Thermodynamic parameters based on partitioning coefficients suggested that the AMI adsorption was an endothermic physisorption at high adsorption levels. At low and higher AMI adsorption levels, the intercalated AMI molecules take a horizontal monolayer and bilayer conformation, respectively. The higher adsorption capacity suggested that SAz-2 could be a good candidate to remove AMI from wastewater and would be an important environmental sink for the fate and transport of AMI in soils and groundwater. PMID:24373983

  7. Adsorption of soluble oil from water to graphene.

    PubMed

    Wang, Na; Zhang, Yuchang; Zhu, Fuzhen; Li, Jingyi; Liu, Shuaishuai; Na, Ping

    2014-05-01

    The toxicity of soluble oil to the aquatic environment has started to attract wide attention in recent years. In the present work, we prepare graphene according to oxidation and thermal reduction methods for the removal of soluble oil from the solution. Characterization of the as-prepared graphene are performed by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectra, Brunauer-Emmett-Teller, X-ray photoelectron spectroscopy, and contact angle analysis. The adsorption behavior of soluble oil on graphene is examined, and the obtained adsorption data are modeled using conventional theoretical models. Adsorption experiments reveal that the adsorption rate of soluble oil on graphene is notably fast, especially for the soluble diesel oil, which could reach equilibrium within 30 min, and the kinetics of adsorption is perfectly consistent with a pseudo-second-order model. Furthermore, it is determined that the adsorption isotherm of soluble diesel oil with graphene fit the Freundlich model best, and graphene has a very strong adsorption capacity for soluble diesel oil in the solution. These results demonstrate that graphene is the material that provided both good adsorptive capacity and good kinetics, implying that it could be used as a promising sorbent for soluble oil removal from wastewater.

  8. Adsorption of mercury on laterite from Guizhou Province, China.

    PubMed

    Yu, Xiaohong; Zhu, Lijun; Guo, Baiwei; He, Shouyang

    2008-01-01

    The adsorption behaviors of Hg(II) on laterite from Guizhou Province, China, were studied and the adsorption mechanism was discussed. The results showed that different mineral compositons in the laterite will cause differences in the adsorption capacity of laterite to Hg(II). Illite and non-crystalloids are the main contributors to enhancing the adsorption capacity of laterite to Hg(II). The pH of the solution is an important factor affecting the adsorption of Hg(II) on laterite. The alkalescent environment (pH 7-9) is favorable to the adsorption of Hg(II). The amount of adsorbed Hg(II) increases with increasing pH. When the pH reaches a certain value, the amount of the adsorbed Hg(II) will reach the maximum level. The amount of adsorbed Hg(II) decreases with increasing pH. The optimal pHs of laterite and kaolinite are 9 and 8, respectively. The optimal initial concentrations of Hg(II) on laterite and kaolinite are 250 and 200 microg/ml, respectively. The adsorption isotherms were described by the Langmuir model. The adsorption of Hg(II) on laterite is a quick process while that of Hg(II) on kaolinite is a slow reaction. Laterite from Guizhou Province is a promising environmental material which can be used in the removal of Hg(II) from wastewater.

  9. Adsorption of Cd, Cu and Zn from aqueous solutions onto ferronickel slag under different potentially toxic metal combination.

    PubMed

    Park, Jong-Hwan; Kim, Seong-Heon; Kang, Se-Won; Kang, Byung-Hwa; Cho, Ju-Sik; Heo, Jong-Soo; Delaune, Ronald D; Ok, Yong Sik; Seo, Dong-Cheol

    2016-01-01

    Adsorption characteristics of potentially toxic metals in single- and multi-metal forms onto ferronickel slag were evaluated. Competitive sorption of metals by ferronickel slag has never been reported previously. The maximum adsorption capacities of toxic metals on ferronickel were in the order of Cd (10.2 mg g(-1)) > Cu (8.4 mg g(-1)) > Zn (4.4 mg g(-1)) in the single-metal adsorption isotherm and Cu (6.1 mg g(-1)) > Cd (2.3 mg g(-1)) > Zn (0.3 mg g(-1)) in the multi-metal adsorption isotherm. In comparison with single-metal adsorption isotherm, the reduction rates of maximum toxic metal adsorption capacity in the multi-metal adsorption isotherm were in the following order of Zn (93%) > Cd (78%) > Cu (27%). The Freundlich isotherm provides a slightly better fit than the Langmuir isotherm equation using ferronickel slag for potentially toxic metal adsorption. Multi-metal adsorption behaviors differed from single-metal adsorption due to competition, based on data obtained from Freundlich and Langmuir adsorption models and three-dimensional simulation. Especially, Cd and Zn were easily exchanged and substituted by Cu during multi-metal adsorption. Further competitive adsorption studies are necessary in order to accurately estimate adsorption capacity of ferronickel slag for potentially toxic metals in natural environments. PMID:26942519

  10. Adsorption of Cd, Cu and Zn from aqueous solutions onto ferronickel slag under different potentially toxic metal combination.

    PubMed

    Park, Jong-Hwan; Kim, Seong-Heon; Kang, Se-Won; Kang, Byung-Hwa; Cho, Ju-Sik; Heo, Jong-Soo; Delaune, Ronald D; Ok, Yong Sik; Seo, Dong-Cheol

    2016-01-01

    Adsorption characteristics of potentially toxic metals in single- and multi-metal forms onto ferronickel slag were evaluated. Competitive sorption of metals by ferronickel slag has never been reported previously. The maximum adsorption capacities of toxic metals on ferronickel were in the order of Cd (10.2 mg g(-1)) > Cu (8.4 mg g(-1)) > Zn (4.4 mg g(-1)) in the single-metal adsorption isotherm and Cu (6.1 mg g(-1)) > Cd (2.3 mg g(-1)) > Zn (0.3 mg g(-1)) in the multi-metal adsorption isotherm. In comparison with single-metal adsorption isotherm, the reduction rates of maximum toxic metal adsorption capacity in the multi-metal adsorption isotherm were in the following order of Zn (93%) > Cd (78%) > Cu (27%). The Freundlich isotherm provides a slightly better fit than the Langmuir isotherm equation using ferronickel slag for potentially toxic metal adsorption. Multi-metal adsorption behaviors differed from single-metal adsorption due to competition, based on data obtained from Freundlich and Langmuir adsorption models and three-dimensional simulation. Especially, Cd and Zn were easily exchanged and substituted by Cu during multi-metal adsorption. Further competitive adsorption studies are necessary in order to accurately estimate adsorption capacity of ferronickel slag for potentially toxic metals in natural environments.

  11. Mercury adsorption properties of sulfur-impregnated adsorbents

    USGS Publications Warehouse

    Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

    2002-01-01

    Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

  12. Novel nano bearings constructed by physical adsorption

    NASA Astrophysics Data System (ADS)

    Zhang, Yongbin

    2015-09-01

    The paper proposes a novel nano bearing formed by the physical adsorption of the confined fluid to the solid wall. The bearing is formed between two parallel smooth solid plane walls sliding against one another, where conventional hydrodynamic lubrication theory predicted no lubricating effect. In this bearing, the stationary solid wall is divided into two subzones which respectively have different interaction strengths with the lubricating fluid. It leads to different physical adsorption and slip properties of the lubricating fluid at the stationary solid wall respectively in these two subzones. It was found that a significant load-carrying capacity of the bearing can be generated for low lubricating film thicknesses, because of the strong physical adsorption and non-continuum effects of the lubricating film.

  13. Adsorption of hydroxyacetone on pure ice surfaces.

    PubMed

    Petitjean, Mélanie; Darvas, Maria; Picaud, Sylvain; Jedlovszky, Pál; Le Calvé, Stéphane

    2010-12-17

    The adsorption of hydroxyacetone molecules at the surface of ice is investigated by means of flow-tube reactor measurements in the temperature range: 213-253 K. The number of molecules adsorbed per surface unit is conventionally plotted as a function of the absolute gas concentration of hydroxyacetone and is compared to that previously obtained for acetone and ethanol. The enthalpy of adsorption and the monolayer capacity at the ice surface are determined. In addition, molecular dynamics simulations are performed to support the experimental results. However, it is shown that the available interaction potential between hydroxyacetone and ice is not accurate enough to allow a robust detailed analysis of the adsorption process. Finally, a rapid estimation of the hydroxyacetone partitioning between the gas phase and ice shows that in the densest ice clouds, up to 29% of hydroxyacetone could be adsorbed on pure ice surfaces at 203 K.

  14. QM and QM/MM Studies of Uranyl Fluorides in the Gas and Aqueous Phases and in the Hydrophobic Cavities of Tetrabrachion

    SciTech Connect

    Odoh, Samuel O.; Walker, Sean M.; Meier, Markus; Stetefeld, Jörg; Schreckenbach, Georg

    2011-04-04

    The structural properties and electronic structures of pentacoordinated uranyl complexes belonging to the [UO₂Fn(H₂O)5-n]2-n series have been studied in the gas and aqueous phases using density functionals with relativistic pseudopotentials and all-electron basis sets in the gas-phase calculations in combination with COSMO in the aqueous phase. In addition, the conformational orientation and structural and electronic properties of [UO₂F₅]³¯ in the hydrophobic cavities of the right-handed coiled-coil (RHCC) protein of tetrabrachion have been determined using the hybrid QM/MM method. Although there is good agreement between the available experimental geometrical parameters and the values obtained in the aqueous phase using pseudopotentials or all-electron basis sets, variation of the uranyl U=O bond with the number of fluoride ligands is only truly captured after the inclusion of five water molecules in the second coordination sphere around the molecules. The docking procedure used in this work shows that there are only two possible orientations of the uranyl group of [UO₂F₅]³¯ embedded in the hydrophobic cavities of the RHCC protein. The two orientations are exclusively along the axes perpendicular to the protein axial channel with no possible orientation of the uranyl group along the axial channel because of both steric effects and interaction with the alkyl chain of the isoleucine residues pointing into the axial channel. In addition, the embedded complex is always positioned nearer to the isoleucine residues at the N-terminal ends of the hydrophobic cavities. Energy analysis, however, reveals that both conformations can only be observed in cavity 2, the largest hydrophobic cavity. The structural and electronic properties of the ligand embedded in this cavity are very similar to those of the gas-phase structure. A comparable study of [Pt(CN)₆]²¯ and the anticancer drug cisplatin, [PtCl₂(NH₃)₂], in cavity 2, revealed

  15. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    SciTech Connect

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  16. Adsorption of lead onto smectite from aqueous solution.

    PubMed

    Mhamdi, M; Galai, H; Mnasri, N; Elaloui, E; Trabelsi-Ayadi, M

    2013-03-01

    The purpose of this research is to study the effect of a new method of adsorption using membrane filtration to determine the maximum amount of lead adsorbed by clay and investigate the behavior of the clay after adsorption of the said metal. Treatment of wastewater contaminated with heavy metals depends on the characteristics of the effluent, the amount of final discharge, the cost of treatment, and the compatibility of the treatment process. The process of adsorption of heavy metals by clays may be a simple, selective, and economically viable alternative to the conventional physical-chemical treatment. This is justified by the importance of the surface developed by this material, the presence of negative charges on the said surface, the possibility of ion exchange taking place, and its wide availability in nature. The removal of lead from wastewater was studied by using the adsorption technique and using clay as the adsorbent. A method was optimized for adsorption through a membrane approaching natural adsorption. This new method is simple, selective, and the lead adsorption time is about 3 days. The various properties of clay were determined. It was observed that the cation exchange capacity of the clay was 56 meq/100 g of hydrated clay for the raw sample and 82 meq/100 g for the purified sample. The total surface area determined by the methylene blue method was equal to 556 and 783 m(2)/g for the raw and purified samples, respectively. The adsorption kinetics depends on several parameters. The Pb(II) clay, obeys the Langmuir, Freundlich, and the Elovich adsorption isotherms with high regression coefficients. The use of this adsorbent notably decreases the cost of treatment. It was concluded that clay shows a strong adsorption capacity on Pb(II), the maximum interaction occurring with purified clay treated at high concentration of lead. It is proposed that this adsorption through a membrane be extended for the treatment of effluents containing other metals. PMID

  17. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    PubMed

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process. PMID:26398038

  18. Cellulose aerogel regenerated from ionic liquid solution for immobilized metal affinity adsorption.

    PubMed

    Oshima, Tatsuya; Sakamoto, Toshihiko; Ohe, Kaoru; Baba, Yoshinari

    2014-03-15

    Surface morphology of cellulosic adsorbents is expected to influence the adsorption behavior of biomacromolecules. In the present study, cellulose aerogel regenerated from ionic liquid solution was prepared for use as a polymer support for protein adsorption. Iminodiacetic acid groups were introduced to the aerogel for immobilized metal affinity adsorption of proteins. A Cu(II)-immobilized iminodiacetic acid cellulose aerogel (Cu(II)-IDA-CA), which has a large specific surface area, showed a higher adsorption capacity than Cu(II)-immobilized iminodiacetic acid bacterial cellulose (Cu(II)-IDA-BC) and Cu(II)-immobilized iminodiacetic acid plant cellulose (Cu(II)-IDA-PC). In contrast, the Cu(II)-immobilized cellulosic adsorbents showed similar adsorption capacities for smaller amino acid and peptides. The results show that cellulose aerogels are useful as polymer supports with high protein adsorption capacities.

  19. A QM/MM Approach Using the AMOEBA Polarizable Embedding: From Ground State Energies to Electronic Excitations.

    PubMed

    Loco, Daniele; Polack, Étienne; Caprasecca, Stefano; Lagardère, Louis; Lipparini, Filippo; Piquemal, Jean-Philip; Mennucci, Benedetta

    2016-08-01

    A fully polarizable implementation of the hybrid quantum mechanics/molecular mechanics approach is presented, where the classical environment is described through the AMOEBA polarizable force field. A variational formalism, offering a self-consistent relaxation of both the MM induced dipoles and the QM electronic density, is used for ground state energies and extended to electronic excitations in the framework of time-dependent density functional theory combined with a state specific response of the classical part. An application to the calculation of the solvatochromism of the pyridinium N-phenolate betaine dye used to define the solvent ET(30) scale is presented. The results show that the QM/AMOEBA model not only properly describes specific and bulk effects in the ground state but it also correctly responds to the large change in the solute electronic charge distribution upon excitation.

  20. A QM/MM Approach Using the AMOEBA Polarizable Embedding: From Ground State Energies to Electronic Excitations.

    PubMed

    Loco, Daniele; Polack, Étienne; Caprasecca, Stefano; Lagardère, Louis; Lipparini, Filippo; Piquemal, Jean-Philip; Mennucci, Benedetta

    2016-08-01

    A fully polarizable implementation of the hybrid quantum mechanics/molecular mechanics approach is presented, where the classical environment is described through the AMOEBA polarizable force field. A variational formalism, offering a self-consistent relaxation of both the MM induced dipoles and the QM electronic density, is used for ground state energies and extended to electronic excitations in the framework of time-dependent density functional theory combined with a state specific response of the classical part. An application to the calculation of the solvatochromism of the pyridinium N-phenolate betaine dye used to define the solvent ET(30) scale is presented. The results show that the QM/AMOEBA model not only properly describes specific and bulk effects in the ground state but it also correctly responds to the large change in the solute electronic charge distribution upon excitation. PMID:27340904

  1. Atomistic insight into the catalytic mechanism of glycosyltransferases by combined quantum mechanics/molecular mechanics (QM/MM) methods.

    PubMed

    Tvaroška, Igor

    2015-02-11

    Glycosyltransferases catalyze the formation of glycosidic bonds by assisting the transfer of a sugar residue from donors to specific acceptor molecules. Although structural and kinetic data have provided insight into mechanistic strategies employed by these enzymes, molecular modeling studies are essential for the understanding of glycosyltransferase catalyzed reactions at the atomistic level. For such modeling, combined quantum mechanics/molecular mechanics (QM/MM) methods have emerged as crucial. These methods allow the modeling of enzymatic reactions by using quantum mechanical methods for the calculation of the electronic structure of the active site models and treating the remaining enzyme environment by faster molecular mechanics methods. Herein, the application of QM/MM methods to glycosyltransferase catalyzed reactions is reviewed, and the insight from modeling of glycosyl transfer into the mechanisms and transition states structures of both inverting and retaining glycosyltransferases are discussed.

  2. Dynamic and equilibrium performance of sensors based on short peptide ligands for affinity adsorption of human IgG using surface plasmon resonance.

    PubMed

    Islam, Nafisa; Shen, Fei; Gurgel, Patrick V; Rojas, Orlando J; Carbonell, Ruben G

    2014-08-15

    This paper characterizes the potential of novel hexameric peptide ligands for on-line IgG detection in bioprocesses. Surface Plasmon Resonance (SPR) was used to study the binding of human IgG to the hexameric peptide ligand HWRGWV, which was covalently grafted to alkanethiol self-assembled monolayers (SAM) on gold surfaces. Peptide coupling on SAMs was verified, followed by covalent grafting of peptides with a removable Fmoc or acetylated N-termini via their C-termini to produce active peptide SPR sensors that were tested for IgG binding. The dynamics and extent of peptide-IgG binding were compared with results from a conventional system using protein A attached on a gold surface via disulfide monolayers. IgG binding to protein A on disulfide monolayers yielded equilibrium dissociation constants of 1.4×10(-7)M. The corresponding dissociation constant value for the acetylated version of the peptide (Ac-HWRGWV) supported on alkanethiol SAM was 5.8×10(-7)M and that for HWRGWV on the alkanethiol SAM (after de-protection of Fmoc-HWRGWVA) was 1.2×10(-6)M. Maximum IgG binding capacities, Qm of 6.7, 3.8, and 4.1mgm(-2) were determined for the protein A and the two forms of HWRGWV-based biosensors, respectively. Real-time data for the kinetics of adsorption were used to determine the apparent rate constants for adsorption and desorption. The results were analyzed to understand the mechanism of IgG binding to the protein and peptide ligands. It was found that the peptide-IgG binding was reaction controlled, however the protein A-IgG binding mechanism was partially mass transfer (diffusion) controlled. The adsorption rate constants, ka, for the protein A ligand increased with decreasing concentration of analyte and the peptide ligand ka values was constant at different IgG concentrations and flow rates.

  3. Adsorption of Gases on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Mbaye, Mamadou Thiao

    This research focus in studying the interaction between various classical and quantum gases with novel carbon nanostructures, mainly carbon nanotubes (CNTs). Since their discovery by the Japanese physicist Sumio Iijima [1] carbon nanotubes have, experimentally and theoretically, been subjected to many scientific investigation. Studies of adsorption on CNTs are particularly directed toward their better usage in gas storage, gas separation, catalyst, drug delivery, and water purification. We explore the adsorption of different gases entrapped in a single, double, or multi-bundles of CNTs using computer simulations. The first system we investigate consists of Ar and Kr films adsorbed on zigzag or armchair nanotubes. Our simulations revealed that Kr atoms on intermediate size zigzag NTs undergo two phase transitions: A liquid-vapor (L→V), and liquid-commensurate (L→CS) with a fractional coverage of one Kr atoms adsorbed for every four carbon atoms. For Ar on zigzag and armchair NTs, the only transition observed is a L→V. In the second problem, we explore the adsorption of CO2 molecules in a nanotube bundle and calculate the isosteric heat of adsorption of the entrapped molecules within the groove. We observed that the lower the temperature, the higher the isosteric of adsorption. Last, we investigate the adsorption of hydrogen, Helium, and Neon gases on the groove site of two parallel nanotubes. At low temperature, the transverse motion on the plane perpendicular to the tubes' axis is frozen out and as a consequence, the heat capacity is reduced to 1/2. At high temperature, the atoms gain more degree of freedom and as a consequence the heat capacity is 5/2.

  4. A Simple Adsorption Experiment

    ERIC Educational Resources Information Center

    Guirado, Gonzalo; Ayllon, Jose A.

    2011-01-01

    The study of adsorption phenomenon is one of the most relevant and traditional physical chemistry experiments performed by chemistry undergraduate students in laboratory courses. In this article, we describe an easy, inexpensive, and straightforward way to experimentally determine adsorption isotherms using pieces of filter paper as the adsorbent…

  5. Identification and characterization of a QM protein as a possible peptidoglycan recognition protein (PGRP) from the giant tiger shrimp Penaeus monodon.

    PubMed

    Udompetcharaporn, Attasit; Junkunlo, Kingkamon; Senapin, Saengchan; Roytrakul, Sittiruk; Flegel, Timothy W; Sritunyalucksana, Kallaya

    2014-10-01

    In an attempt to identify a peptidoglycan recognition protein (PGRP) in Penaeus (Penaeus) monodon, in vitro pull-down binding assays were used between shrimp proteins and purified peptidoglycan (PG). By gel electrophoresis and mass spectrometry followed by Mascot program analysis, proteins from shrimp hemocyte peripheral membrane proteins showed significant homology to records for a QM protein, actin and prophenoloxidase 2 precursor (proPO2), while proteins from cell-free plasma showed significant homology to records for a vitellogenin, a fibrinogen related protein (FREP) and a C-type lectin. Due to time and resource limitations, specific binding to PG was examined only for recombinant PmQM protein and PmLec that were synthesized based on sequences reported in the Genbank database (accession numbers FJ766846 and DQ078266, respectively). An in vitro assay revealed that hemocytes would bind with and encapsulate agarose beads coated with recombinant PmQM (rPmQM) or rPmLec and that melanization followed 2h post-encapsulation. ELISA tests confirmed specific binding of rPmQM protein to PG. This is the first time that PmQM has been reported as a potential PGRP in shrimp or any other crustacean. The two other potential PGRP identified (FREP and the vitellin-like protein present in male P. monodon, unlike other vitellin subunits) should also be expressed heterologously and tested for their ability to activate shrimp hemocytes.

  6. How Can Linoleic Acid Be the Preferential Substrate of the Enzyme 15-Lipoxygenase-1? A QM/MM Approach.

    PubMed

    Soler, Jordi; Saura, Patricia; García-López, Diego; Masgrau, Laura; Lluch, José M; González-Lafont, Àngels

    2016-03-01

    The most common substrate of mammalian lipoxygenases (LOXs) is arachidonic acid (AA). However, 15-LOXs can present dual substrate specificity. These LOXs catalyze the peroxidation of AA, initiated by a H-abstraction step (mainly H13-abstraction) by the Fe(III)-OH(-) cofactor, and the peroxidation of linoleic acid (LA) after H11-abstraction. In this paper, QM(B3LYP)/MM(CHARMM) calculations of the rate-limiting H11-abstraction process of LA catalyzed by rabbit 15-LOX-1 (15-rLOX-1) have been carried out using a complete model of the solvated 15-rLOX-1:LA complex. A total of 26 QM/MM potential energy profiles as a function of the H-transfer reaction coordinate have been computed along with one QM/MM free energy profile obtained using the Free Energy Perturbation method. The molecular origin of substrate specificity of 15-rLOX-1 for LA in comparison with AA has been analyzed. In many of the QM/MM reactive 15-rLOX-1:LA energy minima, LA adopts more elongated conformations than AA, although having a shorter carbon chain, because LA has one double bond between C1 and C11 whereas AA has three double bonds between C1 and C13. Consequently, C11 of LA can be located in the same region of the active site as C13 of AA, a zone where H11-abstraction from LA as well as H13-abstraction from AA is not hindered by bulky residue side chains. This explains at a molecular level how 15-LOXs might accommodate and recognize for catalysis two substrates that are different in length by two carbons. Our results also explain why (9Z,11E)-13-hydro(pero)xyoctadeca-9,11-dienoic acid is the major product of the peroxidation and why LA is the preferential substrate of 15-rLOX-1. PMID:26646740

  7. How Can Linoleic Acid Be the Preferential Substrate of the Enzyme 15-Lipoxygenase-1? A QM/MM Approach.

    PubMed

    Soler, Jordi; Saura, Patricia; García-López, Diego; Masgrau, Laura; Lluch, José M; González-Lafont, Àngels

    2016-03-01

    The most common substrate of mammalian lipoxygenases (LOXs) is arachidonic acid (AA). However, 15-LOXs can present dual substrate specificity. These LOXs catalyze the peroxidation of AA, initiated by a H-abstraction step (mainly H13-abstraction) by the Fe(III)-OH(-) cofactor, and the peroxidation of linoleic acid (LA) after H11-abstraction. In this paper, QM(B3LYP)/MM(CHARMM) calculations of the rate-limiting H11-abstraction process of LA catalyzed by rabbit 15-LOX-1 (15-rLOX-1) have been carried out using a complete model of the solvated 15-rLOX-1:LA complex. A total of 26 QM/MM potential energy profiles as a function of the H-transfer reaction coordinate have been computed along with one QM/MM free energy profile obtained using the Free Energy Perturbation method. The molecular origin of substrate specificity of 15-rLOX-1 for LA in comparison with AA has been analyzed. In many of the QM/MM reactive 15-rLOX-1:LA energy minima, LA adopts more elongated conformations than AA, although having a shorter carbon chain, because LA has one double bond between C1 and C11 whereas AA has three double bonds between C1 and C13. Consequently, C11 of LA can be located in the same region of the active site as C13 of AA, a zone where H11-abstraction from LA as well as H13-abstraction from AA is not hindered by bulky residue side chains. This explains at a molecular level how 15-LOXs might accommodate and recognize for catalysis two substrates that are different in length by two carbons. Our results also explain why (9Z,11E)-13-hydro(pero)xyoctadeca-9,11-dienoic acid is the major product of the peroxidation and why LA is the preferential substrate of 15-rLOX-1.

  8. Advances in binding free energies calculations: QM/MM-based free energy perturbation method for drug design.

    PubMed

    Rathore, R S; Sumakanth, M; Reddy, M Siva; Reddanna, P; Rao, Allam Appa; Erion, Mark D; Reddy, M R

    2013-01-01

    Multiple approaches have been devised and evaluated to computationally estimate binding free energies. Results using a recently developed Quantum Mechanics (QM)/Molecular Mechanics (MM) based Free Energy Perturbation (FEP) method suggest that this method has the potential to provide the most accurate estimation of binding affinities to date. The method treats ligands/inhibitors using QM while using MM for the rest of the system. The method has been applied and validated for a structurally diverse set of fructose 1,6- bisphosphatase (FBPase) inhibitors suggesting that the approach has the potential to be used as an integral part of drug discovery for both lead identification lead optimization, where there is a structure available. In addition, this QM/MM-based FEP method was shown to accurately replicate the anomalous hydration behavior exhibited by simple amines and amides suggesting that the method may also prove useful in predicting physical properties of molecules. While the method is about 5-fold more computationally demanding than conventional FEP, it has the potential to be less demanding on the end user since it avoids development of MM force field parameters for novel ligands and thereby eliminates this time-consuming step that often contributes significantly to the inaccuracy of binding affinity predictions using conventional FEP methods. The QM/MM-based FEP method has been extensively tested with respect to important considerations such as the length of the simulation required to obtain satisfactory convergence in the calculated relative solvation and binding free energies for both small and large structural changes between ligands. Future automation of the method and parallelization of the code is expected to enhance the speed and increase its use for drug design and lead optimization. PMID:23260025

  9. Adsorption of mercury from water by modified multi-walled carbon nanotubes: adsorption behaviour and interference resistance by coexisting anions.

    PubMed

    Chen, Paris Honglay; Hsu, Cheng-Feng; Tsai, David Dah-wei; Lu, Yen-Ming; Huang, Winn-Jung

    2014-08-01

    This investigation reports the use of modified multi-walled carbon nanotubes (MWCNTs) with various functional groups for adsorbing inorganic divalent mercury (Hg(II)) from water samples. To elucidate the behaviours and mechanisms of Hg(II) adsorption by modified MWCNTs, their adsorption capacity was studied by considering adsorption isotherms and kinetics. Particular attention was paid to interference of coexisting inorganic ions with Hg(II) adsorption. The results reveal that functionalization with oxygen-containing groups improved the Hg(II) adsorption capacity of the MWCNTs. Kinetic analysis demonstrated that the adsorption of Hg(II) by MWCNTs was closely described by the pseudo-second-order and Elovich models, suggesting that the adsorption of Hg(II) by MWCNTs was significantly affected by chemical adsorption. The kinetic results were also analysed using the intraparticle diffusion model, which revealed that intraparticle diffusion was not the only rate-controlling mechanism. The adsorption of Hg(II) on MWCNTs fell drastically as the ionic strength increased from 0 to 1.0mol/L chloride ions, and declined significantly as the pH increased from 2.2 to 10.5. The elemental maps obtained by energy-dispersive spectrometer (EDS) revealed the formation of surface complexes of chloride ions with functional groups on MWCNTs, which reduced the number of available sites for the adsorption of Hg(II) and strengthened the repulsive forces between Hg(II) and MWCNTs. The EDS results suggest that chloride ions are important in controlling Hg(II) speciation and adsorption on the surfaces of MWCNTs.

  10. Modeling trapping mechanism for PCB adsorption on activated carbon

    NASA Astrophysics Data System (ADS)

    Jensen, Bjørnar; Kvamme, Bjørn; Kuznetsova, Tatyana; Oterhals, A.˚ge

    2012-12-01

    The levels of polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran (PCDD/F) and dioxin-like polychlorinated biphenyl (DL-PCB) in fishmeal and fish oil produced for use in feed for salmon is above present European legislation levels in some regions of the world and different decontamination approaches have been proposed [1]. One of these is adsorption on activated carbon. This approach appears to be efficient for adsorption of PCDD/F but less efficient for DL-PCB [2]. Activated carbon consists of slit pores with average sizes of 20 - 50 Ångstroms. One hypothesis [2] for the mechanism of trapping DL-PCB is reduced ability for intramolecular movements of the PCB molecules inside the slit pores. In order to investigate this hypothesis we have used quantum mechanics [3] to characterize two DL-PCB congeners, respectively congener 77 (3,3',4,4'-Tetrachlorobiphenyl) and congener 118 (2,3',4,4',5-Pentachlorobiphenyl) and Triolein (18:1) [4] as a major constituent of the solvent fish oil. A model for activated carbon was constructed using a crystal structure of graphite from the American Mineralogist Crystal Structure Database [5]. The crystal structure used was originally from Wyckoff [6]. A small program had to be written to generate the desired graphite structure as it contains no less than 31232 Carbon atoms. Partial atomic charges were estimated using QM with DFT/B3LYP/6-311+g** and SM6 [7].

  11. Strong adsorption of phosphate by amorphous zirconium oxide nanoparticles.

    PubMed

    Su, Yu; Cui, Hang; Li, Qi; Gao, Shian; Shang, Jian Ku

    2013-09-15

    Phosphate removal is important in the control of eutrophication of water bodies. Adsorption is one of the promising approaches for the removal of phosphate, which could serve as a supplement for the biological phosphate removal process commonly used in the wastewater treatment industry to meet the discharge requirement when the biological performance is deteriorated from changes of operation conditions. Amorphous zirconium oxide nanoparticles were synthesized by a simple and low-cost hydrothermal process, and their phosphate removal performance was explored in aqueous environment under various conditions. A fast adsorption of phosphate was observed in the kinetics study, and their adsorption capacity was determined at about 99.01 mg/g at pH 6.2 in the equilibrium adsorption isotherm study. Commonly coexisting anions showed no or minimum effect on their phosphate adsorption performance. The phosphate adsorption showed little pH dependence in the range from pH 2 to 6, while it decreased sharply with the pH increase above pH 7. After adsorption, phosphate on these am-ZrO2 nanoparticles could be easily desorbed by NaOH solution washing. Both the macroscopic and microscopic techniques demonstrated that the phosphate adsorption mechanism of am-ZrO2 nanoparticles followed the inner-sphere complexing mechanism, and the surface hydroxyl groups played a key role in the phosphate adsorption.

  12. A combination of docking, QM/MM methods, and MD simulation for binding affinity estimation of metalloprotein ligands.

    PubMed

    Khandelwal, Akash; Lukacova, Viera; Comez, Dogan; Kroll, Daniel M; Raha, Soumyendu; Balaz, Stefan

    2005-08-25

    To alleviate the problems in the receptor-based design of metalloprotein ligands due to inadequacies in the force-field description of coordination bonds, a four-tier approach was devised. Representative ligand-metalloprotein interaction energies are obtained by subsequent application of (1) docking with metal-binding-guided selection of modes, (2) optimization of the ligand-metalloprotein complex geometry by combined quantum mechanics and molecular mechanics (QM/MM) methods, (3) conformational sampling of the complex with constrained metal bonds by force-field-based molecular dynamics (MD), and (4) a single point QM/MM energy calculation for the time-averaged structures. The QM/MM interaction energies are, in a linear combination with the desolvation-characterizing changes in the solvent-accessible surface areas, correlated with experimental data. The approach was applied to structural correlation of published binding free energies of a diverse set of 28 hydroxamate inhibitors to zinc-dependent matrix metalloproteinase 9 (MMP-9). Inclusion of steps 3 and 4 significantly improved both correlation and prediction. The two descriptors explained 90% of variance in inhibition constants of all 28 inhibitors, ranging from 0.08 to 349 nM, with the average unassigned error of 0.318 log units. The structural and energetic information obtained from the time-averaged MD simulation results helped understand the differences in binding modes of related compounds.

  13. On a Time-Space Operator (and other Non-Self-Adjoint Operators) for Observables in QM and QFT

    NASA Astrophysics Data System (ADS)

    Recami, Erasmo; Zamboni-Rached, Michel; Licata, Ignazio

    The aim of this paper is to show the possible significance, and usefulness, of various non-self-adjoint operators for suitable Observables in non-relativistic and relativistic quantum mechanics (QM), and in quantum electrodynamics. More specifically, this work deals with: (i) the Hermitian (but not self-adjoint) Time operator in non-relativistic QM and in quantum electrodynamics; (ii) idem, the introduction of Time and Space operators; and (iii) the problem of the four-position and four-momentum operators, each one with its Hermitian and anti-Hermitian parts, for relativistic spin-zero particles. Afterwards, other physical applications of non-self-adjoint (and even non-Hermitian) operators are briefly discussed. We mention how non-Hermitian operators can indeed be used in physics [as it was done, elsewhere, for describing Unstable States]; and some considerations are added on the cases of the nuclear optical potential, of quantum dissipation, and in particular of an approach to the measurement problem in QM in terms of a chronon. This paper is largely based on work developed, along the years, in collaboration with V.S. Olkhovsky, and, in smaller parts, with P. Smrz, with R.H.A. Farias, and with S.P. Maydanyuk.

  14. Prediction of molecular crystal structures by a crystallographic QM/MM model with full space-group symmetry.

    PubMed

    Mörschel, Philipp; Schmidt, Martin U

    2015-01-01

    A crystallographic quantum-mechanical/molecular-mechanical model (c-QM/MM model) with full space-group symmetry has been developed for molecular crystals. The lattice energy was calculated by quantum-mechanical methods for short-range interactions and force-field methods for long-range interactions. The quantum-mechanical calculations covered the interactions within the molecule and the interactions of a reference molecule with each of the surrounding 12-15 molecules. The interactions with all other molecules were treated by force-field methods. In each optimization step the energies in the QM and MM shells were calculated separately as single-point energies; after adding both energy contributions, the crystal structure (including the lattice parameters) was optimized accordingly. The space-group symmetry was maintained throughout. Crystal structures with more than one molecule per asymmetric unit, e.g. structures with Z' = 2, hydrates and solvates, have been optimized as well. Test calculations with different quantum-mechanical methods on nine small organic molecules revealed that the density functional theory methods with dispersion correction using the B97-D functional with 6-31G* basis set in combination with the DREIDING force field reproduced the experimental crystal structures with good accuracy. Subsequently the c-QM/MM method was applied to nine compounds from the CCDC blind tests resulting in good energy rankings and excellent geometric accuracies.

  15. Prediction of molecular crystal structures by a crystallographic QM/MM model with full space-group symmetry.

    PubMed

    Mörschel, Philipp; Schmidt, Martin U

    2015-01-01

    A crystallographic quantum-mechanical/molecular-mechanical model (c-QM/MM model) with full space-group symmetry has been developed for molecular crystals. The lattice energy was calculated by quantum-mechanical methods for short-range interactions and force-field methods for long-range interactions. The quantum-mechanical calculations covered the interactions within the molecule and the interactions of a reference molecule with each of the surrounding 12-15 molecules. The interactions with all other molecules were treated by force-field methods. In each optimization step the energies in the QM and MM shells were calculated separately as single-point energies; after adding both energy contributions, the crystal structure (including the lattice parameters) was optimized accordingly. The space-group symmetry was maintained throughout. Crystal structures with more than one molecule per asymmetric unit, e.g. structures with Z' = 2, hydrates and solvates, have been optimized as well. Test calculations with different quantum-mechanical methods on nine small organic molecules revealed that the density functional theory methods with dispersion correction using the B97-D functional with 6-31G* basis set in combination with the DREIDING force field reproduced the experimental crystal structures with good accuracy. Subsequently the c-QM/MM method was applied to nine compounds from the CCDC blind tests resulting in good energy rankings and excellent geometric accuracies. PMID:25537386

  16. Electronic properties of water in liquid environment. A sequential QM/MM study using the free energy gradient method.

    PubMed

    Georg, Herbert C; Canuto, Sylvio

    2012-09-13

    There is a continuous search for theoretical methods that are able to describe the effects of the liquid environment on molecular systems. Different methods emphasize different aspects, and the treatment of both the local and bulk properties is still a great challenge. In this work, the electronic properties of a water molecule in liquid environment is studied by performing a relaxation of the geometry and electronic distribution using the free energy gradient method. This is made using a series of steps in each of which we run a purely molecular mechanical (MM) Monte Carlo Metropolis simulation of liquid water and subsequently perform a quantum mechanical/molecular mechanical (QM/MM) calculation of the ensemble averages of the charge distribution, atomic forces, and second derivatives. The MP2/aug-cc-pV5Z level is used to describe the electronic properties of the QM water. B3LYP with specially designed basis functions are used for the magnetic properties. Very good agreement is found for the local properties of water, such as geometry, vibrational frequencies, dipole moment, dipole polarizability, chemical shift, and spin-spin coupling constants. The very good performance of the free energy method combined with a QM/MM approach along with the possible limitations are briefly discussed.

  17. Fluorocarbon adsorption in hierarchical porous frameworks

    NASA Astrophysics Data System (ADS)

    Motkuri, Radha Kishan; Annapureddy, Harsha V. R.; Vijaykumar, M.; Schaef, H. Todd; Martin, Paul F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-01

    Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g-1 at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g-1 at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane >chlorodifluoromethane >chlorotrifluoromethane >tetrafluoromethane >methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

  18. Fluorocarbon adsorption in hierarchical porous frameworks.

    PubMed

    Motkuri, Radha Kishan; Annapureddy, Harsha V R; Vijaykumar, M; Schaef, H Todd; Martin, Paul F; McGrail, B Peter; Dang, Liem X; Krishna, Rajamani; Thallapally, Praveen K

    2014-07-09

    Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g(-1) at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g(-1) at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane > chlorodifluoromethane > chlorotrifluoromethane > tetrafluoromethane > methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

  19. Fluorocarbon adsorption in hierarchical porous frameworks

    SciTech Connect

    Motkuri, RK; Annapureddy, HVR; Vijaykumar, M; Schaef, HT; Martin, PF; McGrail, BP; Dang, LX; Krishna, R; Thallapally, PK

    2014-07-09

    Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g(-1) at a very low relative saturation pressure (P/P-o) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g(-1) at P/P-o of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane >chlorodifluoromethane >chlorotrifluoromethane >tetrafluoromethane >methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

  20. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values.

  1. Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

    PubMed

    Suriyanon, Nakorn; Permrungruang, Jutima; Kaosaiphun, Jidanan; Wongrueng, Aunnop; Ngamcharussrivichai, Chawalit; Punyapalakul, Patiparn

    2015-10-01

    The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values. PMID:26025186

  2. Enhanced hydrogen storage capacity of copper containing mesoporous silicas prepared using different methods

    NASA Astrophysics Data System (ADS)

    Sekkiou, Housseyn; Boukoussa, Bouhadjar; Ghezini, Rachid; Khenchoul, Zineb; Ouali, Affaf; Hamacha, Rachida; Bengueddach, Abdelkader

    2016-08-01

    This paper focuses on the synthesis of mesoporous materials, Al-MCM-41, doped with copper using different methods. The results show that the method of synthesis affects the structural and textural properties of these solids. Their application in hydrogen storage shows that the adsorption is enhanced when using a solid containing Cu+2 ions, with an adsorption capacity around 1.8 wt% at 77 K, while the solids containing CuO particles present a medium adsorption capacity. Temperature variation plays a very important role in determining the adsorption capacity and the best results are obtained at 77 K.

  3. Poliovirus Adsorption by 34 Minerals and Soils

    PubMed Central

    Moore, Rebecca S.; Taylor, Dene H.; Sturman, Lawrence S.; Reddy, Michael M.; Fuhs, G. Wolfgang

    1981-01-01

    The adsorption of radiolabeled infectious poliovirus type 2 by 34 well-defined soils and mineral substrates was analyzed in a synthetic freshwater medium containing 1 mM CaCl2 and 1.25 mM NaHCO3 at pH 7. In a model system, adsorption of poliovirus by Ottawa sand was rapid and reached equilibrium within 1 h at 4°C. Near saturation, the adsorption could be described by the Langmuir equation; the apparent surface saturation was 2.5 × 106 plaque-forming units of poliovirus per mg of Ottawa sand. At low surface coverage, adsorption was described by the Freundlich equation. The soils and minerals used ranged from acidic to basic and from high in organic content to organic free. The available negative surface charge on each substrate was measured by the adsorption of a cationic polyelectrolyte, polydiallyldimethylammonium chloride. Most of the substrates adsorbed more than 95% of the virus. In general, soils, in comparison with minerals, were weak adsorbents. Among the soils, muck and Genesee silt loam were the poorest adsorbents; among the minerals, montmorillonite, glauconite, and bituminous shale were the least effective. The most effective adsorbents were magnetite sand and hematite, which are predominantly oxides of iron. Correlation coefficients for substrate properties and virus adsorption revealed that the elemental composition of the adsorbents had little effect on poliovirus uptake. Substrate surface area and pH, by themselves, were not significantly correlated with poliovirus uptake. A strong negative correlation was found between poliovirus adsorption and both the contents of organic matter and the available negative surface charge on the substrates as determined by their capacities for adsorbing the cationic polyelectrolyte, polydiallyldimethylammonium chloride. PMID:6274259

  4. Adsorption behavior of heavy metals on biomaterials.

    PubMed

    Minamisawa, Mayumi; Minamisawa, Hiroaki; Yoshida, Shoichiro; Takai, Nobuharu

    2004-09-01

    We have investigated adsorption of Cd(II) and Pb(II) at pH 2-6.7 onto the biomaterials chitosan, coffee, green tea, tea, yuzu, aloe, and Japanese coarse tea, and onto the inorganic adsorbents, activated carbon and zeolite. High adsorptive capabilities were observed for all of the biomaterials at pH 4 and 6.7. In the adsorption of Cd(II), blend coffee, tea, green tea, and coarse tea have comparable loading capacities to activated carbon and zeolite. Although activated carbon, zeolite, and chitosan are utilized in a variety of fields such as wastewater treatment, chemical and metallurgical engineering, and analytical chemistry, these adsorbents are costly. On the other hand, processing of the test biomaterials was inexpensive, and all the biomaterials except for chitosan were able to adsorb large amounts of Pb(II) and Cd(II) ions after a convenient pretreatment of washing with water followed by drying. The high adsorption capability of the biomaterials prepared from plant materials is promising in the development of a novel, low-cost adsorbent. From these results, it is concluded that heavy metal removal using biomaterials would be an effective method for the economic treatment of wastewater. The proposed adsorption method was applied to the determination of amounts of Cd(II) and Pb(II) in water samples.

  5. Phosphate adsorption on granular palygorskite: batch and column studies.

    PubMed

    Fangqun, Gan; Jianmin, Zhou; Huoyan, Wang; Changwen, Du; Wenzhao, Zhang; Xiaoqin, Chen

    2011-02-01

    A method to prepare granular palygorskite (GPA) was put forward in this research, and its potential use to remove phosphate species from aqueous solution was assessed. Batch experiments were performed to study the adsorption equilibrium and influence of contact time and pH on the adsorption and desorption of phosphate onto GPA in water. The maximum phosphate adsorption capacity of GPA was 13.1 mg/g. Kinetic data revealed that more than 90% of phosphate was adsorbed onto GPA within 2 hours. Phosphate adsorption capacity was 0.10 mg/g in column experiments, and co-existing anions could decrease phosphate removal. The saturated column was regenerated by 0.2 mol/L sodium hydroxide, and the GPA could be reused in phosphate removal. The data obtained from both batch and column studies indicated that GPA could be used effectively to remove phosphate from water.

  6. Optimization of salt adsorption rate in membrane capacitive deionization.

    PubMed

    Zhao, R; Satpradit, O; Rijnaarts, H H M; Biesheuvel, P M; van der Wal, A

    2013-04-01

    Membrane capacitive deionization (MCDI) is a water desalination technique based on applying a cell voltage between two oppositely placed porous electrodes sandwiching a spacer channel that transports the water to be desalinated. In MCDI, ion-exchange membranes are positioned in front of each porous electrode to prevent co-ions from leaving the electrode region during ion adsorption, thereby enhancing the salt adsorption capacity. MCDI can be operated at constant cell voltage (CV), or at a constant electrical current (CC). In this paper, we present both experimental and theoretical results for desalination capacity and rate in MCDI (both in the CV- and the CC-mode) as function of adsorption/desorption time, salt feed concentration, electrical current, and cell voltage. We demonstrate how by varying each parameter individually, it is possible to systematically optimize the parameter settings of a given system to achieve the highest average salt adsorption rate and water recovery.

  7. Adsorption of aqueous copper on peanut hulls

    NASA Astrophysics Data System (ADS)

    Davis, Kanika Octavia

    , scanning electron microscopy images coupled with energy dispersive X-ray spectroscopy showed that the percentage of copper on the modified hulls (2.5 %) was greater than on the unmodified hulls (1.6 %). This study concluded that the adsorption of copper using peanut hulls is a potential method for wastewater treatment and delignification and oxidation of the hulls increases the adsorption capacity approximately three-fold.

  8. QM/MM MD simulations of La(III)-phosphopeptide complexes.

    PubMed

    Messner, Christoph B; Bonn, Günther K; Hofer, Thomas S

    2015-01-01

    Several bioanalytical enrichment techniques are based on the interactions of phosphopeptides with Ln(III) ions. In order to gain an improved understanding of these complexes and the respective ion-peptide interactions, hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations of La(III) coordinating to the phosphopeptide VPQLEIVPNSpAEER were conducted. Simulations of di- as well as monoanionic phosphate groups were carried out. The La(III) ion and its first hydration layer, including the sidechain of the phosphoserine residue were treated quantum mechanically at RI-MP2/triple zeta level, whereas the remaining part of the system was treated with classical potentials. The simulation of the dianionic phosphopeptide revealed a 9-fold coordinated La(III) ion, with the phosphopeptide binding bi- as well as monodentate. The mean residence times (τ) of the first shell water molecules were 82 ps and 37 ps for the bi- and monodentate complexes, respectively, which is much higher compared to free La(III) in aqueous solution (τ=17 ps). The simulation of the monoanionic La(III)-phosphopeptide complex revealed a bidentate coordination throughout the 80 ps sampling period. An intramolecular hydrogen bond between the hydrogen of the phosphate group and the backbone was observed and a τ value of 14 ps was obtained, which is much lower as for the dianionic complex.

  9. Binding of piano-stool Ru(II) complexes to DNA; QM/MM study.

    PubMed

    Futera, Zdeněk; Platts, James A; Burda, Jaroslav V

    2012-10-01

    Ru(II) "piano-stool" complexes belong to group of biologically active metallocomplexes with promising anticancer activity. In this study, we investigate the reaction mechanism of [(η(6)-benzene)Ru(II)(en)(H(2)O)](2+) (en = ethylenediamine) complex binding to DNA by hybrid QM/MM computational techniques. The reaction when the Ru(II) complex is coordinated on N7-guanine from major groove is explored. Two reaction pathways, direct binding to N7 position and two-step mechanism passing through O6 position, are considered. It was found that the reaction is exothermic and the direct binding process is preferred kinetically. In analogy to cisplatin, we also explored the possibility of intrastrand cross-link formation where the Ru(II) complex makes a bridge between two adjacent guanines. Two different pathways were found, leading to a final structure with released benzene ligand. This process is exothermic; however, one pathway is blocked by relatively high initial activation barrier. Geometries, energies, and electronic properties analyzed by atoms in molecules and natural population analysis methods are discussed. PMID:22707416

  10. QM/MD studies on graphene growth from small islands on the Ni(111) surface

    NASA Astrophysics Data System (ADS)

    Jiao, Menggai; Song, Wei; Qian, Hu-Jun; Wang, Ying; Wu, Zhijian; Irle, Stephan; Morokuma, Keiji

    2016-01-01

    the nuclei to expand the size of the growing carbon network. The growth of graphene precursors is accompanied by the corresponding changes in the bonding of nickel atoms with the precipitation of subsurface carbon atoms. This is because the carbon-carbon interaction is stronger than the nickel-carbon interaction. In the case of high carbon nucleation densities, the dominant ripening mechanism depends on different growth stages. In the initial stage, the coalescence of carbon islands takes place via the Smoluchowski ripening mechanism. In the later stage the Smoluchowski ripening process is damped owing to the higher diffusion barrier of larger clusters and the restriction of movement by self-assembled nickel step edges. The cross-linking mechanism eventually takes over by the coalescence of extended polyyne chains between graphene islands. In either case, the Ostwald ripening process is not found in our molecular dynamics simulations due to the stability of carbon-carbon bonds within the islands. These investigations should be instructive to the control of graphene growth in experiments. Electronic supplementary information (ESI) available: There are two movies showing the simulation process and they are provided in separate files. Movie S1 is the evolution of QM/MD simulations of the growth of graphene from one C13 on the Ni(111) surface for trajectory D@C13. Movie S2 is the evolution of QM/MD simulations of the growth of graphene from two C13 species on the Ni(111) surface for trajectory C@2C13. Fig. S1 shows the optimized geometries of C13-G and C13-H on the Ni(111) surface. Fig. S2 is the final structures of trajectories A-J@C13 following 400 ps QM/MD simulation for the Ni(111) + C13 system. Fig. S3 is the final structures of trajectories A-J@2C13 following 350 ps QM/MD simulation for the Ni(111) + 2C13 system. Fig. S4 shows average polygonal carbon ring populations formed during graphene growth from the Ni(111) + C13 and Ni(111) + 2C13 systems. Fig. S5 shows the

  11. How Is Acetylcholinesterase Phosphonylated by Soman? An Ab Initio QM/MM Molecular Dynamics Study

    PubMed Central

    2015-01-01

    Acetylcholinesterase (AChE) is a crucial enzyme in the cholinergic nerve system that hydrolyzes acetylcholine (ACh) and terminates synaptic signals by reducing the effective concentration of ACh in the synaptic clefts. Organophosphate compounds irreversibly inhibit AChEs, leading to irreparable damage to nerve cells. By employing Born–Oppenheimer ab initio QM/MM molecular dynamics simulations with umbrella sampling, a state-of-the-art approach to simulate enzyme reactions, we have characterized the covalent inhibition mechanism between AChE and the nerve toxin soman and determined its free energy profile for the first time. Our results indicate that phosphonylation of the catalytic serine by soman employs an addition–elimination mechanism, which is highly associative and stepwise: in the initial addition step, which is also rate-limiting, His440 acts as a general base to facilitate the nucleophilic attack of Ser200 on the soman’s phosphorus atom to form a trigonal bipyrimidal pentacovalent intermediate; in the subsequent elimination step, Try121 of the catalytic gorge stabilizes the leaving fluorine atom prior to its dissociation from the active site. Together with our previous characterization of the aging mechanism of soman inhibited AChE, our simulations have revealed detailed molecular mechanistic insights into the damaging function of the nerve agent soman. PMID:24786171

  12. Reaction mechanism of cobalt-substituted homoprotocatechuate 2,3-dioxygenase: a QM/MM study.

    PubMed

    Cao, Lili; Dong, Geng; Lai, Wenzhen

    2015-04-01

    The reaction mechanisms of cobalt-substituted homoprotocatechuate 2,3-dioxygenase (Co-HPCD) with electron-rich substrate homoprotocatechuate (HPCA) and electron-poor substrate 4-nitrocatechol (4NC) were investigated by quantum mechanical/molecular mechanical (QM/MM) calculations. Our results demonstrated that the Co-O2 adducts has doublet ground state with a Co(III)-O2(•-) character when 4NC was used as the substrate, in good agreement with the EPR spectroscopic experiment. The reactive oxygen species is the doublet Co(III)-O2(•-) for Co-HPCD/4NC and the quartet SQ(•↑)-Co(II)-O2(•-↓) species for Co-HPCD/HPCA, indicating that the substrate plays important roles in the dioxygen activation by Co-HPCD. B3LYP was found to overestimate the rate-limiting barriers in Co-HPCD. TPSSh predicts barriers of 21.5 versus 12.0 kcal/mol for Co-HPCD/4NC versus Co-HPCD/HPCA, which is consistent with the fact that the rate of the reaction is decreased when the substrate was changed from HPCA to 4NC.

  13. Catalytic Mechanism of Nitrile Hydratase Subsequent to Cyclic Intermediate Formation: A QM/MM Study.

    PubMed

    Kayanuma, Megumi; Shoji, Mitsuo; Yohda, Masafumi; Odaka, Masafumi; Shigeta, Yasuteru

    2016-04-01

    The catalytic mechanism of an Fe-containing nitrile hydratase (NHase) subsequent to the formation of a cyclic intermediate was investigated using a hybrid quantum mechanics/molecular mechanics (QM/MM) method. We identified the following mechanism: (i) proton transfer from βTyr72 to the substrate via αSer113, and cleavage of the S-O bond of αCys114-SO(-) and formation of a disulfide bond between αCys109 and αCys114; (ii) direct attack of a water molecule on the sulfur atom of αCys114, which resulted in the generation of both an imidic acid and a renewed sulfenic cysteine; and (iii) isomerization of the imidic acid to the amide. In addition, to clarify the role of βArg56K, which is one of the essential amino residues in the enzyme, we analyzed a βR56K mutant in which βArg56 was replaced by Lys. The results suggest that βArg56 is necessary for the formation of disulfide intermediate by stabilizing the cleavage of the S-O bond via a hydrogen bond with the oxygen atom of αCys114-SO(-). PMID:27007978

  14. Electrostatics of DNA nucleotide-carbon nanotube hybrids evaluated from QM:MM simulations.

    PubMed

    Chehel Amirani, Morteza; Tang, Tian

    2015-12-14

    Biomolecule-functionalized carbon nanotubes (CNTs) have been studied vastly in recent years due to their potential applications for instance in cancer detection, purification and separation of CNTs, and nanoelectronics. Studying the electrostatic potential generated by a biomolecule-CNT hybrid is important in predicting its interactions with the surrounding environment such as charged particles and surfaces. In this paper, we performed atomistic simulations using a QM:MM approach to evaluate the electrostatic potential and charge transfer for a hybrid structure formed by a DNA nucleotide and a CNT in solution. Four types of DNA nucleotides and two CNTs with chiralities of (4,4) and (7,0) were considered. The types of nucleotides and CNTs were both found to play important roles in the electrostatic potential and charge transfer of the hybrid. At the same distance from the CNT axis, the electrostatic potential for the nucleotide-(4,4) CNT hybrids was found to be stronger compared with that for the nucleotide-(7,0) CNT hybrids. Higher electric charge was also shown to be transferred from the DNA nucleotides to the (7,0) CNT compared with the (4,4) CNT. These results correlate with the previous finding that the nucleotides bound more tightly to the (7,0) CNT compared with the (4,4) CNT. PMID:26542447

  15. QM/MD studies on graphene growth from small islands on the Ni(111) surface

    NASA Astrophysics Data System (ADS)

    Jiao, Menggai; Song, Wei; Qian, Hu-Jun; Wang, Ying; Wu, Zhijian; Irle, Stephan; Morokuma, Keiji

    2016-01-01

    the nuclei to expand the size of the growing carbon network. The growth of graphene precursors is accompanied by the corresponding changes in the bonding of nickel atoms with the precipitation of subsurface carbon atoms. This is because the carbon-carbon interaction is stronger than the nickel-carbon interaction. In the case of high carbon nucleation densities, the dominant ripening mechanism depends on different growth stages. In the initial stage, the coalescence of carbon islands takes place via the Smoluchowski ripening mechanism. In the later stage the Smoluchowski ripening process is damped owing to the higher diffusion barrier of larger clusters and the restriction of movement by self-assembled nickel step edges. The cross-linking mechanism eventually takes over by the coalescence of extended polyyne chains between graphene islands. In either case, the Ostwald ripening process is not found in our molecular dynamics simulations due to the stability of carbon-carbon bonds within the islands. These investigations should be instructive to the control of graphene growth in experiments. Electronic supplementary information (ESI) available: There are two movies showing the simulation process and they are provided in separate files. Movie S1 is the evolution of QM/MD simulations of the growth of graphene from one C13 on the Ni(111) surface for trajectory D@C13. Movie S2 is the evolution of QM/MD simulations of the growth of graphene from two C13 species on the Ni(111) surface for trajectory C@2C13. Fig. S1 shows the optimized geometries of C13-G and C13-H on the Ni(111) surface. Fig. S2 is the final structures of trajectories A-J@C13 following 400 ps QM/MD simulation for the Ni(111) + C13 system. Fig. S3 is the final structures of trajectories A-J@2C13 following 350 ps QM/MD simulation for the Ni(111) + 2C13 system. Fig. S4 shows average polygonal carbon ring populations formed during graphene growth from the Ni(111) + C13 and Ni(111) + 2C13 systems. Fig. S5 shows the

  16. Hermann Grid's Dark Diagonals Disprove QM's ``Beliefs,'' Reveal Stringy Electron, Nucleons, Stick Figure Constellations

    NASA Astrophysics Data System (ADS)

    McLeod, Roger David; McLeod, David Matthew

    2011-11-01

    Vision detects electric field amplitude information from spatial Fourier transforms, SFTs, of object space. Optics states: at focal, not image, surfaces, for Hermann, and pincushion, grids. Von B'ek'esy's skin pressure experiments prove brain circuitry interprets focal diffraction patterns as inverse SFTs. This knocks out QM beliefs, enhanced by Schr"odinger's electron assertions. Mc Leods' electron string model, based on a neutrino in chiral embrace with a parallel, magnetically repellant, antineutrino, transversely aligned in continuous pairings along each wave-string's closure. This generalized, in Recife, PE, Brazil, to the three-ring, up quark, down quark, up quark, of our Dumbo Proton, underpass-overpass string. Cut by an antineutrino scissor, and merged with our compressed, neutrino-cut electron, a Mickey Neutron with over- or underpass pairs only, emerges, is unstable, and is of 4/3 e string units length. Dumbo Proton is 5/3 e units; this string theory predicts a Trinitarian Electron, with charge -1/3 e, whatever phase, Standing Wave Up, SWU, Traveling Wave, TW, or Standing Wave Down, SWD. It explains solar neutrino flux factor 3 shortfall. Camcorders capture this electron at gigapower n values. Peruvian Nazcans recorded high energy, composite nucleon trajectories for us, as ``applied optical (VISION) physicists.''

  17. A priori evaluation of aqueous polarization effects through Monte Carlo QM-MM simulations.

    PubMed

    Gao, J; Xia, X

    1992-10-23

    A Monte Carlo quantum mechanical-molecular mechanical (QM-MM) simulation method was used to determine the contributions of the solvent polarization effect to the total interaction energies between solute and solvent for amino acid side chains and nucleotide bases in aqueous solution. In the present AM1-TIP3P approach, the solute molecule is characterized by valence electrons and nucleus cores with Hartree-Fock theory incorporating explicit solvent effects into the total Hamiltonian, while the solvent is approximated by the three-point charge TIP3P model. The polarization energy contributes 10 to 20 percent of the total electrostatic energy in these systems. The performance of the hybrid AM1-TIP3P model was further validated by consideration of bimolecular complexes with water and by computation of the free energies of solvation of organic molecules using statistical perturbation theory. Excellent agreement with ab initio 6-31G(d) results and experimental solvation free energies was obtained.

  18. Insights into structure and redox potential of lignin peroxidase from QM/MM calculations.

    PubMed

    Castro, Ludovic; Crawford, Luke; Mutengwa, Archford; Götze, Jan P; Bühl, Michael

    2016-02-28

    Redox potentials are computed for the active form (compound I) of lignin peroxidase (LiP) using a suitable QM/MM methodology (B3LYP/SDD/6-311G**//BP86/SVP:CHARMM). Allowing for dynamic conformational averaging, a potential of 0.67(33) V relative to ferrocenium/ferrocene is obtained for the active form with its oxoiron(iv) core. The computed redox potential is very sensitive to the charge distribution around the active site: protonation of titratable residues close to the metal center increases the redox potential, thereby rationalising the known pH dependence of LiP activity. A simple MM-charge deletion scheme is used to identify residues that are critical for the redox potential. Two mutant proteins are studied through homology modelling, E40Q and D183N, which are predicted to have an increased redox potential by 140 mV and 190 mV, respectively, relative to the wild type. These mutant proteins are thus promising targets for synthesis and further exploration toward a rational design of biocatalytic systems for oxidative degradation of lignin.

  19. Adsorption kinetics of herbicide paraquat from aqueous solution onto activated bleaching earth.

    PubMed

    Tsai, W T; Lai, C W; Hsien, K J

    2004-05-01

    In the present study, the activated bleaching earth was used as adsorbent for the herbicide paraquat adsorption in a batch adsorber. The rate of adsorption has been investigated under the controlled process parameters like agitation speed, initial paraquat concentration, adsorbent dosage and temperature. A batch kinetic model, based on the assumption of a pseudo-second order mechanism, has been tested to predict the rate constant of adsorption, equilibrium adsorption capacity, time of half-adsorption, and equilibrium concentration by the fittings of the experimental data. The results of the kinetic studies show that the adsorption process can be well described with the pseudo-second order equation. Based on the isotherm data obtained from the fittings of the adsorption kinetics, Freundlich model appears to fit the adsorption better than Langmuir model. In addition, the effective diffusion coefficient has also been estimated based on the restrictive diffusion model.

  20. Adsorption of methylene blue from aqueous solution by graphene.

    PubMed

    Liu, Tonghao; Li, Yanhui; Du, Qiuju; Sun, Jiankun; Jiao, Yuqin; Yang, Guangming; Wang, Zonghua; Xia, Yanzhi; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-02-01

    Graphene was prepared using a modified Hummers' method. The physico-chemical properties of graphene were characterized by TEM, BET specific surface area, FTIR, Raman and XRD measurements. The effect factors including pH, contact time, temperature and dosage on the adsorption properties of methylene blue onto graphene were investigated. The experimental data of isotherm followed the Langmuir isotherm model better than the Freundlich model. The maximum adsorption capacity obtained from Langmuir isotherm equation at 293 K was 153.85 mg/g, indicating graphene is a good adsorbent for the adsorption of MB. The kinetic study illustrated that the adsorption of methylene blue onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of methylene blue onto graphene was an endothermic and spontaneous process.

  1. Adsorption of emerging pollutants on functionalized multiwall carbon nanotubes.

    PubMed

    Patiño, Yolanda; Díaz, Eva; Ordóñez, Salvador; Gallegos-Suarez, Esteban; Guerrero-Ruiz, Antonio; Rodríguez-Ramos, Inmaculada

    2015-10-01

    Adsorption of three representative emerging pollutants - 1,8-dichlorooctane, nalidixic acid and 2-(4-methylphenoxy)ethanol- on different carbon nanotubes was studied in order to determine the influence of the morphological and chemical properties of the materials on their adsorption properties. As adsorbents, multiwall carbon nanotubes (MWCNTs) without functionalization and with oxygen or nitrogen surface groups, as well as carbon nanotubes doped with nitrogen were used. The adsorption was studied in aqueous phase using batch adsorption experiments, results being fitted to both Langmuir and Freundlich models. The adsorption capacity is strongly dependent on both the hydrophobicity of the adsorbates and the morphology of the adsorbents. Thermodynamic parameters were determined observing strong interactions between the aromatic rings of the emerging pollutant and the nitrogen modified adsorbents.

  2. Adsorption of ammonium dinitramide (ADN) from aqueous solutions. 1. Adsorption on powdered activated charcoal.

    PubMed

    Santhosh, G; Venkatachalam, S; Ninan, K N; Sadhana, R; Alwan, S; Abarna, V; Joseph, M A

    2003-03-17

    Investigations on the adsorption of ammonium dinitramide (NH(4)N(NO(2))(2)) (ADN) from aqueous solutions on powdered activated charcoal (PAC) were carried out in order to find out an effective and easier method of separating ADN from aqueous solutions. The effectiveness of PAC in the selective adsorption of ADN from aqueous solutions of ADN (ADN-F) and ADN in presence of sulfate (SO(4)(2-)) and nitrate (NO(3)(-)) ions (ADN-PS) was examined and compared using batch and column methods. The adsorption process follows both Langmuir and Freundlich adsorption isotherms and the isotherm parameters for the models were determined. The observed data favor the formation of monolayer adsorption. The adsorption capacities were found to be 63.3, 119, 105.3 and 82 mg of ADN per g of PAC for ADN-F (batch), ADN-PS (batch), ADN-F (column) and ADN-PS (column), respectively. Break-through curves for ADN-F and ADN-PS were obtained for the optimization of separation of ADN from aqueous solutions. Elution curves were generated for the desorption of ADN from PAC using hot water as eluent.

  3. Solvent Boundary Potentials for Hybrid QM/MM Computations Using Classical Drude Oscillators: A Fully Polarizable Model.

    PubMed

    Boulanger, Eliot; Thiel, Walter

    2012-11-13

    Accurate quantum mechanical/molecular mechanical (QM/MM) treatments should account for MM polarization and properly include long-range electrostatic interactions. We report on a development that covers both these aspects. Our approach combines the classical Drude oscillator (DO) model for the electronic polarizability of the MM atoms with the generalized solvent boundary Potential (GSBP) and the solvated macromolecule boundary potential (SMBP). These boundary potentials (BP) are designed to capture the long-range effects of the outer region of a large system on its interior. They employ a finite difference approximation to the Poisson-Boltzmann equation for computing electrostatic interactions and take into account outer-region bulk solvent through a polarizable dielectric continuum (PDC). This approach thus leads to fully polarizable three-layer QM/MM-DO/BP methods. As the mutual responses of each of the subsystems have to be taken into account, we propose efficient schemes to converge the polarization of each layer simultaneously. For molecular dynamics (MD) simulations using GSBP, this is achieved by considering the MM polarizable model as a dynamical degree of freedom, and hence contributions from the boundary potential can be evaluated for a frozen state of polarization at every time step. For geometry optimizations using SMBP, we propose a dual self-consistent field approach for relaxing the Drude oscillators to their ideal positions and converging the QM wave function with the proper boundary potential. The chosen coupling schemes are evaluated with a test system consisting of a glycine molecule in a water ball. Both boundary potentials are capable of properly reproducing the gradients at the inner-region atoms and the Drude oscillators. We show that the effect of the Drude oscillators must be included in all terms of the boundary potentials to obtain accurate results and that the use of a high dielectric constant for the PDC does not lead to a polarization

  4. Adsorption of cadmium by biochar derived from municipal sewage sludge: Impact factors and adsorption mechanism.

    PubMed

    Chen, Tan; Zhou, Zeyu; Han, Rong; Meng, Ruihong; Wang, Hongtao; Lu, Wenjing

    2015-09-01

    Static equilibrium experiments were carried out to investigate the impact factors and the mechanism of cadmium adsorption on biochar derived from municipal sewage sludge. An appropriate dosage of biochar is sufficient; in the experiment, 0.2% is the optimal dosage for the largest removal capacity, while the removal capacity of biochar reduces with the increasing dosage. pH is another dominant factor of the adsorption process. The removal capacity of biochar is lower than 20 mg·g(-1) when the solution initial pH is lower than 2 pH units, comparatively retaining more than 40 mg·g(-1) at the solution initial pH higher than 3 pH units. Temperature has weak influence on the adsorptive performance. The main mechanism of the adsorption process of biochar for cadmium mainly involves (1) surface precipitation by forming insoluble cadmium compounds in alkaline condition, and (2) ion exchange for cadmium with exchangeable cations in the biochar, such as calcium ions.

  5. Adsorption of cadmium by biochar derived from municipal sewage sludge: Impact factors and adsorption mechanism.

    PubMed

    Chen, Tan; Zhou, Zeyu; Han, Rong; Meng, Ruihong; Wang, Hongtao; Lu, Wenjing

    2015-09-01

    Static equilibrium experiments were carried out to investigate the impact factors and the mechanism of cadmium adsorption on biochar derived from municipal sewage sludge. An appropriate dosage of biochar is sufficient; in the experiment, 0.2% is the optimal dosage for the largest removal capacity, while the removal capacity of biochar reduces with the increasing dosage. pH is another dominant factor of the adsorption process. The removal capacity of biochar is lower than 20 mg·g(-1) when the solution initial pH is lower than 2 pH units, comparatively retaining more than 40 mg·g(-1) at the solution initial pH higher than 3 pH units. Temperature has weak influence on the adsorptive performance. The main mechanism of the adsorption process of biochar for cadmium mainly involves (1) surface precipitation by forming insoluble cadmium compounds in alkaline condition, and (2) ion exchange for cadmium with exchangeable cations in the biochar, such as calcium ions. PMID:25966459

  6. Effects of Humidity Swings on Adsorption Columns for Air Revitalization: Modeling and Experiments

    NASA Technical Reports Server (NTRS)

    LeVan, M. Douglas; Finn, John E.

    1997-01-01

    Air purification systems are necessary to provide clean air in the closed environments aboard spacecraft. Trace contaminants are removed using adsorption. One major factor concerning the removal of trace contaminants is relative humidity. Water can reduce adsorption capacity and, due to constant fluctuations, its presence is difficult to incorporate into adsorption column designs. The purpose of the research was to allow for better design techniques in trace contaminant adsorption systems, especially for feeds with water present. Experiments and mathematical modeling research on effects of humidity swings on adsorption columns for air revitalization were carried out.

  7. [Assessment of legal capacity and testamentary capacity].

    PubMed

    Dreßing, H; Foerster, K; Leygraf, J; Schneider, F

    2014-11-01

    The assessment of legal capacity and testamentary capacity require thorough knowledge of the legal framework and the relevant case law. This paper explains the concept of the legal capacity to contract and the concept of testamentary capacity with respect to German civil law. The relevance of major mental disorders for the assessment of legal capacity and testamentary capacity is discussed.

  8. Adsorption and regenerative oxidation of trichlorophenol with synthetic zeolite: Ozone dosage and its influence on adsorption performance.

    PubMed

    Zhang, Yongjun; Prigent, Bastien; Geißen, Sven-Uwe

    2016-07-01

    Regeneration of loaded adsorbents is a key step for the sustainability of an adsorption process. In this study, ozone was applied to regenerate a synthetic zeolite for the adsorption of trichlorophenol (TCP) as an organic model pollutant. Three initial concentrations of TCP in water phase were used in adsorption tests. After the equilibrium, zeolite loaded different amounts of TCP was dried and then regenerated with ozone gas. It was found that the adsorption capacity of zeolite was increased through three regeneration cycles. However, the adsorption kinetics was compromised after the regeneration with slightly declined 2nd order reaction constants. The ozone demand for the regeneration was highly dependent on the TCP mass loaded onto the zeolite. It was estimated that the mass ratio of ozone to TCP was 1.2 ± 0.3 g O3/g TCP. PMID:27043379

  9. Adsorption of phosphate from aqueous solution by hydrous zirconium oxide.

    PubMed

    Rodrigues, Liana Alvares; Maschio, Leandro José; Coppio, Luciana de Simone Cividanes; Thim, Gilmar Patrocínio; da Silva, Maria Lúcia Caetano Pinto

    2012-06-01

    Synthetic ZrO2 x nH2O was used for phosphate removal from aqueous solution. The optimum adsorbent dose obtained for phosphate adsorption on to hydrous zirconium oxide was 0.1 g. The kinetic process was described very well by a pseudo-second-order rate model. The phosphate adsorption tended to increase with the decrease in pH. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. A phosphate desorption of approximately 74% was obtained using water at pH 12.

  10. Adsorptive separation in bioprocess engineering

    SciTech Connect

    Huang, E.W.Y.

    1987-01-01

    The invention and development of an energy-efficient separation technique for recovery of desired chemicals from biomass conversion would greatly enhance the economic viability of this bioprocess. Adsorptive separation of several chemicals from aqueous solution was studied in this thesis. The desired species were recovered from the dilute aqueous solution by using crosslinked polyvinylpyridine resin to effect selective sorption. The sorbed chemicals were then removed from the resin by either thermal regeneration or elution with some appropriate desorbents. The effects of temperature, pH value, and solute concentration on resin swelling were investigated. The adsorption equilibrium isotherms, resin capacities and resin selectivities of methanol, ethanol, 1-propanol, isopropanol, glycerol, acetone, 1-butanol, tert-butanol, and 2,3-butanediol were determined to study the homologies. Furthermore, acetic acid, butyric acid, hydrochloric acid, lactic acid, and sulfuric acid were recovered from very dilute aqueous solutions. The concentration of the sorbed chemical in the stationary phase can be many times higher than in the mobile phase for some acids. Finally, different types of equilibrium isotherms were used to fit the experimental data. A mathematical model was developed by using the theory of interference to predict the breakthrough curves and the process efficiency to provide information for large-scale process design and development.

  11. [Toluene, Benzene and Acetone Adsorption by Activated Carbon Coated with PDMS].

    PubMed

    Liu, Han-bing; Jiang, Xin; Wang, Xin; Yang, Bing; Xue, Nan-dong; Zhang, Shi-lei

    2016-04-15

    To improve the adsorption selectivity of volatile organic compounds ( VOCs) , activated carbon ( AC) was modified by polydimethylsiloxane (PDMS) and characterized by BET analysis and Boehm titration. Dynamic adsorption column experiments were conducted and Yoon-Neslon(Y-N) model was used to identify adsorption effect for toluene, beuzene and acetone on AC when relative humidity was 0%, 50% and 90%, respectively. The results showed that the BET area, micropore volume and surface functional groups decreased with the PDMS modification, and surface hydrophobicity of the modified AC was enhanced leading to a lower water adsorption capacity. The results of dynamic adsorption showed that the adsorption kinetics and capacity of Bare-AC decreased with the increase of relative humidity, and the adsorption capacities of PDMS coated AC were 1.86 times (toluene) and 1.92 times (benzene) higher than those of Bare-AC, while a significant improvement of adsorption capacity for acetone was not observed. These findings suggest that polarity of molecule can be an important influencing factor for adsorption on hydrophobic surface developed by PDMS. PMID:27548948

  12. [Toluene, Benzene and Acetone Adsorption by Activated Carbon Coated with PDMS].

    PubMed

    Liu, Han-bing; Jiang, Xin; Wang, Xin; Yang, Bing; Xue, Nan-dong; Zhang, Shi-lei

    2016-04-15

    To improve the adsorption selectivity of volatile organic compounds ( VOCs) , activated carbon ( AC) was modified by polydimethylsiloxane (PDMS) and characterized by BET analysis and Boehm titration. Dynamic adsorption column experiments were conducted and Yoon-Neslon(Y-N) model was used to identify adsorption effect for toluene, beuzene and acetone on AC when relative humidity was 0%, 50% and 90%, respectively. The results showed that the BET area, micropore volume and surface functional groups decreased with the PDMS modification, and surface hydrophobicity of the modified AC was enhanced leading to a lower water adsorption capacity. The results of dynamic adsorption showed that the adsorption kinetics and capacity of Bare-AC decreased with the increase of relative humidity, and the adsorption capacities of PDMS coated AC were 1.86 times (toluene) and 1.92 times (benzene) higher than those of Bare-AC, while a significant improvement of adsorption capacity for acetone was not observed. These findings suggest that polarity of molecule can be an important influencing factor for adsorption on hydrophobic surface developed by PDMS.

  13. Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers

    USGS Publications Warehouse

    Mangun, C.L.; DeBarr, J.A.; Economy, J.

    2001-01-01

    A series of activated carbon fibers (ACFs) and ammonia-treated ACFs prepared from phenolic fiber precursors have been studied to elucidate the role of pore size, pore volume, and pore surface chemistry on adsorption of sulfur dioxide and its catalytic conversion to sulfuric acid. As expected, the incorporation of basic functional groups into the ACFs was shown as an effective method for increasing adsorption of sulfur dioxide. The adsorption capacity for dry SO2 did not follow specific trends; however the adsorption energies calculated from the DR equation were found to increase linearly with nitrogen content for each series of ACFs. Much higher adsorption capacities were achieved for SO2 in the presence of oxygen and water due to its catalytic conversion to H2SO4. The dominant factor for increasing adsorption of SO2 from simulated flue gas for each series of fibers studied was the weight percent of basic nitrogen groups present. In addition, the adsorption energies calculated for dry SO2 were shown to be linearly related to the adsorption capacity of H2SO4 from this flue gas for all fibers. It was shown that optimization of this parameter along with the pore volume results in higher adsorption capacities for removal of SO2 from flue gases. ?? 2001 Elsevier Science Ltd. All rights reserved.

  14. Collagen fiber immobilized Myrica rubra tannin and its adsorption to UO2(2+).

    PubMed

    Liao, Xuepin; Lu, Zhongbi; Du, Xiao; Liu, Xin; Shi, Bi

    2004-01-01

    Tannins, which are rich in ortho-hydroxyl groups, have a high affinity for UO2(2+). In this paper, Myrica rubra tannin was immobilized on collagen fiber by an aldehydic cross-linking reaction to prepare a novel adsorbent for uranium (UO2(2+)) recovery from wastewater. The adsorption equilibrium, the adsorption kinetics, and the effects of temperature and pH on the adsorption equilibrium were investigated in detail. It was found that the Myrica rubra tannin immobilized on collagen fiber exhibits an excellent adsorption capacity for UO2(2+). The adsorption capacity at 293 K and pH 5.0 was as high as 1.19 mmol UO2(2+)/g (283.3 mgU/g) when the initial concentration of UO2(2+) in solution was 7.5 mmol/L. The adsorption isotherms could be described by the Freundlich equation, and the increase of temperature promoted the adsorption to UO2(2+) . The adsorption kinetics data were fitted very well by the pseudosecond-order rate model, and the equilibrium adsorption capacity calculated by the pseudo-second-order rate model was almost the same as that determined by the actual measurement with the error < or = 4%. The pH has a significant effect on the adsorption process. According to our experiments, the suitable pH scope should be 5-8.

  15. Adsorption of tetracycline from aqueous solutions onto multi-walled carbon nanotubes with different oxygen contents

    PubMed Central

    Yu, Fei; Ma, Jie; Han, Sheng

    2014-01-01

    Oxidized multi-walled carbon nanotubes (MWCNTs) with different oxygen contents were investigated for the adsorption of tetracycline (TC) from aqueous solutions. As the surface oxygen content of the MWCNTs increased, the maximum adsorption capacity and adsorption coefficient of TC increased to the largest values and then decreased. The relation can be attributed to the interplay between the nanotubes' dispersibility and the water cluster formation upon TC adsorption. The overall adsorption kinetics of TC onto CNTs-3.2%O might be dependent on both intra-particle diffusion and boundary layer diffusion. The maximum adsorption capacity of TC on CNTs-3.2%O was achieved in the pH range of 3.3–8.0 due to formation of water clusters or H-bonds. Furthermore, the presence of Cu2+ could significantly enhanced TC adsorption at pH of 5.0. However, the solution ionic strength did not exhibit remarkable effect on TC adsorption. In addition, when pH is beyond the range (3.3–8.0), the electrostatic interactions caused the decrease of TC adsorption capacity. Our results indicate that surface properties and aqueous solution chemistry play important roles in TC adsorption on MWCNTs. PMID:24937315

  16. AgII doped MIL-101 and its adsorption of iodine with high speed in solution

    NASA Astrophysics Data System (ADS)

    Mao, Ping; Qi, Bingbing; Liu, Ying; Zhao, Lei; Jiao, Yan; Zhang, Yi; Jiang, Zheng; Li, Qiang; Wang, Jinfeng; Chen, Shouwen; Yang, Yi

    2016-05-01

    In order to improve the adsorption speed of iodine from water, MIL-101 with extra-large specific surface area (3054 m2/g) was chosen as a base material, and then, Ag was doped into MIL-101 to enhance its adsorption capacity through an incipient-wetness impregnation method. With the characterization of SEM-EDS, TEM, XRD, XPS, TGA, IR, and BET techniques, the resulting Ag was identified to be stay in the framework of MIL-101 stably in the form of AgII (generally, AgII cation is not stable). However, after the adsorption of I- anions, AgII stay in the cages of MIL-101 in the form of AgI/AgI3. It is important to note that, all adsorbents show high adsorption speed of iodine in solution. The equilibrium adsorption time of the adsorbents were acquired by only a few minutes, which can be attributed to its large BET surface area. An interesting note is that, when the doping amount of Ag is less than 9%, the iodine anions adsorption capacity of Ag@MIL-101 is greater than its theoretical adsorption capacity. It shows that both physical adsorption and chemical adsorption are existed in the adsorption process. This study hopefully leads to a new and highly efficient Ag-based adsorbent for iodide adsorb from solutions.

  17. Atrazine adsorption removal with nylon6/polypyrrole core-shell nanofibers mat: possible mechanism and characteristics.

    PubMed

    Yang, Bi-Yi; Cao, Yang; Qi, Fei-Fei; Li, Xiao-Qing; Xu, Qian

    2015-01-01

    A functionalized nylon6/polypyrrole core-shell nanofibers mat (PA6/PPy NFM) was prepared via situ polymerization on nylon6 electrospun nanofibers mat (PA6 NFM) template and used as an adsorbent to remove atrazine from aqueous solutions. The core-shell structure of PA6/PPy NFM can be clearly proved under scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The effects of initial solution pH and ionic strength, as well as the comparison of the adsorption capacity of functionalized (PA6/PPy NFM) and non-functionalized (PA6 NFM) adsorbent, were examined to reveal the possible adsorption mechanism. The results indicated that π-π interaction and electrostatic interaction should play a key role in the adsorption process. The kinetics and thermodynamics studies also further elucidated the detailed adsorption characteristics of atrazine removal by PA6/PPy NFM. The adsorption of atrazine could be well described by the pseudo-second-order equation. The adsorption equilibrium data was well fitted with the Freundlich isotherm model with a maximum adsorption capacity value of 14.8 mg/g. In addition, the increase of adsorption rate caused by a temperature increase could be felicitously explained by the endothermic reaction. The desorption results showed that the adsorption capacity remained almost unchanged after six adsorption/desorption cycles. These results suggest that PA6/PPy NFM could be employed as an efficient adsorbent for removing atrazine from contaminated water sources. PMID:25991912

  18. Quaternized dimethylaminoethyl methacrylate strong base anion exchange fibers for As(V) adsorption

    NASA Astrophysics Data System (ADS)

    Kavaklı, Cengiz; Akkaş Kavaklı, Pınar; Turan, Burcu Dila; Hamurcu, Aslı; Güven, Olgun

    2014-09-01

    N,N-Dimethylaminoethyl methacrylate (DMAEMA) grafted polyethylene/polypropylene (PE/PP) nonwoven fibers (DMAEMA-g-PE/PP) was prepared by radiation-induced graft polymerization. DMAEMA graft chains on nonwoven fibers were quaternized with dimethyl sulfate solution for the preparation of strong base anion exchange fibers (QDMAEMA-g-PE/PP). Fiber structures were characterized by FTIR, XPS and SEM techniques. The effect of solution pH, contact time, initial As(V) ion concentration and coexisting ions on the As(V) adsorption capacity of the QDMAEMA-g-PE/PP fibers were investigated by performing batch adsorption experiments. The adsorption of As(V) by QDMAEMA-g-PE/PP fibers was found to be independent on solution pH in the range 4.00-10.00. Kinetic experiments show that the As(V) adsorption rate was rapid and As(V) adsorption follows pseudo second-order kinetic model. As(V) adsorption equilibrium data were analyzed using Langmuir and Freundlich adsorption isotherm model equations. Langmuir and Freundlich adsorption isotherm models fitted the experimental data well. The maximum adsorption capacity (qmax) calculated from Langmuir isotherm was found to be 83.33 mg As(V)/g polymer at pH 7.00. The adsorbent was used for three cycles without significant loss of adsorption capacity. The adsorbed As(V) ions were desorbed effectively by a 0.1 M NaOH solution.

  19. Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution.

    PubMed

    Prarat, Panida; Ngamcharussrivichai, Chawalit; Khaodhiar, Sutha; Punyapalakul, Patiparn

    2011-09-15

    The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS. PMID:21752539

  20. Atrazine adsorption removal with nylon6/polypyrrole core-shell nanofibers mat: possible mechanism and characteristics

    NASA Astrophysics Data System (ADS)

    Yang, Bi-Yi; Cao, Yang; Qi, Fei-Fei; Li, Xiao-Qing; Xu, Qian

    2015-05-01

    A functionalized nylon6/polypyrrole core-shell nanofibers mat (PA6/PPy NFM) was prepared via situ polymerization on nylon6 electrospun nanofibers mat (PA6 NFM) template and used as an adsorbent to remove atrazine from aqueous solutions. The core-shell structure of PA6/PPy NFM can be clearly proved under scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The effects of initial solution pH and ionic strength, as well as the comparison of the adsorption capacity of functionalized (PA6/PPy NFM) and non-functionalized (PA6 NFM) adsorbent, were examined to reveal the possible adsorption mechanism. The results indicated that π-π interaction and electrostatic interaction should play a key role in the adsorption process. The kinetics and thermodynamics studies also further elucidated the detailed adsorption characteristics of atrazine removal by PA6/PPy NFM. The adsorption of atrazine could be well described by the pseudo-second-order equation. The adsorption equilibrium data was well fitted with the Freundlich isotherm model with a maximum adsorption capacity value of 14.8 mg/g. In addition, the increase of adsorption rate caused by a temperature increase could be felicitously explained by the endothermic reaction. The desorption results showed that the adsorption capacity remained almost unchanged after six adsorption/desorption cycles. These results suggest that PA6/PPy NFM could be employed as an efficient adsorbent for removing atrazine from contaminated water sources.

  1. Adsorption properties of Congo Red from aqueous solution onto surfactant-modified montmorillonite.

    PubMed

    Wang, Li; Wang, Aiqin

    2008-12-15

    A series of surfactant-modified montmorillonites (MMT) were prepared using octyltrimethylammonium bromide (OTAB), dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) and stearyltrimethylammonium bromide (STAB), and the organification of MMT was proved by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron micrographic (SEM) and transmission electron microscope (TEM). The adsorption of Congo Red (CR) anionic dye from aqueous solution onto surfactant-modified MMT was carried out. Compared with MMT, the adsorption capacity of surfactant-modified MMT for CR was greatly enhanced and MMT modified with CTAB (2.0 CEC) exhibited the higher adsorption capacity. The effects of pH value of the dye solution, adsorption temperature, adsorption time and the initial dye concentration on the adsorption capacity of CR on CTAB-MMT have been investigated. The results showed that the adsorption kinetic of CR on CTAB-MMT could be best described by the pseudo-second-order model and that the adsorption isotherm of CR was in good agreement with the Langmuir equation. The IR spectra and SEM analysis also revealed that the adsorption of CTAB-MMT was a chemical adsorption process between CTAB and the NH(2), -N=N- and SO(3) groups of CR. PMID:18400385

  2. Assessing the adsorption properties of shales

    NASA Astrophysics Data System (ADS)

    Pini, Ronny

    2015-04-01

    Physical adsorption refers to the trapping of fluid molecules at near liquid-like densities in the pores of a given adsorbent material. Fine-grained rocks, such as shales, contain a significant amount of nanopores that can significantly contribute to their storage capacity. As a matter of fact, the current ability to extract natural gas that is adsorbed in the rock's matrix is limited, and current technology focuses primarily on the free gas in the fractures (either natural or stimulated), thus leading to recovery efficiencies that are very low. Shales constitute also a great portion of so-called cap-rocks above potential CO2 sequestration sites; hereby, the adsorption process may limit the CO2 mobility within the cap-rock, thus minimizing the impact of leakage on the whole operation. Whether it is an unconventional reservoir or a cap-rock, understanding and quantifying the mechanisms of adsorption in these natural materials is key to improve the engineering design of subsurface operations. Results will be presented from a laboratory study that combines conventional techniques for the measurement of adsorption isotherms with novel methods that allows for the imaging of adsorption using x-rays. Various nanoporous materials are considered, thus including rocks, such as shales and coals, pure clay minerals (a major component in mudrocks) and engineered adsorbents with well-defined nanopore structures, such as zeolites. Supercritical CO2 adsorption isotherms have been measured with a Rubotherm Magnetic Suspension balance by covering the pressure range 0.1-20~MPa. A medical x-ray CT scanner has been used to identify three-dimensional patterns of the adsorption properties of a packed-bed of adsorbent, thus enabling to assess the spatial variability of the adsorption isotherm in heterogeneous materials. The data are analyzed by using thermodynamically rigorous measures of adsorption, such as the net- and excess adsorbed amounts and a recently developed methodology is

  3. Hybrid adsorptive membrane reactor

    NASA Technical Reports Server (NTRS)

    Tsotsis, Theodore T. (Inventor); Sahimi, Muhammad (Inventor); Fayyaz-Najafi, Babak (Inventor); Harale, Aadesh (Inventor); Park, Byoung-Gi (Inventor); Liu, Paul K. T. (Inventor)

    2011-01-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  4. Hybrid adsorptive membrane reactor

    DOEpatents

    Tsotsis, Theodore T.; Sahimi, Muhammad; Fayyaz-Najafi, Babak; Harale, Aadesh; Park, Byoung-Gi; Liu, Paul K. T.

    2011-03-01

    A hybrid adsorbent-membrane reactor in which the chemical reaction, membrane separation, and product adsorption are coupled. Also disclosed are a dual-reactor apparatus and a process using the reactor or the apparatus.

  5. Adsorption of fluoride to UiO-66-NH2 in water: Stability, kinetic, isotherm and thermodynamic studies.

    PubMed

    Lin, Kun-Yi Andrew; Liu, Yu-Ting; Chen, Shen-Yi

    2016-01-01

    To provide safe drinking water, fluoride in water must be removed and adsorption processes appear to be the most widely used method. Metal organic frameworks (MOFs) represent a new class of adsorbents that have been used in various adsorption applications. To study the adsorption mechanism of fluoride to MOFs in water and obtain related adsorption parameters, we synthesized a zirconium-based MOF with a primary amine group on its ligand, named UiO-66-NH2. The kinetics, adsorption isotherm and thermodynamics of fluoride adsorption to UiO-66-NH2 were investigated. The crystalline structure of UiO-66-NH2 remained intact and the local structure of zirconium in UiO-66-NH2 did not change significantly after being exposed to fluoride. The kinetics of the fluoride adsorption in UiO-66-NH2 could be well represented by the pseudo second order rate law. The enthalpy of the adsorption indicates that the F(-) adsorption to UiO-66-NH2 was classified as a physical adsorption. However, the comparison between the adsorption capacities of UiO-66-NH2 and UiO-66 suggests that the fluoride adsorption to UiO-66-NH2 might primarily involve a strong interaction between F(-) and the metal site. The fluoride adsorption capacity of UiO-66-NH2 was found to decrease when pH>7. While the presence of chloride/bromide ions did not noticeably change the adsorption capacity of UiO-66-NH2, the ionic surfactants slightly affected the adsorption capacity of UiO-66-NH2. These findings provide insights to further optimize the adsorption process for removal of fluoride using zirconium-based MOFs. PMID:26397913

  6. Immobilization of Acetobacter aceti on cellulose ion exchangers: adsorption isotherms

    SciTech Connect

    Bar, R.; Gainer, J.L.; Kirwan, D.J.

    1986-08-01

    The adsorptive behavior of cells of Acetobacter aceti, ATCC 23746, on DEAE-, TEAE-, and DEHPAE-cellulose ion exchangers in a modified Hoyer's medium at 30 degrees Centigrade was investigated. The maximum observed adsorption capacities varied from 46 to 64 mg dry wt/g resin. The Langmuir isotherm form was used to fit the data, since the cells formed a monolayer on the resin and exhibited saturation. The equilibrium constant in the Langmuir expression was qualitatively correlated with the surface charge density of the resin. The adsorption was also ''normalized'' by considering the ionic capacities of the resins. The exceptionally high normalized adsorption capacity of ECTEOLA-cellulose, 261 mg dry/meq, may be explained by an interaction between the cell wall and the polyglyceryl chains of the exchanging groups in addition to the electrostatic effects. The effect of pH on the bacterial adsorption capacity of ECTEOLA-, TEAE-, and phosphate-cellulose resins was studied and the pH of the bacteria was estimated to be 3.0. 17 references.

  7. EFFECT OF MOLECULAR OXYGEN ON THE ACTIVATED CARBON ADSORPTION OF NATURAL ORGANIC MATTER IN OHIO RIVER WATER

    EPA Science Inventory

    Recently published data show that the adsorptive capacity of granular activated carbon for phenois increases significantly in the presence of molecular oxygen (Vidic, Suidan,Traegner and Nakhla, 1990). in this study, the effect of molecular oxygen on the adsorptive capacity of a...

  8. Dynamics and thermodynamics of toxic metals adsorption onto soil-extracted humic acid.

    PubMed

    Shaker, Medhat A; albishri, Hassan M

    2014-09-01

    Humic acids, HA represent a large portion of natural organic matter in soils, sediments and waters. They are environmentally important materials due to their extensive ubiquity and strong complexation ability, which can influence heavy metal removal and transportation in waters. The thermodynamics and kinetics of the adsorption of Cd(II) and Cr(VI) onto solid soil-derived HA have been investigated at optimum conditions of pH (5.5±0.1), metal concentration (10-100mmolL(-1)) and different temperatures (293-323K). The suitability of adsorption models such as Freundlich and Langmuir to equilibrium data was investigated. The adsorption was well described by Langmuir isotherm model in multi-detectable steps. Adsorption sites, i (i=A, B, C) with different capacities, νi are characterized. The stoichiometric site capacity is independent of temperature and equilibrium constant, Ki. Adsorption sites A and B are selectively occupied by Cr(VI) cations while sites A and C are selectively occupied by Cd(II) cations. The thermodynamic parameters of adsorption systems are correlated for each adsorption step. The adsorption is endothermic, spontaneous and favorable. Different kinetic models are applied and the adsorption of these heavy metals onto HA follows pseudo-second-order kinetics and equilibrium is achieved within 24h. The adsorption reaction is controlled by diffusion processes and the type of the adsorption is physical. PMID:24997970

  9. [Adsorption of Congo red from aqueous solution on hydroxyapatite].

    PubMed

    Zhan, Yan-Hui; Lin, Jian-Wei

    2013-08-01

    The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

  10. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    PubMed Central

    2012-01-01

    The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (ΔH0, ΔS0, and ΔG0) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment. PMID:22269298

  11. Adsorptive removal of PPCPs by biomorphic HAP templated from cotton.

    PubMed

    Huang, Bin; Xiong, Dan; Zhao, Tingting; He, Huan; Pan, Xuejun

    2016-01-01

    Biomorphic nano-hydroxyapatite (HAP) was fabricated by a co-precipitation method using cotton as bio-templates and employed in adsorptive removal of ofloxacin (OFL) and triclosan (TCS) that are two representative pharmaceuticals and personal care products (PPCPs). The surface area and porosity, crystal phase, functional group, morphology and micro-structure of the synthesized HAP were characterized by Brunauer-Emmett-Teller isotherm, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron macroscopic and transmission electron microscopy. The effects of initial pH, ionic strength, initial concentration, contact time and temperature on the removal of PPCPs were studied in a batch experiment. The adsorption of OFL and TCS was rapid and almost accomplished within 50 min. Kinetic studies indicated that the adsorption process of OFL and TCS followed the pseudo-first-order and pseudo-second-order models, respectively. The Freundlich isotherm described the OFL adsorption process well but the adsorption of TCS fitted the Langmuir isotherm better. Thermodynamics and isotherm parameters suggested that both OFL and TCS adsorption were feasible and spontaneous. Hydrogen bond and Lewis acid-base reaction may be the dominating adsorption mechanism of OFL and TCS, respectively. Compared to other adsorbents, biomorphic HAP is environmentally friendly and has the advantages of high adsorption capacity, exhibiting potential application for PPCPs removal. PMID:27387006

  12. Adsorption of Pyrene onto the Agricultural By-Product: Corncob.

    PubMed

    Li, Xiaojun; Tong, Dongli; Allinson, Graeme; Jia, Chunyun; Gong, Zongqing; Liu, Wan

    2016-01-01

    The adsorption behavior of pyrene on corncob was studied to provide a theoretical basis for the possible use of this material as an immobilized carrier for improving the bioremediation of PAH-contaminated soil. The results were as follows. Kinetic experiments showed that the adsorption processes obeyed a pseudo-second-order model. The intraparticle diffusion of Weber-Morris model fitting showed that the film and intraparticle diffusions were the key rate-limiting processes, and the adsorption process mainly consisted of three steps: boundary layer diffusion and two intra-particle diffusions. Experimental adsorption data for pyrene were successfully described by the adsorption-partition equilibrium model. The maximum adsorption capacity at 25°C was 214.8 μg g(-1). The adsorption contribution decreased significantly when the Ce/Sw (the equilibrium concentration/solubility in water) was higher than 1. Adsorption decreased with increased temperature. Based on the above results, the corncob particles could be helpful in the bioremediation of pyrene-contaminated soil.

  13. Adsorption of Pyrene onto the Agricultural By-Product: Corncob.

    PubMed

    Li, Xiaojun; Tong, Dongli; Allinson, Graeme; Jia, Chunyun; Gong, Zongqing; Liu, Wan

    2016-01-01

    The adsorption behavior of pyrene on corncob was studied to provide a theoretical basis for the possible use of this material as an immobilized carrier for improving the bioremediation of PAH-contaminated soil. The results were as follows. Kinetic experiments showed that the adsorption processes obeyed a pseudo-second-order model. The intraparticle diffusion of Weber-Morris model fitting showed that the film and intraparticle diffusions were the key rate-limiting processes, and the adsorption process mainly consisted of three steps: boundary layer diffusion and two intra-particle diffusions. Experimental adsorption data for pyrene were successfully described by the adsorption-partition equilibrium model. The maximum adsorption capacity at 25°C was 214.8 μg g(-1). The adsorption contribution decreased significantly when the Ce/Sw (the equilibrium concentration/solubility in water) was higher than 1. Adsorption decreased with increased temperature. Based on the above results, the corncob particles could be helpful in the bioremediation of pyrene-contaminated soil. PMID:26573838

  14. [Adsorption of Congo red from aqueous solution on hydroxyapatite].

    PubMed

    Zhan, Yan-Hui; Lin, Jian-Wei

    2013-08-01

    The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution. PMID:24191561

  15. Electrostatics of DNA nucleotide-carbon nanotube hybrids evaluated from QM:MM simulations

    NASA Astrophysics Data System (ADS)

    Chehel Amirani, Morteza; Tang, Tian

    2015-11-01

    Biomolecule-functionalized carbon nanotubes (CNTs) have been studied vastly in recent years due to their potential applications for instance in cancer detection, purification and separation of CNTs, and nanoelectronics. Studying the electrostatic potential generated by a biomolecule-CNT hybrid is important in predicting its interactions with the surrounding environment such as charged particles and surfaces. In this paper, we performed atomistic simulations using a QM:MM approach to evaluate the electrostatic potential and charge transfer for a hybrid structure formed by a DNA nucleotide and a CNT in solution. Four types of DNA nucleotides and two CNTs with chiralities of (4,4) and (7,0) were considered. The types of nucleotides and CNTs were both found to play important roles in the electrostatic potential and charge transfer of the hybrid. At the same distance from the CNT axis, the electrostatic potential for the nucleotide-(4,4) CNT hybrids was found to be stronger compared with that for the nucleotide-(7,0) CNT hybrids. Higher electric charge was also shown to be transferred from the DNA nucleotides to the (7,0) CNT compared with the (4,4) CNT. These results correlate with the previous finding that the nucleotides bound more tightly to the (7,0) CNT compared with the (4,4) CNT.Biomolecule-functionalized carbon nanotubes (CNTs) have been studied vastly in recent years due to their potential applications for instance in cancer detection, purification and separation of CNTs, and nanoelectronics. Studying the electrostatic potential generated by a biomolecule-CNT hybrid is important in predicting its interactions with the surrounding environment such as charged particles and surfaces. In this paper, we performed atomistic simulations using a QM:MM approach to evaluate the electrostatic potential and charge transfer for a hybrid structure formed by a DNA nucleotide and a CNT in solution. Four types of DNA nucleotides and two CNTs with chiralities of (4,4) and (7

  16. Electronic properties of disordered organic semiconductors via QM/MM simulations.

    PubMed

    Difley, Seth; Wang, Lee-Ping; Yeganeh, Sina; Yost, Shane R; Van Voorhis, Troy

    2010-07-20

    Organic semiconductors (OSCs) have recently received significant attention for their potential use in photovoltaic, light emitting diode, and field effect transistor devices. Part of the appeal of OSCs is the disordered, amorphous nature of these materials, which makes them more flexible and easier to process than their inorganic counterparts. In addition to their technological applications, OSCs provide an attractive laboratory for examining the chemistry of heterogeneous systems. Because OSCs are both electrically and optically active, researchers have access to a wealth of electrical and spectroscopic probes that are sensitive to a variety of localized electronic states in these materials. In this Account, we review the basic concepts in first-principles modeling of the electronic properties of disordered OSCs. There are three theoretical ingredients in the computational recipe. First, Marcus theory of nonadiabatic electron transfer (ET) provides a direct link between energy and kinetics. Second, constrained density functional theory (CDFT) forms the basis for an ab initio model of the diabatic charge states required in ET. Finally, quantum mechanical/molecular mechanical (QM/MM) techniques allow us to incorporate the influence of the heterogeneous environment on the diabatic states. As an illustration, we apply these ideas to the small molecule OSC tris(8- hydroxyquinolinato)aluminum (Alq(3)). In films, Alq(3) can possess a large degree of short-range order, placing it in the middle of the order-disorder spectrum (in this spectrum, pure crystals represent one extreme and totally amorphous structures the opposite extreme). We show that the QM/MM recipe reproduces the transport gap, charge carrier hopping integrals, optical spectra, and reorganization energies of Alq(3) in quantitative agreement with available experiments. However, one cannot specify any of these quantities accurately with a single number. Instead, one must characterize each property by a

  17. A QM/MM study of the catalytic mechanism of nicotinamidase.

    PubMed

    Sheng, Xiang; Liu, Yongjun

    2014-02-28

    Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications. PMID:24413890

  18. Comparison of extracellular cellulase activities of ClosTridium thermocellum LQRI and trichoderma reesei QM9414

    SciTech Connect

    Ng, T.K.; Zeikus, J.G.

    1981-08-01

    The crude extracellular cellulase of Clostridium thermocellum LQRI (virgin strain) was very active and solubilized microcrystalline cellulose at one-half the rate observed for the extracellular cellulase of Trichoderma reesei QM9414 (mutant strain). Clostridium thermocellum cellulase activity differed considerably from that of Trichoderma reesei as follows: higher endoglucanase/exoglucanase activity ratio; absence of extracellular cellobiase or beta-xylosidase activity; long-chain oligosaccharides instead of short-chain oligosaccharides as initial (15-min) hydrolytic products on microcrystalline cellulose; mainly cellobiose or xylobiose as long-term (24-h) hydrolysis products of Avicel and MN300 or xylan; and high activity and stability at 60 to 70 degrees Celcius. Under optimized reaction conditions, the kinetic properties (V max, 0.4 mu mol/min per mg of protein; energy of activation, 33 kJ; temperature coefficient, 1.8) of Clostridium thermocellum cellulose-solubilizing activity were comparable to those reported for Trichoderma reesei, except that the dyed Avicel concentration at half-maximal velocity was twofold higher (182 mu M). The cellulose-solubilizing activity of the two crude cellulases differed considerably in response to various enzyme inhibitors. Most notably, Ag/sup 2 +/ and Hg/sup 2 +/ effectively inhibited Clostridium thermocellum but not Trichoderma reesei cellulase at less than 20 mu M, whereas Ca/sup 2 +/, Mg/sup 2 +/, and Mn/sup 2 +/ inhibited Trichoderma reesei but not Clostridium thermocellum cellulase at greater than 10 mM. Both enzymes were inhibited by Cu/sup 2 +/ (greater than 20 mM), Zn2+ (greater than 10 mM), and ethylene glycol-bis (beta-aminoethyl ether)-N, N-tetraacetic acid (greater than 10 mM). The overal rates of cellooligosaccharide degradation were higher for Trichoderma reesei than for Clostridium thermocellum cellulase, except that the rates of conversion of cellohexaose to cellotrisse were equivalent.

  19. QM/MD simulation of SWNT nucleation on transition-metal carbide nanoparticles.

    PubMed

    Page, Alister J; Yamane, Honami; Ohta, Yasuhito; Irle, Stephan; Morokuma, Keiji

    2010-11-10

    The mechanism and kinetics of single-walled carbon nanotube (SWNT) nucleation from Fe- and Ni-carbide nanoparticle precursors have been investigated using quantum chemical molecular dynamics (QM/MD) methods. The dependence of the nucleation mechanism and its kinetics on environmental factors, including temperature and metal-carbide carbon concentration, has also been elucidated. It was observed that SWNT nucleation occurred via three distinct stages, viz. the precipitation of the carbon from the metal-carbide, the formation of a "surface/subsurface" carbide intermediate species, and finally the formation of a nascent sp(2)-hybidrized carbon structure supported by the metal catalyst. The SWNT cap nucleation mechanism itself was unaffected by carbon concentration and/or temperature. However, the kinetics of SWNT nucleation exhibited distinct dependences on these same factors. In particular, SWNT nucleation from Ni(x)C(y) nanoparticles proceeded more favorably compared to nucleation from Fe(x)C(y) nanoparticles. Although SWNT nucleation from Fe(x)C(y) and Ni(x)C(y) nanoparticle precursors occurred via an identical route, the ultimate outcomes of these processes also differed substantially. Explicitly, the Ni(x)-supported sp(2)-hybridized carbon structures tended to encapsulate the catalyst particle itself, whereas the Fe(x)-supported structures tended to form isolated SWNT cap structures on the catalyst surface. These differences in SWNT nucleation kinetics were attributed directly to the relative strengths of the metal-carbon interaction, which also dictates the precipitation of carbon from the nanoparticle bulk and the longevity of the resultant surface/subsurface carbide species. The stability of the surface/subsurface carbide was also influenced by the phase of the nanoparticle itself. The observations agree well with experimentally available data for SWNT growth on iron and nickel catalyst particles.

  20. How Mitogen-Activated Protein Kinases Recognize and Phosphorylate Their Targets: A QM/MM Study

    PubMed Central

    Turjanski, Adrian Gustavo; Hummer, Gerhard; Gutkind, J. Silvio

    2009-01-01

    Mitogen-activated protein kinase (MAPK) signaling pathways play an essential role in the transduction of environmental stimuli to the nucleus, thereby regulating a variety of cellular processes, including cell proliferation, differentiation and programmed cell death. The components of the MAPK extracellular activated protein kinase (ERK) cascade represent attractive targets for cancer therapy as their aberrant activation is a frequent event among highly prevalent human cancers. To understand how MAPKs recognize and phosphorylate their targets is key to unravel their function. However, these events are still poorly understood due to the lack of complex structures of MAPKs with their bound targets in the active site. Here, we have modeled the interaction of ERK with a target peptide and analyzed the specificity towards Ser/Thr-Pro motifs. By using a Quantum Mechanics/Molecular Mechanics (QM/MM) approach we propose a mechanism for the phosphoryl transfer catalyzed by ERK that offers new insights into MAPK function. Our results suggest that 1) the proline residue has a role both in specificity and phospho transfer efficiency; 2) the reaction occurs in one step with ERK2 Asp147 acting as the catalytic base; 3) a conserved Lys in the kinase superfamily usually mutated to check kinase activity strongly stabilizes the transition state; and 4) the reaction mechanism is similar with either one or two Mg2+ ions in the active site. Taken together, our results provide a detailed description of the molecular events involved in the phosphorylation reaction catalyzed by MAPK and contributes to the general understanding of kinase activity. PMID:19361221

  1. Discerning the catalytic mechanism of Staphylococcus aureus sortase A with QM/MM free energy calculations.

    PubMed

    Shrestha, Pooja; Wereszczynski, Jeff

    2016-06-01

    Sortases are key virulence factors in Gram-positive bacteria. These enzymes embed surface proteins in the cell wall through a transpeptidation reaction that involves recognizing a penta-peptide "sorting signal" in a target protein, cleaving it, and covalently attaching it to a second substrate that is later inserted into the cell wall. Although well studied, several aspects of the mechanism by which sortases perform these functions remains unclear. In particular, experiments have revealed two potential sorting signal binding motifs: a "Threonine-Out" (Thr-Out) structure in which the catalytically critical threonine residues protrudes into solution, and a "Threonine-In" (Thr-In) configuration in which this residue inserts into the binding site. To determine which of these is the biologically relevant state, we have performed a series of conventional and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations of the Staphylococcus aureus sortase A (SrtA) enzyme bound to a sorting signal substrate. Through the use of multi-dimensional metadynamics, our simulations were able to both map the acylation mechanism of SrtA in the Thr-In and Thr-Out states, as well as determine the free energy minima and barriers along these reactions. Results indicate that in both states the catalytic mechanisms are similar, however the free energy barriers are lower in the Thr-In configuration, suggesting that Thr-In is the catalytically relevant state. This has important implications for advancing our understanding of the mechanisms of sortase enzymes, as well we for future structure based drug design efforts aimed at inhibiting sortase function in vivo.

  2. Exploring the aldol reaction using catalytic antibodies and "on water" organocatalysts from QM/MM calculations.

    PubMed

    Armacost, Kira; Acevedo, Orlando

    2014-01-01

    The aldol reaction between benzaldehyde and acetone has been investigated using QM/MM Monte Carlo calculations and free-energy perturbation theory to determine the origin of the enhanced rates and enantioselectivities (% ee) derived from an enamine-based catalytic antibody 33F12 and a chiral organocatalyst. Electrostatic stabilization of the general acid/base TyrL36 by TrpH103, SerH100, and AsnL34 enabled the 33F12 active site to exclusively adopt an si-face benzaldehyde orientation for C-C bond formation with the LysH93-enamine. Whereas preorganization was responsible for the exclusive (S)-aldol product in the antibody, the organocatalyst featuring a chiral diphenyl amino alcohol moiety instead derived its preferred (R)-aldol product from an interplay between sterics and electronic stabilization. The si-face benzaldehyde conformation had unfavorable interactions with the organocatalyst in contrast to the re-face. Gas-phase calculations predicted a 73% ee; however, solution boosted the % ee values despite similar reaction geometries. An "on water" environment, defined as a reaction that proceeds in an aqueous organic emulsion, yielded a computed 94% ee (exptl 93% ee) compared to a calculated 87% ee in "neat" acetone (exptl 85% ee). Specific hydrogen bonding between the interfacial waters and an amide oxygen on the catalyst was found to control the % ee. A more compact si-face transition structure reduced solvent accessibility to the amide oxygen with a "closed state" steric barrier compared to an "open state" for the re-face. New insight into the synthetically important aldol reaction and state-of-the-art methodology is presented herein.

  3. Discerning the catalytic mechanism of Staphylococcus aureus sortase A with QM/MM free energy calculations.

    PubMed

    Shrestha, Pooja; Wereszczynski, Jeff

    2016-06-01

    Sortases are key virulence factors in Gram-positive bacteria. These enzymes embed surface proteins in the cell wall through a transpeptidation reaction that involves recognizing a penta-peptide "sorting signal" in a target protein, cleaving it, and covalently attaching it to a second substrate that is later inserted into the cell wall. Although well studied, several aspects of the mechanism by which sortases perform these functions remains unclear. In particular, experiments have revealed two potential sorting signal binding motifs: a "Threonine-Out" (Thr-Out) structure in which the catalytically critical threonine residues protrudes into solution, and a "Threonine-In" (Thr-In) configuration in which this residue inserts into the binding site. To determine which of these is the biologically relevant state, we have performed a series of conventional and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations of the Staphylococcus aureus sortase A (SrtA) enzyme bound to a sorting signal substrate. Through the use of multi-dimensional metadynamics, our simulations were able to both map the acylation mechanism of SrtA in the Thr-In and Thr-Out states, as well as determine the free energy minima and barriers along these reactions. Results indicate that in both states the catalytic mechanisms are similar, however the free energy barriers are lower in the Thr-In configuration, suggesting that Thr-In is the catalytically relevant state. This has important implications for advancing our understanding of the mechanisms of sortase enzymes, as well we for future structure based drug design efforts aimed at inhibiting sortase function in vivo. PMID:27172839

  4. Mutational Analysis of Bacillus megaterium QM B1551 Cortex-Lytic Enzymes ▿ †

    PubMed Central

    Christie, Graham; Üstok, Fatma Isık; Lu, Qiaozhi; Packman, Len C.; Lowe, Christopher R.

    2010-01-01

    Molecular-genetic and muropeptide analysis techniques have been applied to examine the function in vivo of the Bacillus megaterium QM B1551 SleB and SleL proteins. In common with Bacillus subtilis and Bacillus anthracis, the presence of anhydromuropeptides in B. megaterium germination exudates, which is indicative of lytic transglycosylase activity, is associated with an intact sleB structural gene. B. megaterium sleB cwlJ double mutant strains complemented with engineered SleB variants in which the predicted N- or C-terminal domain has been deleted (SleB-ΔN or SleB-ΔC) efficiently initiate and hydrolyze the cortex, generating anhydromuropeptides in the process. Additionally, sleB cwlJ strains complemented with SleB-ΔN or SleB-ΔC, in which glutamate and aspartate residues have individually been changed to alanine, all retain the ability to hydrolyze the cortex to various degrees during germination, with concomitant release of anhydromuropeptides to the surrounding medium. These data indicate that while the presence of either the N- or C-terminal domain of B. megaterium SleB is sufficient for initiation of cortex hydrolysis and the generation of anhydromuropeptides, the perceived lytic transglycosylase activity may be derived from an enzyme(s), perhaps exclusively or in addition to SleB, which has yet to be identified. B. megaterium SleL appears to be associated with the epimerase-type activity observed previously in B. subtilis, differing from the glucosaminidase function that is apparent in B. cereus/B. anthracis. PMID:20729357

  5. High Efficiency Adsorption Chillers: High Efficiency Adsorption Cooling Using Metal Organic Heat Carriers

    SciTech Connect

    2010-10-01

    BEETIT Project: PNNL is incorporating significant improvements in materials that adsorb liquids or gases to design more efficient adsorption chillers. An adsorption chiller is a type of air conditioner that is powered by heat, solar or waste heat, or combustion of natural gas. Unlike typical chillers, this type has few moving parts and uses almost no electricity to operate. PNNL is designing adsorbent materials at the molecular level with at least 3 times higher refrigerant capacity and up to 20 times faster kinetics than adsorbents used in current chillers. By using the new adsorbent, PNNL is able to create a chiller that is significantly smaller, has twice the energy efficiency, and lower costs for materials and assembly time compared to conventional adsorption chillers.

  6. [Adsorption characteristics of f2 bacteriophages by four substrates in constructed wetland].

    PubMed

    Chen, Di; Zheng, Xiang; Wei, Yuan-Song; Yang, Yong

    2013-10-01

    Performance of f2 phages adsorption by four substrates including anthracite coal, steel slag, zeolite and forsterite was investigated through batch and dynamic experiments. Results of batch experiments showed that the removal efficiency of f2 phages by these four substrates was in the order of anthracite > steel slag > forsterite approximately zeolite. The adsorption of f2 phages by anthracite experienced fast, medium and slow stages, and the removal efficiency of f2 phages increased gradually with the increase of anthracite dosage, e. g. the optimized dosage of anthracite was 8.0 g at a solid/liquid ratio of 1:12.5 (m/V). The isothermal adsorption of all four substrates was described with Freundlich and Langmuir isothermal adsorption equation very well, and the adsorption of f2 phages by both anthracite and steel slag fitted pseudo-second order adsorption kinetics at their theoretical adsorption capacities of 3. 35 x 10(8) PFU.g-1 and 2.56 x 10(8) PFU.g-1, respectively, nearly the same as the equilibrium adsorption capacities obtained under the experiment conditions. And the liquid diffusion process was a rate-limiting step of the adsorption of f2 phage by both anthracite and steel slag, but not the only one. The results of dynamic adsorption experiments showed that the adsorption process of f2 phages in the three adsorption columns including anthracite, steel slag and zeolite experienced four stages of adaption, adsorption, pulse adsorption and adsorption equilibrium, and the total removal rates of f2 phages were more than 2. 55 Ig.

  7. Modification of porous starch for the adsorption of heavy metal ions from aqueous solution.

    PubMed

    Ma, Xiaofei; Liu, Xueyuan; Anderson, Debbie P; Chang, Peter R

    2015-08-15

    Porous starch xanthate (PSX) and porous starch citrate (PSC) were prepared in anticipation of the attached xanthate and carboxylate groups respectively forming chelation and electrostatic interactions with heavy metal ions in the subsequent adsorption process. The lead(II) ion was selected as the model metal and its adsorption by PSX and PSC was characterized. The adsorption capacity was highly dependent on the carbon disulfide/starch and citric acid/starch mole ratios used during preparation. The adsorption behaviors of lead(II) ion on PSXs and PSCs fit both the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity from the Langmuir isotherm equation reached 109.1 and 57.6 mg/g for PSX and PSC when preparation conditions were optimized, and the adsorption times were just 20 and 60 min, respectively. PSX and PSC may be used as effective adsorbents for removal of heavy metals from contaminated liquid. PMID:25794731

  8. Modification of porous starch for the adsorption of heavy metal ions from aqueous solution.

    PubMed

    Ma, Xiaofei; Liu, Xueyuan; Anderson, Debbie P; Chang, Peter R

    2015-08-15

    Porous starch xanthate (PSX) and porous starch citrate (PSC) were prepared in anticipation of the attached xanthate and carboxylate groups respectively forming chelation and electrostatic interactions with heavy metal ions in the subsequent adsorption process. The lead(II) ion was selected as the model metal and its adsorption by PSX and PSC was characterized. The adsorption capacity was highly dependent on the carbon disulfide/starch and citric acid/starch mole ratios used during preparation. The adsorption behaviors of lead(II) ion on PSXs and PSCs fit both the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity from the Langmuir isotherm equation reached 109.1 and 57.6 mg/g for PSX and PSC when preparation conditions were optimized, and the adsorption times were just 20 and 60 min, respectively. PSX and PSC may be used as effective adsorbents for removal of heavy metals from contaminated liquid.

  9. Carbon dioxide and nitrogen adsorption on cation-exchanged SSZ-13 zeolites.

    PubMed

    Pham, Trong D; Liu, Qingling; Lobo, Raul F

    2013-01-15

    Samples of high-silica SSZ-13, ion exchanged with protons and alkali-metal cations Li(+), Na(+), and K(+), were investigated using adsorption isotherms of CO(2) and N(2). The results show that Li-, Na-SSZ-13 have excellent CO(2) capacity at ambient temperature and pressure; in general, Li-SSZ-13 shows the highest capacity for N(2), CO(2) particularly in the low-pressure region. The effect of cation type and Si/Al ratio (6 and 12) on the adsorption properties was investigated through analysis of adsorption isotherms and heats of adsorption. The separation of CO(2) in a flue gas mixture was evaluated for these adsorbents in the pressure swing adsorption and vacuum pressure adsorption processes. PMID:23249267

  10. Investigation on efficient adsorption of cationic dyes on porous magnetic polyacrylamide microspheres.

    PubMed

    Yao, Tong; Guo, Song; Zeng, Changfeng; Wang, Chongqing; Zhang, Lixiong

    2015-07-15

    We report here the preparation of porous magnetic polyacrylamide microspheres for efficient removal of cationic dyes by a simple polymerization-induced phase separation method. Characterizations by various techniques indicate that the microspheres show porous structures and magnetic properties. They can adsorb methylene blue with high efficiency, with adsorption capacity increasing from 263 to 1977 mg/g as the initial concentration increases from 5 to 300 mg/L. Complete removal of methylene blue can be obtained even at very low concentrations. The equilibrium data is well described by the Langmuir isotherm models, exhibiting a maximum adsorption capacity of 1990 mg/g. The adsorption capacity increases with increasing initial pH and reaches a maximum at pH 8, revealing an electrostatic interaction between the microspheres and the methylene blue molecules. The microspheres also show high adsorption capacities for neutral red and gentian violet of 1937 and 1850 mg/g, respectively, as well as high efficiency in adsorption of mixed-dye solutions. The dye-adsorbed magnetic polyacrylamide microspheres can be easily desorbed, and can be repeatedly used for at least 6 cycles without losing the adsorption capacity. The adsorption capacity and efficiency of the microspheres are much higher than those of reported adsorbents, which exhibits potential practical application in removing cationic dyes.

  11. Characterization of trichloroethylene adsorption onto waste biocover soil in the presence of landfill gas.

    PubMed

    He, Ruo; Su, Yao; Kong, Jiaoyan

    2015-09-15

    Waste biocover soils (WBS) have been demonstrated to have great potential in mitigating trichloroethylene (TCE) emission from landfills, due to the relatively high TCE-degrading capacity. In this study, the characteristics of TCE adsorption on WBS in the presence of the major landfill gas components (i.e., CH4 and CO2) were investigated in soil microcosms. The adsorption isotherm of TCE onto WBS was fitted well with linear model within the TCE concentrations of 7000 ppmv. The adsorption capacity of TCE onto WBS was affected by temperature, soil moisture content and particle size, of which, temperature was the dominant factor. The adsorption capacity of TCE onto the experimental materials increased with the increasing organic matter content. A significantly positive correlation was observed between the adsorption capacity of TCE and the organic matter content of experimental materials that had relatively higher organic content (r = 0.988, P = 0.044). To better understand WBS application in practice, response surface methodology was developed to predict TCE adsorption capacity and emissions through WBS in different landfills in China. These results indicated that WBS had high adsorption capacity of TCE in LFG and temperature should be paid more attention to manipulate WBS to reduce TCE emissions from landfills.

  12. Characterization of trichloroethylene adsorption onto waste biocover soil in the presence of landfill gas.

    PubMed

    He, Ruo; Su, Yao; Kong, Jiaoyan

    2015-09-15

    Waste biocover soils (WBS) have been demonstrated to have great potential in mitigating trichloroethylene (TCE) emission from landfills, due to the relatively high TCE-degrading capacity. In this study, the characteristics of TCE adsorption on WBS in the presence of the major landfill gas components (i.e., CH4 and CO2) were investigated in soil microcosms. The adsorption isotherm of TCE onto WBS was fitted well with linear model within the TCE concentrations of 7000 ppmv. The adsorption capacity of TCE onto WBS was affected by temperature, soil moisture content and particle size, of which, temperature was the dominant factor. The adsorption capacity of TCE onto the experimental materials increased with the increasing organic matter content. A significantly positive correlation was observed between the adsorption capacity of TCE and the organic matter content of experimental materials that had relatively higher organic content (r = 0.988, P = 0.044). To better understand WBS application in practice, response surface methodology was developed to predict TCE adsorption capacity and emissions through WBS in different landfills in China. These results indicated that WBS had high adsorption capacity of TCE in LFG and temperature should be paid more attention to manipulate WBS to reduce TCE emissions from landfills. PMID:25909498

  13. Breakthrough CO₂ adsorption in bio-based activated carbons.

    PubMed

    Shahkarami, Sepideh; Azargohar, Ramin; Dalai, Ajay K; Soltan, Jafar

    2015-08-01

    In this work, the effects of different methods of activation on CO2 adsorption performance of activated carbon were studied. Activated carbons were prepared from biochar, obtained from fast pyrolysis of white wood, using three different activation methods of steam activation, CO2 activation and Potassium hydroxide (KOH) activation. CO2 adsorption behavior of the produced activated carbons was studied in a fixed-bed reactor set-up at atmospheric pressure, temperature range of 25-65°C and inlet CO2 concentration range of 10-30 mol% in He to determine the effects of the surface area, porosity and surface chemistry on adsorption capacity of the samples. Characterization of the micropore and mesopore texture was carried out using N2 and CO2 adsorption at 77 and 273 K, respectively. Central composite design was used to evaluate the combined effects of temperature and concentration of CO2 on the adsorption behavior of the adsorbents. The KOH activated carbon with a total micropore volume of 0.62 cm(3)/g and surface area of 1400 m(2)/g had the highest CO2 adsorption capacity of 1.8 mol/kg due to its microporous structure and high surface area under the optimized experimental conditions of 30 mol% CO2 and 25°C. The performance of the adsorbents in multi-cyclic adsorption process was also assessed and the adsorption capacity of KOH and CO2 activated carbons remained remarkably stable after 50 cycles with low temperature (160°C) regeneration.

  14. Preparation of granular activated carbons from yellow mombin fruit stones for CO2 adsorption.

    PubMed

    Fiuza, Raildo Alves; Medeiros de Jesus Neto, Raimundo; Correia, Laise Bacelar; Carvalho Andrade, Heloysa Martins

    2015-09-15

    Stones of yellow mombin, a native fruit of the tropical America and West Indies, were used as starting materials to produce activated carbons, subsequently used as adsorbent for CO2 capture. The carbonaceous materials were either chemically activated with HNO3, H3PO4 and KOH or physically activated with CO2. The carbon samples were characterized by SEM, EDX, TG/DTA, Raman spectroscopy, physical adsorption for textural analysis and by acid-base titrations. The CO2 adsorption capacity and adsorption cycles were investigated by TG. The results indicate that the capacity of CO2 adsorption may be maximized on highly basic surfaces of micropores smaller than 1 nm. The KOH activated carbon showed high and stable capacity of CO2 adsorption after 10 cycles.

  15. Technical note: Adsorption capacity of GAC for synthetic organics

    SciTech Connect

    Speth, T.F.; Miltner, R.J.

    1990-01-01

    Isotherms are presented for 58 compounds in distilled-deionized water, filtered river water, and filtered groundwater. The compounds, which ranged from volatile organics to insecticides, are either regulated or being considered for regulation by the US Environmental Protection Agency.

  16. Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

    PubMed

    Futera, Zdeněk; Burda, Jaroslav V

    2014-07-15

    Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA.

  17. Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

    PubMed

    Futera, Zdeněk; Burda, Jaroslav V

    2014-07-15

    Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA. PMID:24865949

  18. Modeling reactive scattering of F(2P) at a liquid squalane interface: a hybrid QM/MM molecular dynamics study.

    PubMed

    Radak, Brian K; Yockel, Scott; Kim, Dongwook; Schatz, George C

    2009-07-01

    To better understand the reactivity of gases with liquid surfaces, experimentalists have recently probed the reactive scattering of atomic fluorine at the surface of liquid squalane (C(30)H(62)). In this paper we further this research by simulating this scattering process at collision energies of 0.5 and 1.0 eV using a hybrid QM/MM molecular dynamics scheme. To model the structure of the liquid surface, classical molecular dynamics calculations were performed utilizing the OPLS-AA force field. During the F + squalane molecular dynamics simulation, QM/MM calculations are performed at every trajectory step by combining the MSINDO semiempirical Hamiltonian with OPLS-AA and using a dynamic partitioning of the atoms in the QM or MM regions via a "seed atom" method. This computational model provides a type of "on-the-fly" direct dynamics applicable to larger scale chemical processes that include the making/breaking of chemical bonds not available in standard force field models. Our results show that H abstraction is the only reactive scattering pathway and that most trajectories result in reactive scattering. Reaction statistics at the squalane surface are discussed, including variation of the results with incident angle and collision energy, and the probability of reaction as a function of carbon atom type, collision depth, and residence time. Product states, including angular distributions and final translational and rovibrational energies, are also considered and found to be significantly affected by the exothermic reaction energy for H abstraction. The vibrational distributions are in good agreement with recent experiments, but the rotational distributions are dominated by a nonthermal component while the experiments, which involve thermal incident energies, show comparable thermal and nonthermal contributions. Results for O + squalane at 1.0 eV, which we also present, show analogous comparisons with experiment, with OH vibrational distributions which are cold and

  19. Evaluation of competitive adsorption in anaerobic GAC reactors

    SciTech Connect

    Nakhla, G.F.; Suidan, M.T.

    1995-10-01

    This study primarily investigates the role of competition in completely mixed anaerobic granular activated carbon (GAC) reactors treating a synthetic wastewater consisting of acetic acid, phenol, and o-cresol, and also addresses dual substrate biodegradation. The fate of the biodegradable nonadsorbable substrate followed very closely that of the biodegradable adsorbable substrate. As adsorption complemented biodegradation in this system, with the two being oppositely influenced by the GAC replacement rate, the removal of both biodegradable substrates exhibited both a maximum and minimum at GAC residence times of 30 and 12 days, respectively. On comparing the experimental capacities for o-cresol, which resisted biodegradation in the GAC reactors, with the o-cresol isotherm capacities, the effect of phenol competition for adsorption was found to be negligible when the effluent o-cresol concentrations were orders of magnitude higher than the concentrations of the biodegradable phenol. Competition effects decreased the adsorptive capacities of the reactors` GAC for o-cresol when phenol and o-cresol concentrations were of the same order of magnitude, although phenol sorptive capacities were predicted much more closely than at very low phenol concentration. The ideal adsorbed solution theory (IAST) was found to fairly describe the competition for adsorption between phenol and o-cresol despite some discrepancies between the experimental and the model-predicted capacities at low adsorbate concentrations.

  20. [Study on treatment of methylene blue wastewater by fly ash adsorption-Fenton and thermal regeneration].

    PubMed

    Bai, Yu-Jie; Zhang, Ai-Li; Zhou, Ji-Ti

    2012-07-01

    The physicochemical properties of water-washed fly ash (FA) and acid modified fly ash (M-FA) were investigated. The adsorption of methylene blue by FA and M-FA were studied by batch experiments. Two methods, Fenton-drive oxidation regeneration and thermal regeneration, were used for regeneration of the used FA and M-FA. The result showed that the rate of adsorption process followed the second order kinetics and the adsorption followed Langmuir isotherms. The adsorption equilibrium time was 30 min, and the equilibrium adsorption capacity of FA and M-FA were 4.22 mg x g(-1) and 5.98 mg x g(-1) respectively. The adsorption capability of M-FA was higher than that of FA. In the range of pH 2-12, the adsorption capacity of M-FA increased with the increase of pH, whereas the adsorption capacity of FA decreased slowly until the pH 8 and then increased. Electrostatic adsorption was the major factor on the adsorption capacity. Around 61% and 55% percentage regeneration (PR) were obtained for FA and M-FA respectively when 78.4 mmol x L(-1) H2O2 and 0.72 mmol x L(-1) Fe2+ were used. When the condition of thermal regeneration was 400 degrees C and 2 h, a positive correlation can be found between the PRs of FA and regeneration times, the PRs were 102%, 104% and 107% in three cycles of adsorption-thermal regeneration process. However a negative correlation can be found between the PRs of M-FA and regeneration times, the PRs were 82%, 75% and 74% in three cycles of adsorption-thermal regeneration process. The PR of FA was higher than that of M-FA, and thermal regeneration was superior to Fenton-drive regeneration. PMID:23002621

  1. [Study on treatment of methylene blue wastewater by fly ash adsorption-Fenton and thermal regeneration].

    PubMed

    Bai, Yu-Jie; Zhang, Ai-Li; Zhou, Ji-Ti

    2012-07-01

    The physicochemical properties of water-washed fly ash (FA) and acid modified fly ash (M-FA) were investigated. The adsorption of methylene blue by FA and M-FA were studied by batch experiments. Two methods, Fenton-drive oxidation regeneration and thermal regeneration, were used for regeneration of the used FA and M-FA. The result showed that the rate of adsorption process followed the second order kinetics and the adsorption followed Langmuir isotherms. The adsorption equilibrium time was 30 min, and the equilibrium adsorption capacity of FA and M-FA were 4.22 mg x g(-1) and 5.98 mg x g(-1) respectively. The adsorption capability of M-FA was higher than that of FA. In the range of pH 2-12, the adsorption capacity of M-FA increased with the increase of pH, whereas the adsorption capacity of FA decreased slowly until the pH 8 and then increased. Electrostatic adsorption was the major factor on the adsorption capacity. Around 61% and 55% percentage regeneration (PR) were obtained for FA and M-FA respectively when 78.4 mmol x L(-1) H2O2 and 0.72 mmol x L(-1) Fe2+ were used. When the condition of thermal regeneration was 400 degrees C and 2 h, a positive correlation can be found between the PRs of FA and regeneration times, the PRs were 102%, 104% and 107% in three cycles of adsorption-thermal regeneration process. However a negative correlation can be found between the PRs of M-FA and regeneration times, the PRs were 82%, 75% and 74% in three cycles of adsorption-thermal regeneration process. The PR of FA was higher than that of M-FA, and thermal regeneration was superior to Fenton-drive regeneration.

  2. High capacity carbon dioxide sorbent

    DOEpatents

    Dietz, Steven Dean; Alptekin, Gokhan; Jayaraman, Ambalavanan

    2015-09-01

    The present invention provides a sorbent for the removal of carbon dioxide from gas streams, comprising: a CO.sub.2 capacity of at least 9 weight percent when measured at 22.degree. C. and 1 atmosphere; an H.sub.2O capacity of at most 15 weight percent when measured at 25.degree. C. and 1 atmosphere; and a