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Sample records for adsorption capacity qm

  1. Impacts of amount of impregnated iron in granular activated carbon on arsenate adsorption capacities and kinetics.

    PubMed

    Chang, Qigang; Lin, Wei; Ying, Wei-Chi

    2012-06-01

    Iron-impregnated granular activated carbons (Fe-GAC) can remove arsenic effectively from water. In this study, Fe-GACs with iron content of 1.64 to 28.90% were synthesized using a new multi-step procedure for the investigation of effects of iron amount on arsenic adsorption capacities and kinetics. Langmuir model satisfactorily fit arsenic adsorption on Fe-GACs. The maximum arsenic adsorption capacity (q(m)) increased significantly with iron impregnation and reached 1,867 to 1,912 microg/g with iron content of 9.96 to 13.59%. Further increase of iron content (> 13.59%) caused gradual decrease of q(m). It was found that the amount of impregnated iron showed little impact on the affinity for arsenate. Kinetic study showed that the amount of impregnated iron affected the arsenic intraparticle diffusion rate greatly. The pseudo-second-order kinetic model fit arsenic adsorption kinetics on Fe-GACs better than the pseudo-first-order model. The arsenic adsorption rate increased with increasing of iron content from 1.64% to 13.59%, and then decreased with more impregnated iron (13.59 to 28.90%).

  2. Gas adsorption capacity of wood pellets

    DOE PAGES

    Yazdanpanah, F.; Sokhansanj, Shahabaddine; Lim, C. Jim; ...

    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

  3. Gas adsorption capacity of wood pellets

    SciTech Connect

    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 challenging 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.

  4. 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.

  5. Predicting protein dynamic binding capacity from batch adsorption tests.

    PubMed

    Carta, Giorgio

    2012-10-01

    The dynamic binding capacity (DBC) and its dependence on residence time influence the design and productivity of adsorption columns used in protein capture applications. This paper offers a very simple approach to predict the DBC of an adsorption column based on a measurement of the equilibrium binding capacity (EBC) and of the time needed to achieve one-half of the EBC in a batch adsorption test. The approach is based on a mass transfer kinetics model that assumes pore diffusion with a rectangular isotherm; however, the same approach is also shown to work for other systems where solute transport inside the particle occurs through other transport mechanisms.

  6. 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.

  7. 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.

  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. 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.

  10. 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.

  11. 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.

  12. Proteomic analysis of protein adsorption capacity of different haemodialysis membranes.

    PubMed

    Urbani, Andrea; Lupisella, Santina; Sirolli, Vittorio; Bucci, Sonia; Amoroso, Luigi; Pavone, Barbara; Pieroni, Luisa; Sacchetta, Paolo; Bonomini, Mario

    2012-04-01

    Protein-adsorptive properties are a key feature of membranes used for haemodialysis treatment. Protein adsorption is vital to the biocompatibility of a membrane material and influences membrane's performance. The object of the present study is to investigate membrane biocompatibility by correlating the adsorbed proteome repertoire with chemical feature of the membrane surfaces. Dialyzers composed of either cellulose triacetate (Sureflux 50 L, effective surface area 0.5 m(2); Nipro Corporation, Japan) or the polysulfone-based helixone (FX40, effective surface area 0.4 m(2); Fresenius Medical Care AG, Germany) materials were employed to develop an ex vivo apparatus to study protein adsorption. Adsorbed proteins were eluted by a strong chaotropic buffer condition and investigated by a proteomic approach. The profiling strategy was based on 2D-electrophoresis separation of desorbed protein coupled to MALDI-TOF/TOF analysis. The total protein adsorption was not significantly different between the two materials. An average of 179 protein spots was visualised for helixone membranes while a map of retained proteins of cellulose triacetate membranes was made up of 239 protein spots. The cellulose triacetate material showed a higher binding capacity for albumin and apolipoprotein. In fact, a number of different protein spots belonging to the gene transcript of albumin were visible in the cellulose triacetate map. In contrast, helixone bound only a small proportion of albumin, while proved to be particularly active in retaining protein associated with the coagulation cascade, such as the fibrinogen isoforms. Our data indicate that proteomic techniques are a useful approach for the investigation of proteins surface-adsorbed onto haemodialysis membranes, and may provide a molecular base for the interpretation of the efficacy and safety of anticoagulation treatment during renal replacement therapy.

  13. Chemical modification of oxalate decarboxylase to improve adsorption capacity.

    PubMed

    Lin, Rihui; He, Junbin; Wu, Jia; Cai, Xinghua; Long, Han; Chen, Shengfeng; Liu, Haiqian

    2017-02-03

    In order to enhance the adsorption capacity of oxalate decarboxylase (Oxdc) on calcium oxalate monohydrate crystals and improve the application performance of Oxdc, chemical modification of Oxdc with ethylenediaminetetraacetic dianhydride (EDTAD) was investigated in this work. The sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and liquid chromatography tandem mass spectrometry (LC/MS) analysis results demonstrated that Oxdc and EDTAD have been covalently bound, and suggested that the chemical modification occurred at the free amino of the side chain and the α-amine of the N-terminus of Oxdc. Fluorescene and circular dichroic measurement showed that the structure and conformation of Oxdc were tinily altered after modification by EDTAD. The optimum pH of EDTAD-modified Oxdc was shifted to the alkaline side about 1.5 unit and it has a higher thermostability. The analysis of kinetic parameters indicated that the EDTAD-modified Oxdc showed a higher affinity towards the substrate. Through modification the adsorption capacity of Oxdc onto CaOx monohydrate crystals was increased by 42.42%.

  14. Enhanced chromium adsorption capacity via plasma modification of natural zeolites

    NASA Astrophysics Data System (ADS)

    Cagomoc, Charisse Marie D.; Vasquez, Magdaleno R., Jr.

    2017-01-01

    Natural zeolites such as mordenite are excellent adsorbents for heavy metals. To enhance the adsorption capacity of zeolite, sodium-exchanged samples were irradiated with 13.56 MHz capacitively coupled radio frequency (RF) argon gas discharge. Hexavalent chromium [Cr(VI)] was used as the test heavy metal. Pristine and plasma-treated zeolite samples were soaked in 50 mg/L Cr solution and the amount of adsorbed Cr(VI) on the zeolites was calculated at predetermined time intervals. Compared with untreated zeolite samples, initial Cr(VI) uptake was 70% higher for plasma-treated zeolite granules (50 W 30 min) after 1 h of soaking. After 24 h, all plasma-treated zeolites showed increased Cr(VI) uptake. For a 2- to 4-month period, Cr(VI) uptake increased about 130% compared with untreated zeolite granules. X-ray diffraction analyses between untreated and treated zeolite samples revealed no major difference in terms of its crystal structure. However, for plasma-treated samples, an increase in the number of surface defects was observed from scanning electron microscopy images. This increase in the number of surface defects induced by plasma exposure played a crucial role in increasing the number of active sorption sites on the zeolite surface.

  15. 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.

  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.

  17. High-capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework.

    PubMed

    Xiao, Bo; Wheatley, Paul S; Zhao, Xuebo; Fletcher, Ashleigh J; Fox, Sarah; Rossi, Adriano G; Megson, Ian L; Bordiga, S; Regli, L; Thomas, K Mark; Morris, Russell E

    2007-02-07

    Gas adsorption experiments have been carried out on a copper benzene tricarboxylate metal-organic framework material, HKUST-1. Hydrogen adsorption at 1 and 10 bar (both 77 K) gives an adsorption capacity of 11.16 mmol H2 per g of HKUST-1 (22.7 mg g(-)1, 2.27 wt %) at 1 bar and 18 mmol per g (36.28 mg g(-)1, 3.6 wt %) at 10 bar. Adsorption of D2 at 1 bar (77 K) is between 1.09 (at 1 bar) and 1.20(at <100 mbar) times the H2 values depending on the pressure, agreeing with the theoretical expectations. Gravimetric adsorption measurements of NO on HKUST-1 at 196 K (1 bar) gives a large adsorption capacity of approximately 9 mmol g(-1), which is significantly greater than any other adsorption capacity reported on a porous solid. At 298 K the adsorption capacity at 1 bar is just over 3 mmol g(-1). Infra red experiments show that the NO binds to the empty copper metal sites in HKUST-1. Chemiluminescence and platelet aggregometry experiments indicate that the amount of NO recovered on exposure of the resulting complex to water is enough to be biologically active, completely inhibiting platelet aggregation in platelet rich plasma.

  18. Methane Adsorption on Aggregates of Fullerenes: Site-Selective Storage Capacities and Adsorption Energies

    PubMed Central

    Kaiser, Alexander; Zöttl, Samuel; Bartl, Peter; Leidlmair, Christian; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Echt, Olof; Scheier, Paul

    2013-01-01

    Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118–281 meV are in the optimal range for high-density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane–methane and fullerene–methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes. PMID:23744834

  19. Methane adsorption on aggregates of fullerenes: site-selective storage capacities and adsorption energies.

    PubMed

    Kaiser, Alexander; Zöttl, Samuel; Bartl, Peter; Leidlmair, Christian; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Echt, Olof; Scheier, Paul

    2013-07-01

    Methane adsorption on positively charged aggregates of C60 is investigated by both mass spectrometry and computer simulations. Calculated adsorption energies of 118-281 meV are in the optimal range for high-density storage of natural gas. Groove sites, dimple sites, and the first complete adsorption shells are identified experimentally and confirmed by molecular dynamics simulations, using a newly developed force field for methane-methane and fullerene-methane interaction. The effects of corrugation and curvature are discussed and compared with data for adsorption on graphite, graphene, and carbon nanotubes.

  20. Efficient removal and highly selective adsorption of Hg2+ by polydopamine nanospheres with total recycle capacity

    NASA Astrophysics Data System (ADS)

    Zhang, Xiulan; Jia, Xin; Zhang, Guoxiang; Hu, Jiamei; Sheng, Wenbo; Ma, Zhiyuan; Lu, Jianjiang; Liu, Zhiyong

    2014-09-01

    This study reported a new method for efficient removal of Hg2+ from contaminated water using highly selective adsorptive polydopamine (PDA) nanospheres, which were uniform and had a small diameter (150-200 nm). The adsorption isotherms, kinetics, thermodynamics were investigated. Also, the effects of ionic strength, co-existing ions on removing ability of PDA nanospheres for Hg2+ were studied. Adsorption of Hg2+ was very fast and efficient as adsorption equilibrium was completed within 4 h and the maximum adsorption capacities were 1861.72 mg/g, 2037.22 mg/g, and 2076.81 mg/g at 298 K, 313 K, and 328 K respectively, increasing with increasing of temperature. The PDA nanospheres exhibited highly selective adsorption of Hg2+ and had a total desorption capacity of 100% in hydrochloric acid solution, pH 1. The results showed that the structure of PDA nanospheres remained almost unchanged after recycling five times. Furthermore, X-ray photoelectron spectroscopy (XPS) was employed to determine the elements of PDA nanospheres before and after Hg2+ adsorption. Considering their efficient and highly Hg2+ selective adsorption, total recycle capacity, and high stability, PDA nanospheres will be feasible in a number of practical applications.

  1. 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.

  2. Reduction of adsorption capacity of coconut shell activated carbon for organic vapors due to moisture contents.

    PubMed

    Abiko, Hironobu; Furuse, Mitsuya; Takano, Tsuguo

    2010-01-01

    In occupational hygiene, activated carbon produced from coconut shell is a common adsorbent material for harmful substances including organic vapors due to its outstanding adsorption capacity and cost advantage. However, moisture adsorption of the carbon generally decreases the adsorption capacity for organic vapors. In a previous report, we prepared several coconut shell activated carbons which had been preconditioned by equilibration with moisture at different relative humidities and measured the breakthrough times for 6 kinds of organic vapor, in order to clarify the effect of preliminary moisture content in activated carbon on the adsorption capacity in detail. We found that the relative percent weight increase due to moisture adsorption of the carbon specimen had a quantitative effect, reducing the breakthrough time. In this report, we carried out further measurements of the effect of moisture content on the adsorption of 13 kinds of organic vapor, and investigated the relationship between moisture adsorption and the reduction of the breakthrough time of activated carbon specimens. We also applied the data to the Wood's breakthrough time estimation model which is an extension of the Wheeler-Jonas equation.

  3. Better adsorption capacity of SnO2 nanoparticles with different graphene addition

    NASA Astrophysics Data System (ADS)

    Paramarta, V.; Taufik, A.; Saleh, R.

    2016-11-01

    The adsorption capacity of SnO2 nanoparticle has been studied by graphene and nanographene platelets (NGP) additions using co-precipitation method. The crystalline phase, composition, and morphology of the samples are analyzed using X-Ray Diffraction (XRD), Energy Dispersive X-Ray (EDX), Fourier Transform Infrared Spectroscopy (FT-IR), and Transmission Electron Microscope (TEM). Tetragonal structure of SnO2 is shown for the nanoparticle and its composites. The presence of graphene and NGP is also confirmed. The adsorption capacity of the nanoparticle and its composites are analyzed by observing the degradation of methylene blue (MB) as the organic dye model using UV-Vis Spectroscopy. The result shows that SnO2 composite with graphene achieves higher adsorption capacity of about 20% than the composite with NGP. The fitting of equilibrium adsorption capacity result indicates that the adsorption mechanism of SnO2 composite with graphene tends to follow the Langmuir adsorption-isotherm model.

  4. 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.

  5. 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.

  6. 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.

  7. High-Capacity and Photoregenerable Composite Material for Efficient Adsorption and Degradation of Phenanthrene in Water.

    PubMed

    Liu, Wen; Cai, Zhengqing; Zhao, Xiao; Wang, Ting; Li, Fan; Zhao, Dongye

    2016-10-18

    We report a novel composite material, referred to as activated charcoal supported titanate nanotubes (TNTs@AC), for highly efficient adsorption and photodegradation of a representative polycyclic aromatic hydrocarbon (PAH), phenanthrene. TNTs@AC was prepared through a one-step hydrothermal method, and is composed of an activated charcoal core and a shell of carbon-coated titanate nanotubes. TNTs@AC offered a maximum Langmuir adsorption capacity of 12.1 mg/g for phenanthrene (a model PAH), which is ∼11 times higher than the parent activated charcoal. Phenanthrene was rapidly concentrated onto TNTs@AC, and subsequently completely photodegraded under UV light within 2 h. The photoregenerated TNTs@AC can then be reused for another adsorption-photodegradation cycle without significant capacity or activity loss. TNTs@AC performed well over a wide range of pH, ionic strength, and dissolved organic matter. Mechanistically, the enhanced adsorption capacity is attributed to the formation of carbon-coated ink-bottle pores of the titanate nanotubes, which are conducive to capillary condensation; in addition, the modified microcarbon facilitates transfer of excited electrons, thereby inhibiting recombination of the electron-hole pairs, resulting in high photocatalytic activity. The combined high adsorption capacity, photocatalytic activity, and regenerability/reusability merit TNTs@AC a very attractive material for concentrating and degrading a host of micropollutants in the environment.

  8. 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.

  9. Influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays.

    PubMed

    Sánchez-Martín, M J; Dorado, M C; del Hoyo, C; Rodríguez-Cruz, M S

    2008-01-15

    Adsorption of three surfactants of different nature, Triton X-100 (TX100) (non-ionic), sodium dodecylsulphate (SDS) (anionic) and octadecyltrimethylammonium bromide (ODTMA) (cationic) by four layered (montmorillonite, illite, muscovite and kaolinite) and two non-layered (sepiolite and palygorskite) clay minerals was studied. The objective was to improve the understanding of surfactant behaviour in soils for the possible use of these compounds in remediation technologies of contaminated soils by toxic organic compounds. Adsorption isotherms were obtained using surfactant concentrations higher and lower than the critical micelle concentration (cmc). These isotherms showed different adsorption stages of the surfactants by the clay minerals, and were classified in different subgroups of the L-, S- or H-types. An increase in the adsorption of SDS and ODTMA by all clay minerals is observed up to the cmc of the surfactant in the equilibrium solution is reached. However, there was further TX100 adsorption when the equilibrium concentration was well above the cmc. Adsorption constants from Langmuir and Freundlich equations (TX100 and ODTMA) or Freundlich equation (SDS) were used to compare adsorption of different surfactants by clay minerals studied. These constants indicated the surfactant adsorption by clay minerals followed this order ODTMA>TX100>SDS. The adsorption of TX100 and ODTMA was higher by montmorillonite and illite, and the adsorption of SDS was found to be higher by kaolinite and sepiolite. Results obtained show the influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays, and they indicate the interest to consider the soil mineralogical composition when one surfactant have to be selected in order to establish more efficient strategies for the remediation of soils and water contaminated by toxic organic pollutants.

  10. 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.

  11. Non-contact analysis of the adsorptive ink capacity of nano silica pigments on a printing coating base.

    PubMed

    Jiang, Bo; Huang, Yu Dong

    2014-01-01

    Near infrared spectra combined with partial least squares were proposed as a means of non-contact analysis of the adsorptive ink capacity of recording coating materials in ink jet printing. First, the recording coating materials were prepared based on nano silica pigments. 80 samples of the recording coating materials were selected to develop the calibration of adsorptive ink capacity against ink adsorption (g/m2). The model developed predicted samples in the validation set with r2  = 0.80 and SEP = 1.108, analytical results showed that near infrared spectra had significant potential for the adsorption of ink capacity on the recording coating. The influence of factors such as recording coating thickness, mass ratio silica: binder-polyvinyl alcohol and the solution concentration on the adsorptive ink capacity were studied. With the help of the near infrared spectra, the adsorptive ink capacity of a recording coating material can be rapidly controlled.

  12. [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).

  13. 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.

  14. Assessment of CO₂ adsorption capacity on activated carbons by a combination of batch and dynamic tests.

    PubMed

    Balsamo, Marco; Silvestre-Albero, Ana; Silvestre-Albero, Joaquín; Erto, Alessandro; Rodríguez-Reinoso, Francisco; Lancia, Amedeo

    2014-05-27

    In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance of three different activated carbons (AC) obtained from olive stones by chemical activation followed by physical activation with CO2 at varying times (i.e., 20, 40, and 60 h). Kinetic and thermodynamic CO2 adsorption tests from simulated flue gas at different temperatures and CO2 pressures are carried out under both batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with a CO2/N2 mixture) conditions. The textural characterization of the AC samples shows a direct dependence of both micropore and ultramicropore volume on the activation time; hence, AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that when CO2 pressure is lower than 0.3 bar, the lower the activation time, the higher CO2 adsorption capacity; a ranking of ω(eq)(AC20) > ω(eq)(AC40) > ω(eq)(AC60) can be exactly defined when T = 293 K. This result is likely ascribed to the narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of flue gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight the fact that the adsorption of N2 on the synthesized AC samples can be considered to be negligible. Finally, the importance of proper analysis for data characterization and adsorption experimental results is highlighted for the correct assessment of the CO2 removal performance of activated carbons at different CO2 pressures and operating temperatures.

  15. 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...

  16. 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...

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Modified inverse micelle synthesis for mesoporous alumina with a high D4 siloxane adsorption capacity

    SciTech Connect

    Zhong, Wei; Jiang, Ting; Jafari, Tahereh; Poyraz, Altug S.; Wu, Wei; Kriz, David A.; Du, Shoucheng; Biswas, Sourav; Thompson Pettes, Michael; Suib, Steven L.

    2016-10-18

    In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlled by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.

  4. Modified inverse micelle synthesis for mesoporous alumina with a high D4 siloxane adsorption capacity

    DOE PAGES

    Zhong, Wei; Jiang, Ting; Jafari, Tahereh; ...

    2016-10-18

    In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlledmore » by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.« less

  5. 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.

  6. 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

  7. Activated carbons prepared from wood particleboard wastes: characterisation and phenol adsorption capacities.

    PubMed

    Girods, P; Dufour, A; Fierro, V; Rogaume, Y; Rogaume, C; Zoulalian, A; Celzard, A

    2009-07-15

    The problems of valorisation of particleboard wastes on one hand, and contamination of aqueous effluents by phenolic compounds on the other hand, are simultaneously considered in this work. Preparation of activated carbons from a two steps thermo-chemical process, formerly designed for generating combustible gases, is suggested. The resultant carbonaceous residue is activated with steam at 800 degrees C. Depending on the preparation conditions, surface areas within the range 800-1300 m(2)/g are obtained, close to that of a commercial activated carbon (CAC) specially designed for water treatment and used as a reference material. The present work shows that particleboard waste-derived activated carbons (WAC) are efficient adsorbents for the removal of phenol from aqueous solutions, with maximum measured capacities close to 500 mg/g. However, most of times, the adsorption capacities are slightly lower than that of the commercial material in the same conditions, i.e., at equilibrium phenol concentrations below 300 ppm. Given the extremely low cost of activated carbons prepared from particleboard waste, it should not be a problem to use it in somewhat higher amounts than what is required with a more expensive commercial material. Phenol adsorption isotherms at 298 K were correctly fitted by various equations modelling type I and type II isotherms for CAC and WAC, respectively. Phenol adsorption isotherms of type II were justified by a 3-stages adsorption mechanism.

  8. Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis dehn. bark.

    PubMed

    Patnukao, Phussadee; Kongsuwan, Apipreeya; Pavasant, Prasert

    2008-01-01

    Powdered activated carbon (PAC) prepared from Eucalyptus camaldulensis Dehn. bark was tested for its adsorption capacity for Cu(II) and Pb(II). The experiment was conducted to investigate the effects of pH, contact time, initial metal concentration, and temperature. The best adsorption of both Cu(II) and Pb(II) occurred at pH 5, where the adsorption reached equilibrium within 45 min for the whole range of initial heavy metal concentrations (0.1-10 mmol/L). The adsorption kinetics was found to follow the pseudo-second order model where equilibrium adsorption capacities and adsorption rate constants increased with initial heavy metal concentrations. The adsorption isotherm followed Langmuir better than Freundlich models within the temperature range (25-60 degrees C). The maximum adsorption capacities (qm) occurred at 60 degrees C, where qm for Cu(II) and Pb(II) were 0.85 and 0.89 mmol/g, respectively. The enthalpies of Cu(II) and Pb(II) adsorption were 43.26 and 58.77 kJ/mol, respectively. The positive enthalpy of adsorption indicated an endothermic nature of the adsorption.

  9. CoFe2O4@MIL-100(Fe) hybrid magnetic nanoparticles exhibit fast and selective adsorption of arsenic with high adsorption capacity

    NASA Astrophysics Data System (ADS)

    Yang, Ji-Chun; Yin, Xue-Bo

    2017-01-01

    In this study, we report the synthesis and application of mesoporous CoFe2O4@MIL-100(Fe) hybrid magnetic nanoparticles (MNPs) for the simultaneous removal of inorganic arsenic (iAs). The hybrid adsorbent had a core-shell and mesoporous structure with an average diameter of 260 nm. The nanoscale size and mesoporous character impart a fast adsorption rate and high adsorption capacity for iAs. In total, 0.1 mg L‑1 As(V) and As(III) could be adsorbed within 2 min, and the maximum adsorption capacities were 114.8 mg g‑1 for As(V) and 143.6 mg g‑1 for As(III), higher than most previously reported adsorbents. The anti-interference capacity for iAs adsorption was improved by the electrostatic repulsion and size exclusion effects of the MIL-100(Fe) shell, which also decreased the zero-charge point of the hybrid absorbent for a broad pH adsorption range. The adsorption mechanisms of iAs on the MNPs are proposed. An Fe-O-As structure was formed on CoFe2O4@MIL-100(Fe) through hydroxyl substitution with the deprotonated iAs species. Monolayer adsorption of As(V) was observed, while hydrogen bonding led to the multi-layer adsorption of neutral As(III) for its high adsorption capacity. The high efficiency and the excellent pH- and interference-tolerance capacities of CoFe2O4@MIL-100(Fe) allowed effective iAs removal from natural water samples, as validated with batch magnetic separation mode and a portable filtration strategy.

  10. CoFe2O4@MIL-100(Fe) hybrid magnetic nanoparticles exhibit fast and selective adsorption of arsenic with high adsorption capacity

    PubMed Central

    Yang, Ji-Chun; Yin, Xue-Bo

    2017-01-01

    In this study, we report the synthesis and application of mesoporous CoFe2O4@MIL-100(Fe) hybrid magnetic nanoparticles (MNPs) for the simultaneous removal of inorganic arsenic (iAs). The hybrid adsorbent had a core-shell and mesoporous structure with an average diameter of 260 nm. The nanoscale size and mesoporous character impart a fast adsorption rate and high adsorption capacity for iAs. In total, 0.1 mg L−1 As(V) and As(III) could be adsorbed within 2 min, and the maximum adsorption capacities were 114.8 mg g−1 for As(V) and 143.6 mg g−1 for As(III), higher than most previously reported adsorbents. The anti-interference capacity for iAs adsorption was improved by the electrostatic repulsion and size exclusion effects of the MIL-100(Fe) shell, which also decreased the zero-charge point of the hybrid absorbent for a broad pH adsorption range. The adsorption mechanisms of iAs on the MNPs are proposed. An Fe-O-As structure was formed on CoFe2O4@MIL-100(Fe) through hydroxyl substitution with the deprotonated iAs species. Monolayer adsorption of As(V) was observed, while hydrogen bonding led to the multi-layer adsorption of neutral As(III) for its high adsorption capacity. The high efficiency and the excellent pH- and interference-tolerance capacities of CoFe2O4@MIL-100(Fe) allowed effective iAs removal from natural water samples, as validated with batch magnetic separation mode and a portable filtration strategy. PMID:28102334

  11. High adsorption capacity of V-doped TiO2 for decolorization of methylene blue

    NASA Astrophysics Data System (ADS)

    Nguyen, Thanh-Binh; Hwang, Moon-Jin; Ryu, Kwang-Sun

    2012-07-01

    In this study, pure TiO2 (V-TiO2-0) and V-doped TiO2 (V-TiO2-x, x = 1-10 mol%) were synthesized using a new sol-gel method. The adsorption capacity of the V-TiO2-x samples was evaluated by measuring the removal of methylene blue (MB) from aqueous solution via decolorization. Since the adsorption capacity was affected by the specific surface area, the interaction between adsorbate (MB) and adsorbent (V-TiO2-x), and the structure of the adsorbent, the physicochemical properties of the samples were investigated. Among the V-doped TiO2-x samples, the V-TiO2-10 sample showed the highest adsorption capacity, which was 11.36 times greater than that of pure TiO2, removing 85.2% of the MB after 2 h. Moreover, changing the molar ratio of the reactants in the V-TiO2-10 sample improved the performance of the material so that 91.6% of the MB was removed after 2 h.

  12. Adsorption of heavy metals on to sugar cane bagasse: improvement of adsorption capacities due to anaerobic degradation of the biosorbent.

    PubMed

    Joseph, Osnick; Rouez, Maxime; Métivier-Pignon, Hélène; Bayard, Rémy; Emmanuel, Evens; Gourdon, Rémy

    2009-12-01

    In this work, anaerobic degradation of sugar cane bagasse was studied with a dual objective: the production of biogas and the improvement of the material's characteristics for its implementation in adsorption processes. The biogas production was determined by means of biomethane potential tests carried out over two months of incubation at 35 degrees C. Biogas and methane cumulative productions were assumed to follow a first-order rate of decay. Theoretical cumulative methane and biogas productions were calculated using Buswell's equation. The anaerobic digestion resulted in a 92% decrease in the leachable organic fraction and a 40% mass loss of bagasse. The average productions of biogas and methane from the whole set of experiments were 293 +/- 6 and 122 +/- 4 mL g(-1) of volatile solids, respectively. The anaerobic incubation of the raw material led to an increase in adsorption capacities towards metal ions, which were multiplied by around 2.0 for Zn2+ and 2.3 for Cd2+.

  13. 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.

  14. Construction of horizontal stratum landform-like composite foams and their methyl orange adsorption capacity

    NASA Astrophysics Data System (ADS)

    Chen, Jiajia; Shi, Xiaowen; Zhan, Yingfei; Qiu, Xiaodan; Du, Yumin; Deng, Hongbing

    2017-03-01

    Chitosan (CS)/rectorite (REC)/carbon nanotubes (CNTs) composite foams with good mechanical properties were successfully fabricated by unidirectional freeze-casting technique. The morphology of the foam showed the well-ordered porous three-dimensional layers and horizontal stratum landform-like structure. The holes on the layers looked like the wings of butterfly. Additionally, the X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy results indicated the successful addition of CNTs and REC. The intercalated REC with CS chains was confirmed by small-angle X-ray diffraction. The surface structure of the foams was also analyzed by Raman spectroscopy. The adsorption experiments showed that when the mass ratio of CS to REC was 10:1 and CNTs content was 20%, the composite foam performed best in adsorbing low concentration methyl orange, and the largest adsorption capacity was 41.65 mg/g.

  15. 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.

  16. Trimodal nanoporous silica as a support for amine-based CO2 adsorbents: Improvement in adsorption capacity and kinetics

    NASA Astrophysics Data System (ADS)

    Chen, Chao; Bhattacharjee, Samiran

    2017-02-01

    A trimodal nanoporous silica (TS) having unique trimodal pore structure viz., internal mesopores, textural mesopores and interconnected macropores, has been functionalized with amine using two different methods covalent grafting and wet impregnation. Both were studied as nanocomposite sorbents for CO2 capture. The effects of the amine loading, immobilization processes and the type of support were investigated. Commercially available silica gel (SG) with a purely mesoporous structure was studied as the support for the amine in order to compare differences in pore structure and amine loading with differences in CO2 adsorption capacity and kinetics. Amine-grafted TS exhibited much faster CO2 adsorption kinetics at 35 °C than amine-grafted SG. At the same amine loading, amine-impregnated TS showed higher CO2 adsorption capacity and faster CO2 adsorption kinetics than amine-impregnated SG. The CO2 adsorption capacity of amine-impregnated TS increased as the amine loading increased until 70%, with the highest value of 172 mg/g, while the amine-impregnated SG reached the highest CO2 adsorption capacity of only 78 mg/g at 40% amine loading. More importantly, amine-impregnated as-prepared TS exhibited even higher CO2 capture capacity than amine-impregnated TS when the amine loading was below 60%. Results suggest that amine-modified trimodal nanoporous silica sorbents meet the challenges of current CO2 capture technology.

  17. Quantitative analysis of the binding strength and adsorption capacity of zinc oxide nanoparticles onto unmodified and modified cotton fiber

    NASA Astrophysics Data System (ADS)

    Printz, Stephen Robert

    Risk of bacterial infection is always a concern in hospitals, so it is important to find ways to minimize this risk. One method for reducing the risk of infection is by using textiles with antimicrobial properties. Zinc oxide nanoparticles have antimicrobial properties, and can be adsorbed onto cotton fibers to pass these properties to the cloth. However, the binding of the zinc oxide nanoparticles to cotton is weak, so the particles desorb from the cloth after repeated washings. The goal of this project was to quantify the binding strength of zinc oxide nanoparticles onto different types of cotton fiber. The cotton was modified by grafting cyclodextrin onto it with citric acid as a crosslinking agent. Adsorption was tested with desized, unbleached cotton print cloth; desized, bleached cotton print cloth; and desized, bleached, mercerized cotton print cloth. As expected, adsorption to unmodified cloth was poor. Unbleached cloth had the highest adsorption capacity (Q 0 = 22 +/- 4 mg ZnO/g cloth), and bleached cloth had the lowest adsorption capacity (Q0 = 17 +/- 4 mg ZnO=g cloth). Mercerized cloth had the lowest strength (b = 0.010 +/- 0.003 ppm-1), and bleached cloth had the highest binding strength (b = 0.04 +/- 0.01 ppm-1). Modification with alpha-cyclodextrin increased adsorption capacity over unmodified cloth by 61, 80, and 70% for mercerized/bleached cloth, bleached cloth, and unbleached cloth, respectively, and increased b by 1601, 126, and 90% respectively. Modification with beta-cyclodextrin increased adsorption capacities by 80, 94, and 112%, respectively, and increased b by 2027, 427, and 46%. As a result, beta-CD modified unbleached cloth had the highest adsorption capacity and one of the lowest binding strengths. However, beta-cyclodextrin modified mercerized cloth has both a high adsorption capacity and a high binding strength, and would likely be the best candidate for use in antimicrobial textiles.

  18. 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.

  19. An adsorbent with a high adsorption capacity obtained from the cellulose sludge of industrial residues.

    PubMed

    Orlandi, Géssica; Cavasotto, Jéssica; Machado, Francisco R S; Colpani, Gustavo L; Magro, Jacir Dal; Dalcanton, Francieli; Mello, Josiane M M; Fiori, Márcio A

    2017-02-01

    One of the major problems in effluent treatment plants of the cellulose and paper industry is the large amount of residual sludge generated. Therefore, this industry is trying to develop new methods to treat such residues and to use them as new products, such as adsorbents. In this regard, the objective of this work was to develop an adsorbent using the raw activated sludge generated by the cellulose and paper industry. The activated cellulose sludge, after being dried, was chemically activated with 42.5% (v/v) phosphoric acid at 85 °C for 1 h and was charred at 500 °C, 600 °C and 700 °C for 2 h. The efficiency of the obtained adsorbent materials was evaluated using kinetic tests with methylene blue solutions. Using the adsorption kinetics, it was verified that the three adsorbents showed the capacity to adsorb dye, and the adsorbent obtained at a temperature of 600 °C showed the highest adsorption capacity of 107.1 mg g(-1). The kinetic model that best fit the experimental data was pseudo-second order. The Langmuir-Freudlich isotherm adequately described the experimental data. As a result, the cellulose sludge generated by the cellulose and paper industries could be used as an adsorbent.

  20. Amine-functionalized PVA-co-PE nanofibrous membrane as affinity membrane with high adsorption capacity for bilirubin.

    PubMed

    Wang, Wenwen; Zhang, Hao; Zhang, Zhifeng; Luo, Mengying; Wang, Yuedan; Liu, Qiongzhen; Chen, Yuanli; Li, Mufang; Wang, Dong

    2017-02-01

    In this study, poly(vinyl alcohol-co-ethylene) (PVA-co-PE) nanofibrous membrane was activated by sodium hydroxide and cyanuric chloride, and then the activated membranes were functionalized by 1,3-propanediamine, hexamethylenediamine and diethylenetriamine to be affinity membranes for bilirubin removal, respectively. The chemical structures and morphologies of membranes were investigated by SEM, FTIR and XPS. And the adsorption ability of different amine-functionalized nanofibrous membranes for bilirubin was characterized. Furthermore, the effects of temperature, initial concentration of bilirubin, NaCl concentration and BSA concentration on the adsorption capacity for bilirubin of diethylenetriamine-functionalized nanofibrous membrane were studied. Results indicated that the adsorption capacity for bilirubin of diethylenetriamine-functionalized nanofibrous membrane could reach 85mg/g membrane when the initial bilirubin concentration was 200mg/L while the adsorption capacity could be increased to 110mg/g membrane if the initial bilirubin concentration was more than 400mg/L. The dynamic adsorption of diethylenetriamine-functionalized nanofibrous membrane showed that the ligands of amine groups on the membrane surface could be used as far as possible by recirculating the plasma with certain flow rates. Therefore, the diethylenetriamine-functionalized PVA-co-PE nanofibrous membrane possessed high adsorption capacity for bilirubin and it can be candidate as affinity membrane for bilirubin removal.

  1. 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.

  2. 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.

  3. Hydrophobic interaction chromatography of proteins. IV. Protein adsorption capacity and transport in preparative mode.

    PubMed

    To, Brian C S; Lenhoff, Abraham M

    2011-01-21

    The adsorption isotherms of four model proteins (lysozyme, α-lactalbumin, ovalbumin, and BSA) on eight commercial phenyl hydrophobic interaction chromatography media were measured. The isotherms were softer than those usually seen in ion-exchange chromatography of proteins, and the static capacities of the media were lower, ranging from 30 to 110 mg/mL, depending on the ammonium sulfate concentration and the protein and adsorbent types. The protein-accessible surface area appears to be the main factor determining the binding capacity, and little correlation was seen with the protein affinities of the adsorbents. Breakthrough experiments showed that the dynamic capacities of the adsorbents at 10% breakthrough were 20-80% of the static capacities, depending on adsorbent type. Protein diffusivities in the adsorbents were estimated from batch uptake experiments using the pore diffusion and homogeneous diffusion models. Protein transport was affected by the adsorbent pore structures. Apparent diffusivities were higher at lower salt concentrations and column loadings, suggesting that adsorbed proteins may retard intraparticle protein transport. The diffusivities estimated from the batch uptake experiments were used to predict column breakthrough behavior. Analytical solutions developed for ion-exchange systems were able to provide accurate predictions for lysozyme breakthrough but not for ovalbumin. Impurities in the ovalbumin solutions used for the breakthrough experiments may have affected the ovalbumin uptake and led to the discrepancies between the predictions and the experimental results.

  4. 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.

  5. 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

  6. 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

  7. Adsorption capacities of poly-γ-glutamic acid and its sodium salt for cesium removal from radioactive wastewaters.

    PubMed

    Sakamoto, Shigeki; Kawase, Yoshinori

    2016-12-01

    Cesium removal from radioactive wastewaters was examined using water-insoluble poly-γ-glutamic acid (γ-PGA) and water-soluble sodium salt form poly-γ-L-glutamic acid (γ-PGANa) as biosorbents. The maximum adsorption capacities at equilibrium of γ-PGA and γ-PGANa for Cs were 345 mg-Cs(g-γ-PGA)(-1) at pH 6.0 and 290 mg-Cs(g-γ-PGANa)(-1) at pH 9.0, respectively. At lower pH < pKa, the carboxyl groups of γ-PGA primarily remained in the protonated form and adsorption of Cs only slightly occurred. At higher pH > pKa, the adsorption of Cs was significantly facilitated due to ionization of carboxyl groups to carboxylate ion. Adsorption of Cs at pH > 9.0 was inhibited due to the hydrolysis of Cs. The Langmuir model could successfully describe the isotherm data. For γ-PGA and γ-PGANa, the maximum adsorption capacities at equilibrium in the Langmuir model were 446 and 333 mg-Cs(g-adsorbent)(-1), respectively. The high adsorption capacities confirmed a potential utilization of γ-PGA and γ-PGANa for Cs removal. The adsorption of Cs by both γ-PGA and γ-PGANa attained the equilibrium within 0.5 min. The very quick equilibration is a benefit from the viewpoint of practical application. The spectra of FT-IR and XPS before and after adsorption confirmed the adsorption of Cs onto γ-PGA and γ-PGANa via electrostatic interaction with carboxylate anions.

  8. 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.

  9. 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.

  10. The effects of urease immobilization on the transport characteristics and protein adsorption capacity of cellulose acetate based hemodialysis membranes.

    PubMed

    Mahlicli, Filiz Yasar; Altinkaya, Sacide Alsoy

    2009-10-01

    In this study, cellulose acetate (CA) based hemodialysis membranes were prepared by a dry phase inversion method and the influences of urease immobilization on the clearing performance and protein adsorption capacity of the membranes were investigated. Permeation experiments have shown that modification of CA membranes with urease immobilization not only enhanced the transport rate of urea but also increased the permeation coefficients of uric acid and creatinine by changing the structure of the membrane. Furthermore, the protein adsorption capacity of the CA membranes decreased. On the other hand, the mechanical strength of the modified CA membrane did not change significantly compared with that of the unmodified one. A mathematical model was derived to determine the rate of mass transfer of urea through modified CA membranes. Model predictions along with the experimental data suggest that urease immobilization can be used as an alternative method in preparing CA based hemodialysis membranes with improved transport characteristics and biocompatibility through reduced protein adsorption capacities.

  11. A geometric pore adsorption model for predicting the drug loading capacity of insoluble drugs in mesoporous carbon.

    PubMed

    Gao, Yikun; Zhu, Wenquan; Liu, Jia; Di, Donghua; Chang, Di; Jiang, Tongying; Wang, Siling

    2015-05-15

    In this work, a simple and accurate geometric pore-adsorption model was established and experimentally validated for predicting the drug loading capacity in mesoporous carbon. The model was designed according to the shape of pore channels of mesoporous carbon and the arrangement of drug molecules loaded in the pores. Three different small molecule drugs (celecoxib, fenofibrate and carvedilol) were respectively loaded in mesoporous carbon with different pore sizes. In order to test the accuracy of the established model, nitrogen adsorption-desorption analysis was employed to confirm the pore structure of mesoporous carbon and to calculate the occupation volume of the adsorbed drugs. The adsorption isotherms of celecoxib were systematically investigated to describe the adsorption process. It was found that the experimental results of adsorption capacity were all in the range of the predicted values for all the tested drugs and mesoporous carbon. The occupation volumes calculated from the model also agreed well with the experimental data. These results demonstrated that the established model could accurately provide the range of drug loading capacity, which may provide a useful option for the prediction of the drug loading capacity of small molecule drugs in mesoporous materials.

  12. 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.

  13. 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.

  14. Synthesis of multi-walled carbon nanotubes/β-FeOOH nanocomposites with high adsorption capacity

    NASA Astrophysics Data System (ADS)

    Song, Hao-Jie; Liu, Lei; Jia, Xiao-Hua; Min, Chunying

    2012-12-01

    A hybrid nanostructure of multi-walled carbon nanotubes (CNTs) and β-ferric oxyhydroxide (β-FeOOH) nanoparticles is synthesized by ultrasonic-assisted in situ hydrolysis of the precursor ferric chloride and CNTs. Characterization by X-ray diffraction, scanning electron microscopy , and transmission electron microscopy establishes the nanohybrid structure of the synthesized sample. The results revealed that the surface of CNTs was uniformly assembled by numerous β-FeOOH nanoparticles and had an average diameter of 3 nm. The formation route of anchoring β-FeOOH nanoparticles onto CNTs was proposed as the intercalation and adsorption of iron ions onto the wall of CNTs, followed by the nucleation and growth of β-FeOOH nanoparticles. The values of remanent magnetization ( M r) and coercivity ( H c) of the as-synthesized CNTs/β-FeOOH nanocomposites were 0.1131 emu g, and 490.824 Oe, respectively. Furthermore, CNTs/β-FeOOH nanocomposites showed a very high adsorption capacity of Congo red and thus these nanocomposites can be used as good adsorbents and can be used for the removal of the dye of Congo red from the waste water system.

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

    PubMed

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

    2006-11-01

    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 (HgCl2) 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 degrees 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 HgCl2 at room temperature. The equilibrium adsorptive capacity of HgCl2 for WPAC measured in this study was 1.49 x 10(-1) mg HgCl2/g PAC at 25 degrees C with an initial HgCI2 concentration of 25 microg/m3. With the increase of adsorption temperature < or = 150 degrees C, the equilibrium adsorptive capacity of HgCl2 for WPAC was decreased to 1.34 x 10(-1) mg HgCl2/g PAC. Furthermore, WPAC with higher sulfur contents could adsorb even more HgCl2 because of the reactions between sulfur and Hg2+ at 150 degrees C. It was demonstrated that the mechanisms for adsorbing HgCl2 onto WPAC were physical adsorption and chemisorption at 25 and 150 degrees C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) > 0.998 for HgCl2 adsorption at 25 and 150 degrees C. Moreover, the equilibrium adsorptive capacity of HgCl2 for virgin WPAC was similar to that for CPAC at 25 degrees C, whereas it was slightly higher for sulfurized WPAC than for

  16. 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.

  17. Effect of the both texture and electrical properties of activated carbon on the CO{sub 2} adsorption capacity

    SciTech Connect

    Djeridi, W.; Ouederni, A.; Mansour, N.Ben; Llewellyn, P.L.; Alyamani, A.; El Mir, L.

    2016-01-15

    Highlights: • A series of activated carbon pellet without binder was prepared by chemical activation. • Carbon dioxide storage isotherm at 30 °C and up to 25 bars was measured for the microporous carbon. • Adsorption enthalpies have been correlated with the carbon dioxide uptake. • Pyrolysis temperature effect on the electrical conductivity of the samples. • Impact of the both texture and electrical properties on CO{sub 2} adsorption capacity have been deducted - Abstract: A series of activated carbon pellets (ACP) based on olive stones were studied for CO{sub 2} storage application. The surface area, pore volume, and pore diameter were evaluated from the analysis of N{sub 2} adsorption isotherm data. The characterization of carbon materials was performed by scanning electron microscopy (SEM), the powder X-ray diffraction (PXRD) and transmission electron microscopy (TEM). The adsorption enthalpies were obtained by microcalorimetry. The effect of pyrolysis temperature on textural, electrical conductivity and gas adsorption capacities of the ACP were investigated by adsorbing CO{sub 2} at 303 K in the pressure range of 0–2.3 MPa. In fact the electrical conductivity is strongly affected by the microporosity of the samples and the size of the micropore. It increases when the pore size decreases which affect the CO{sub 2} adsorption. Also with increases temperature the free electrons concentration on the surface increases which affect the interaction of the adsorbed gas molecules.

  18. Adsorption characteristics of adsorbent resins and antioxidant capacity for enrichment of phenolics from two-phase olive waste.

    PubMed

    Wang, Zhihong; Wang, Chengzhang; Yuan, Jiaojiao; Zhang, Changwei

    2017-01-01

    In this study, the adsorption properties of nine resins including polyamide resin (30-60), polyamide resin (60-100) AB-8, S-8, D-101, NKA-9, NKA-II, XDA-1 and XDA-4 for enrichment phenolics of the olive waste were investigated. XDA-1 and NKA-II were chosen for further study due to their outstanding adsorption and desorption capacity. XDA-1 and NKA-II had similar adsorption and desorption behaviors for phenolics of olive waste. The adsorption mechanism could be better explained by pseudo second-order kinetics model and Freundlich isotherm model, and the adsorption processes were spontaneously and exothermic. The experiment of gradient elution were carried out through treated XDA-1 resins column, the result indicated the total phenolics were mainly obtained from the 40% and 60% ethanol fraction. The order of antioxidant capacity by DPPH  , ABTS(+) radical and FRAP assay was similar with the content of phenolics from fraction elution. The compositions of phenolics from different elution fractions were determined by reversed phase-HPLC-DAD method. Gallic acid, hydroxytyrosol, tyrosol and ferulic acid were the major constituent in the fraction elute, and the content of hydroxytyrosol reached to the 41.69mg/g. The above results revealed the synergistic effects of the different phenolics contribute to the antioxidant capacity.

  19. 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.

  20. Expanded porous MOF-505 analogue exhibiting large hydrogen storage capacity and selective carbon dioxide adsorption.

    PubMed

    Zheng, Baishu; Yun, Ruirui; Bai, Junfeng; Lu, Zhiyong; Du, Liting; Li, Yizhi

    2013-03-18

    An expanded 4,4-paddlewheel-connected porous MOF-505-type metal-organic framework (MOF), [Cu2(PDEB)(H2O)2]·xS (NJU-Bai12; NJU-Bai represents the Nanjing University Bai group and S represents noncoordinated solvent molecules) has been designed from a nanosized rectangular diisophthalate linker containing alkyne groups 5,5'-(1,4-phenylenedi-2,1-ethynediyl)bis(1,3-benzenecarboxylic acid). This MOF material possesses permanent microporosity with the highest Brunauer-Emmett-Teller surface area of 3038 m(2)·g(-1) and the largest unsaturated total hydrogen storage capacity of 62.7 mg·g(-1) at 77 K and 20 bar among reported MOF-505 analogues. Additionally, NJU-Bai12 also exhibits excellent carbon dioxide (CO2) uptake capacity (23.83 and 19.85 mmol·g(-1) at 20 bar for 273 and 298 K, respectively) and selective gas adsorption properties with CO2/CH4 selectivity of 5.0 and CO2/N2 selectivity of 24.6 at room temperature.

  1. 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.

  2. High adsorption capacity of heavy metals on two-dimensional MXenes: an ab initio study with molecular dynamics simulation.

    PubMed

    Guo, Xun; Zhang, Xitong; Zhao, Shijun; Huang, Qing; Xue, Jianming

    2016-01-07

    Density functional theory (DFT) calculation is employed to study the adsorption properties of Pb and Cu on recently synthesized two-dimensional materials MXenes, including Ti3C2, V2C1 and Ti2C1. The influence of surface decoration with functional groups such as H, OH and F have also been investigated. Most of these studied MXenes exhibit excellent capability to adsorb Pb and Cu, especially the adsorption capacity of Pb on Ti2C1 is as high as 2560 mg g(-1). Both the binding energies and the adsorption capacities are sensitive to the functional groups attached to the MXenes' surface. Ab initio molecular dynamics (ab-init MD) simulation confirms that Ti2C1 remains stable at room temperature after adsorbing Pb atoms. Our calculations imply that these newly emerging two-dimensional MXenes are promising candidates for wastewater treatment and ion separation.

  3. 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...

  4. High adsorption capacity NaOH-activated carbon for dye removal from aqueous solution.

    PubMed

    Wu, Feng-Chin; Tseng, Ru-Ling

    2008-04-15

    In this study, the surface coverage ratio (Sc/Sp) and monolayer cover adsorption amount per unit surface area (qmon/Sp) were employed to investigate the adsorption isotherm equilibrium of the adsorption of dyes (AB74, BB1 and MB) on NaOH-activated carbons (FWNa2, FWNa3 and FWNa4); the adsorption rate of the Elovich equation (1/b) and the ratio of 1min adsorption amount of adsorbate to the monolayer cover amount of adsorbate (q1/qmon) were employed to investigate adsorption kinetics. The qmon/Sp of NaOH-activated carbons was better than that of KOH-activated carbons prepared from the same raw material (fir wood). The Sc/Sp values of the adsorption of all adsorbates on adsorbent FWNa3 in this study were found to be higher than those in related literature. Parameters 1/b and q1 of the adsorption of dyes on activated carbons in this study were higher than those on KOH-activated carbons; the q1/qmon value of FWNa3 was the highest. The pore structure and the TPD measurement of the surface oxide groups were employed to explain the superior adsorption performance of FWNa3. A high surface activated carbon (FWNa3) with excellent adsorption performance on dyes with relation to adsorption isotherm equilibrium and kinetics was obtained in this study. Several adsorption data processing methods were employed to describe the adsorption performance.

  5. 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

  6. Adsorption capacity of poly(ether imide) microparticles to uremic toxins.

    PubMed

    Tetali, Sarada D; Jankowski, Vera; Luetzow, Karola; Kratz, Karl; Lendlein, Andreas; Jankowski, Joachim

    2016-01-01

    Uremia is a phenomenon caused by retention of uremic toxins in the plasma due to functional impairment of kidneys in the elimination of urinary waste products. Uremia is presently treated by dialysis techniques like hemofiltration, dialysis or hemodiafiltration. However, these techniques in use are more favorable towards removing hydrophilic than hydrophobic uremic toxins. Hydrophobic uremic toxins, such as hydroxy hipuric acid (OH-HPA), phenylacetic acid (PAA), indoxyl sulfate (IDS) and p-cresylsulfate (pCRS), contribute substantially to the progression of chronic kidney disease (CKD) and cardiovascular disease. Therefore, objective of the present study is to test adsorption capacity of highly porous microparticles prepared from poly(ether imide) (PEI) as an alternative technique for the removal of uremic toxins. Two types of nanoporous, spherically shaped microparticles were prepared from PEI by a spraying/coagulation process.PEI particles were packed into a preparative HPLC column to which a mixture of the four types of uremic toxins was injected and eluted with ethanol. Eluted toxins were quantified by analytical HPLC. PEI particles were able to adsorb all four toxins, with the highest affinity for PAA and pCR. IDS and OH-HPA showed a partially non-reversible binding. In summary, PEI particles are interesting candidates to be explored for future application in CKD.

  7. 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.

  8. Dye-adsorption capacity of high surface-area hydrogen titanate nanosheets processed via modified hydrothermal method.

    PubMed

    Padinhattayil, Hareesh; Augustine, Rimesh; Shukla, Satyajit

    2013-04-01

    High surface-area (380 m2 x g(-1)) hydrogen titanate nanosheets (HTNS) processed via the modified hydrothermal method have been utilized for the removal of methylene blue (MB) dye from an aqueous solution via the surface-adsorption process involving the electrostatic attraction mechanism. The HTNS have been characterized using the transmission electron microscope (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) specific surface-area measurement techniques. The amount of MB dye adsorbed on the surface of HTNS at equilibrium (q(e)) has been examined as a function of contact time, initial dye-concentration, and initial solution-pH. Within the investigated range of initial solution-pH (2.5-11), the MB dye adsorption on the surface of HTNS has been observed to follow the pseudo-second-order kinetics with the dye-adsorption capacity of 119 mg x g(-1) at the initial solution-pH of - 10. The adsorption equilibrium follows the Langmuir isotherm within the initial solution-pH range of 2.5-10. However, in a highly basic solution (initial solution-pH -11), the adsorption equilibrium has been observed to follow the Langmuir, Freundlich, and Dubinin-Kaganer-Radushkevich (DKR) models in the different ranges of initial MB dye concentration. The mere dependence on the DKR model has not been observed within the investigated range of initial solution-pH. The differences in the dye-adsorption characteristics and capacity of HTNS, compared with those of hydrogen titanate nanotubes, have been attributed to the difference in their specific surface-area. Irrespective of the morphology, the maximum coverage of MB dye on the surface of hydrogen titanate has been noted to be the same (52%).

  9. 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.

  10. 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.

  11. Summary of Adsorption Capacity and Adsorption Kinetics of Uranium and Other Elements on Amidoxime-based Adsorbents from Time Series Marine Testing at the Pacific Northwest National Laboratory

    SciTech Connect

    Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.; Wood, Jordana R.; Schlafer, Nicholas J.; Janke, Christopher J.; Das, Sadananda; Mayes, Richard; Saito, Tomonori; Brown, Suree S.; Tsouris, Constantinos; Tsouris, Costas; Wai, Chien M.; Pan, Horng-Bin

    2016-09-29

    The Pacific Northwest National Laboratory (PNNL) has been conducting marine testing of uranium adsorbent materials for the Fuel Resources Program, Department of Energy, Office of Nuclear Energy (DOE-NE) beginning in FY 2012. The marine testing program is being conducted at PNNL’s Marine Sciences Laboratory (MSL), located at Sequim Bay, along the coast of Washington. One of the main efforts of the marine testing program is the determination of adsorption capacity and adsorption kinetics for uranium and selected other elements (e.g. vanadium, iron, copper, nickel, and zinc) for adsorbent materials provided primarily by Oak Ridge National Laboratory (ORNL), but also includes other Fuel Resources Program participants. This report summarizes the major marine testing results that have been obtained to date using time series sampling for 42 to 56 days using either flow-through column or recirculating flume exposures. The major results are highlighted in this report, and the full data sets are appended as a series of Excel spreadsheet files. Over the four year period (2012-2016) that marine testing of amidoxime-based polymeric adsorbents was conducted at PNNL’s Marine Science Laboratory, there has been a steady progression of improvement in the 56-day adsorbent capacity from 3.30 g U/kg adsorbent for the ORNL 38H adsorbent to the current best performing adsorbent prepared by a collaboration between the University of Tennessee and ORNL to produce the adsorbent SB12-8, which has an adsorption capacity of 6.56 g U/kg adsorbent. This nearly doubling of the adsorption capacity in four years is a significant advancement in amidoxime-based adsorbent technology and a significant achievement for the Uranium from Seawater program. The achievements are evident when compared to the several decades of work conducted by the Japanese scientists beginning in the 1980’s (Kim et al., 2013). The best adsorbent capacity reported by the Japanese scientists was 3.2 g U/kg adsorbent for a

  12. Relationship between the adsorption capacity of pesticides by wood residues and the properties of woods and pesticides.

    PubMed

    Rodriguez-Cruz, Sonia; Andrades, Maria S; Sanchez-Camazano, Maria; Sanchez-Martin, Maria J

    2007-05-15

    With the aim to explore the potential use of wood residues in technologies aimed at preventing the pollution of soil and water, we studied the adsorption of four non-ionic pesticides (linuron, alachlor, metalaxyl, and chlorpyrifos) and two ionic pesticides (dicamba and paraquat) with a Kow range of -4.5 to 4.7 by nine types of wood with lignin content in the 18.2-26.9% range. The Freundlich Kf values were considered as indicators of the adsorption capacity. A statistical study was carried out using simple and multiple correlations to establish the degree to which the different parameters of the woods and of the pesticides were involved in adsorption. In the case of the non-ionic pesticides, positive and negative significant correlations were observed between Kf and the lignin (r = 0.73-0.83, p < 0.05-0.01), and soluble C contents of the woods (r = 0.66-0.84), p < 0.1-0.01). For dicamba, a correlation between Kf and pH (r = -0.66, p < 0.1) of the woods was found, while for paraquat, this was seen between Kf and the cation exchange capacity (r = 0.71, p < 0.1) of the woods. No significant correlation was observed between Kf and the total C content of the woods. A highly significant correlation between Kf and Kow values (r > or = 0.93, p < 0.01) was found in the adsorption of the pesticides by the woods (with the exception of paraquat) showing that this parameter is very important in this adsorption process. The determination coefficient of the multiple correlation between Kf and the parameters Kow, soluble C, and lignin contents accounts for nearly 100% of the variability in adsorption for non-ionic pesticides. Based on the results of our study and of those of the literature related to the adsorption of aromatic hydrocarbons, we used the Kow values to define a predictive model of adsorption of hydrophobic organic compounds in general by the woods.

  13. Selection and Validation of Charge and Lennard-Jones Parameters for QM/MM Simulations of Hydrocarbon Interactions with Zeolites.

    PubMed

    Zimmerman, Paul M; Head-Gordon, Martin; Bell, Alexis T

    2011-06-14

    Quantum mechanics/molecular mechanics (QM/MM) models are an appealing method for performing zeolite simulations. In QM/MM, a small cluster chosen to encompass the active center is described by QM, while the rest of the zeolite is described by MM. In the present study, we demonstrate that the charges and Lennard-Jones parameters on Si and O must be chosen properly for QM/MM calculations of adsorption energies and activation energies to agree closely with full QM calculations. The selection of parameters for Si and O is based on using the ωB97X-D functional for DFT calculations of the QM region, which is effective in capturing the effects of van der Waals interactions. A comparison of the heats of adsorption for a variety of adsorbates and activation energies for the cracking of propane and butane reveals that energies derived from QM/MM calculation carried out with appropriately selected MM parameters agree to within an rms error of ∼1.5 kcal/mol with QM calculations. To avoid reparametrization for new substrates, Lennard-Jones zeolite parameters are chosen to be compatible with existing CHARMM parameters. Transferability of these parameters is demonstrated by tests utilizing the B3LYP density functional and simulations of MFI and FAU zeolites. Moreover, the computational time for QM/MM calculations is considerably lower than that for QM calculations, and the ratio of computational times decreases rapidly with increasing size of the cluster used to represent the zeolite.

  14. Molecular basis for the high CO2 adsorption capacity of chabazite zeolites.

    PubMed

    Pham, Trong D; Hudson, Matthew R; Brown, Craig M; Lobo, Raul F

    2014-11-01

    CO2 adsorption in Li-, Na-, K-CHA (Si/Al=6,=12), and silica chabazite zeolites was investigated by powder diffraction. Two CO2 adsorption sites were found in all chabazites with CO2 locating in the 8-membered ring (8MR) pore opening being the dominant site. Electric quadrupole-electric field gradient and dispersion interactions drive CO2 adsorption at the middle of the 8 MRs, while CO2 polarization due to interaction with cation sites controls the secondary CO2 site. In Si-CHA, adsorption is dominated by dispersion interactions with CO2 observed on the pore walls and in 8 MRs. CO2 adsorption complexes on dual cation sites were observed on K-CHA, important for K-CHA-6 samples due to a higher probability of two K(+) cations bridging CO2. Trends in isosteric heats of CO2 adsorption based on cation type and concentration can be correlated with adsorption sites and CO2 quantity. A decrease in the hardness of metal cations results in a decrease in the direct interaction of these cations with CO2.

  15. Quantitative evaluation of the effect of moisture contents of coconut shell activated carbon used for respirators on adsorption capacity for organic vapors.

    PubMed

    Abiko, Hironobu; Furuse, Mitsuya; Takano, Tsuguo

    2010-01-01

    Activated carbon is an elemental material used for hygienic applications, particularly as an adsorbent for harmful gases and vapors. In Japanese industrial and occupational hygiene, activated carbon produced from coconut shell is a traditional and popular adsorbent material due to its excellent adsorption ability and cost advantage. In this research, in order to clarify the effect of the preliminary content of moisture on the adsorption capacity in detail, we prepared several coconut shell activated carbons which were preconditioned by equilibration with moisture at different relative humidities. We measured their adsorption capacities as breakthrough times for 6 kinds of organic vapor, and attempted to determine the relationships between the relative weight increase of water adsorption and the decrease of adsorption capacities of the activated carbon specimens for the organic vapors. The procedure of the quantitative evaluation of the effect of moisture and the results are useful for practical applications of activated carbon, particularly those used as adsorbents in workplaces.

  16. High gas storage capacities and stepwise adsorption in a UiO type metal-organic framework incorporating Lewis basic bipyridyl sites.

    PubMed

    Li, Liangjun; Tang, Sifu; Wang, Chao; Lv, Xiaoxia; Jiang, Min; Wu, Huaizhi; Zhao, Xuebo

    2014-03-04

    A UiO type MOF with Lewis basic bipyridyl sites was synthesized and structurally characterized. After being activated by Soxhlet-extraction, this MOF exhibits high storage capacities for H2, CH4 and CO2, and shows unusual stepwise adsorption for liquid CO2 and solvents, indicating a sequential filling mechanism on different adsorption sites.

  17. Simultaneous activation/sulfurization method for production of sulfurized activated carbons: characterization and Hg(II) adsorption capacity.

    PubMed

    Shamsijazeyi, Hadi; Kaghazchi, Tahereh

    2014-01-01

    As an inexpensive method for modification of activated carbons (ACs), sulfurization has attracted significant attention. However, the resulting sulfurized activated carbons (SACs) often are less porous than the original ACs. In this work, we propose a new method for concurrent sulfurization/activation that can lead to preparation of SACs with more porosity than the corresponding non-sulfurized ACs. By using scanning electron microscopy, nitrogen adsorption/desorption, and iodine number experiments, the porous structure of the SACs has been compared with that of non-sulfurized ACs. The specific surface areas of SACs are higher than the corresponding ACs, regardless of the type of activation agents used. For instance, the specific surface area of SAC and AC activated with phosphoric acid is 1,637 and 1,338 m(2)/g, respectively. Additionally, sulfur contents and surface charges (pHpzc) of the SACs and non-sulfurized ACs are compared. In fact, the SACs have higher sulfur contents and more acidic surfaces. Furthermore, the Hg(II) adsorption capacity of SACs has been compared with the corresponding non-sulfurized ACs. The Hg(II) adsorption isotherms on a selected SAC is measured at different pH values and temperatures. Hg(II) adsorptions as high as 293 mg/g are observed by using SACs prepared by the method proposed in this study.

  18. QM/MM methods in inorganic chemistry.

    PubMed

    Bo, Carles; Maseras, Feliu

    2008-06-14

    Quantum mechanics/molecular mechanics (QM/MM) methods are a useful tool for the computational study of inorganic systems. They allow a quantitative description of systems larger than those treatable with pure QM methods, in principle with a comparable quality. QM/MM calculations are being currently applied to the research in a variety of topics, including structural effects of ligand bulk, selectivity in homogeneous catalysis and mechanical embedding in heterogeneous catalysis. The QM/MM approach is also useful for the separation of steric and electronic contributions, and as an auxiliary tool for geometry optimization when full QM methods are mandatory. The power of QM/MM methods in inorganic chemistry is illustrated in this Perspective with a summary of recent representative applications.

  19. 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

  20. 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.

  1. Effect of the concentration of inherent mineral elements on the adsorption capacity of coconut shell-based activated carbons.

    PubMed

    Afrane, G; Achaw, Osei-Wusu

    2008-09-01

    Coconut shells of West Africa Tall, a local variety of the coconut species Cocos nucifera L., were taken from five different geographical locations in Ghana and examined for the presence and concentration levels of some selected mineral elements using atomic absorption spectrometer. Activated carbons were subsequently made from the shells by the physical method. The iodine adsorption characteristics of the activated carbons measured showed a definite relationship to the concentration levels of potassium and other mineral elements in the precursor shell. Samples with lower total minerals content recorded higher iodine numbers. It was observed that the origin of the shells was related to the concentration levels of the analyzed mineral elements in the shells, which in turn affected the adsorption capacity of the activated carbons. The results of this study have important implications for the sourcing of coconuts whose shells are used in the manufacture of activated carbons.

  2. Effect of heat on the adsorption capacity of an activated carbon for decolorizing/deodorizing yellow zein.

    PubMed

    Sessa, D J; Palmquist, D E

    2008-09-01

    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. Yellow color is due to xanthophylls; a contributor to off-odor is diferuloylputrescine. The off-odor component absorbs ultraviolet (UV) light at about 325 nm and its removal coincides with removal of yellow color. A spectrophotometric method based on UV absorbances 280 nm for protein and 325 nm for the off-odor component was used to monitor their adsorptions onto activated carbon. Equilibrium studies were performed over temperature range from 25 to 60 degrees C for zein dissolved in 70% aqueous ethanol. Runs made at 55 degrees C adsorbed significantly more of the color/odor components than the protein.

  3. 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.

  4. Summary of QM02 Measurements

    SciTech Connect

    Fisher, Andrew

    2010-12-03

    This note summarizes both the beam-based and various laboratory measurements of quadrupole magnets, units 387 and 428, used for QM02 in the LCLS Injector. These were undertaken because of a consistent discrepancy between accelerator model predictions and beam observations which seemed to indicate a weak QM02. A report 'QM02 Strength Measurement', by Welch and Wu, describes the discrepancy and beam-based measurements on unit 387. Subsequently, unit 387 was replaced by unit 428, refinements were made to analysis of the beam-based measurements were made, and additional magnetic measurements were made on unit 387 in the lab. These new results are summarized in this note. The principle results are: (1) Laboratory measurements of integrated gradient for the same magnet, or for different magnets of the same type, are all within 1% of each other at gradients of interest. These cases cover three independent types of measurements, disassembly/reassembly of the units, and extended periods of time between measurements. (2) Standardization, or lack thereof, can cause integrated gradient errors of approximately 0.2 kG, which can amount to a few percent of the strength of the magnet depending on the setting. (3) Model-independent beam-based measurements indicate the magnets are actually weaker than expected by about 2 percent, but these measurements are subject to the uncertainty of the BPMS1 location. (4) The standardization cycle is effective. (5) The stainless steel BPM vacuum chamber inside the magnets has no significant effect on the beam. The discrepancy between the accelerator model predictions and the actual orbit response is not resolved, but the evidence points away from magnetic strength errors as the source. Differences between the model locations and effective locations of BPM's is a possible culprit. This idea is explored in Section 2. Table 1 summarizes the measurement activities that were performed on the units. The dates listed correspond to the date when the

  5. 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

  6. Properties of poly(1-naphthylamine)/Fe3O4 composites and arsenic adsorption capacity in wastewater

    NASA Astrophysics Data System (ADS)

    Tran, Minh Thi; Nguyen, Thi Huyen Trang; Vu, Quoc Trung; Nguyen, Minh Vuong

    2016-03-01

    The research results of poly(1-naphthylamine)/Fe3O4 (PNA/Fe3O4) nanocomposites synthesized by a chemical method for As(III) wastewater treatment are presented in this paper. XRD patterns and TEM images showed that the Fe3O4 grain size varied from 13 to 20 nm. The results of Raman spectral analysis showed that PNA participated in part of the PNA/Fe3O4 composite samples. The grain size of PNA/Fe3O4 composite samples is about 25-30 nm measured by SEM. The results of vibrating sample magnetometer measurements at room temperature showed that the saturation magnetic moment of PNA/Fe3O4 samples decreased from 63.13 to 43.43 emu/g, while the PNA concentration increased from 5% to 15%. The nitrogen adsorption-desorption isotherm of samples at 77 K at a relative pressure P/ P 0 of about 1 was studied in order to investigate the surface and porous structure of nanoparticles by the BET method. Although the saturation magnetic moments of samples decreased with the polymer concentration increase, the arsenic adsorption capacity of the PNA/Fe3O4 sample with the PNA concentration of 5% is better than that of Fe3O4 in a solution with pH = 7. In the solution with pH > 14, the arsenic adsorption of magnetic nanoparticles is insignificant.

  7. Hyperbranched-polyol-tethered poly (amic acid) electrospun nanofiber membrane with ultrahigh adsorption capacity for boron removal

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Wu, Zhongyu; Zhang, Yufeng; Meng, Jianqiang

    2017-04-01

    The development of efficient adsorbents with high sorption capacity remains as a challenge for the removal of micropollutants occurred globally in water resources. In this work, poly (amic acid) (PAA) electrospun nanofiber membranes grafted with hyperbranched polyols were synthesized and used for boron removal. The PAA nanofiber was reacted with hyperbranched polyethylenimine (HPEI) and further with glycidol to introduce the vicinal hydroxyl groups. The chemical composition and surface characteristics of the obtained PAA-g-PG membranes were evaluated by FESEM, FTIR, XPS and water contact angles (WCA) measurements. The boron adsorption thermodynamics and kinetics were investigated systematically. The results showed that the PAA nanofiber spun from concentration of 15% had uniform morphology and narrow diameter distribution. The PAA-g-PG nanofiber membrane had a maximum boron uptake of 5.68 mmol/g and could adsorb 0.82 mmol/g boron from a 5 mg/L solution in 15 min. Both the high surface area of nanofibers and the hyperbranched structure should contribute to the high boron uptake and high adsorption rate. The nanofiber membrane obeyed the Langmuir adsorption model and the pseudo-first-order kinetic model. The regeneration efficiency of the nanofiber membrane remained 93.9% after 10 cycled uses, indicating good regenerability of the membrane.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Superfine powdered activated carbon incorporated into electrospun polystyrene fibers preserve adsorption capacity.

    PubMed

    Apul, Onur G; Hoogesteijn von Reitzenstein, Natalia; Schoepf, Jared; Ladner, David; Hristovski, Kiril D; Westerhoff, Paul

    2017-03-17

    A composite material consisted of superfine powdered activated carbon (SPAC) and fibrous polystyrene (PS) was fabricated for the first time by electrospinning. SPAC is produced by pulverizing powdered activated carbon. The diameter of SPAC (100-400nm) is more than one hundred times smaller than conventional powdered activated carbon, but it maintains the internal pore structure based on organic micropollutant adsorption isotherms and specific surface area measurements. Co-spinning SPAC into PS fibers increased specific surface area from 6m(2)/g to 43m(2)/g. Unlike metal oxide nanoparticles, which are non-accessible for sorption from solution, electrospinning with SPAC created porous fibers. Composite SPAC-PS electrospun fibers, containing only 10% SPAC, had 30% greater phenanthrene sorption compared against PS fibers alone. SPAC particles embedded within the polymer were either partially or fully incorporated, and the accessibility of terminal adsorption sites were conserved. Conserving the adsorptive functionality of SPAC particles in electrospun non-woven polymeric fiber scaffolding can enable their application in environmental applications such as drinking water treatment.

  17. Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures.

    PubMed

    Zhao, Yonggang; Wu, Haohan; Emge, Thomas J; Gong, Qihan; Nijem, Nour; Chabal, Yves J; Kong, Lingzhu; Langreth, David C; Liu, Hui; Zeng, Heping; Li, Jing

    2011-04-26

    Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials.

  18. One-step synthesis of a novel N-doped microporous biochar derived from crop straws with high dye adsorption capacity.

    PubMed

    Lian, Fei; Cui, Guannan; Liu, Zhongqi; Duo, Lian; Zhang, Guilong; Xing, Baoshan

    2016-07-01

    N-doping is one of the most promising strategies to improve the adsorption capacity and selectivity of carbon adsorbents. Herein, synthesis, characterization and dye adsorption of a novel N-doped microporous biochar derived from direct annealing of crop straws under NH3 is presented. The resultant products exhibit high microporosity (71.5%), atomic percentage of nitrogen (8.81%), and adsorption capacity to dyes, which is about 15-20 times higher than that of original biochar. Specifically, for the sample NBC800-3 pyrolyzed at 800°C in NH3 for 3 h, its adsorption for acid orange 7 (AO7, anionic) and methyl blue (MB, cationic) is up to 292 mg g(-1) and 436 mg g(-1), respectively, which is among the highest ever reported for carbonaceous adsorbents. The influences of N-doping and porous structure on dye adsorption of the synthesized carbons are also discussed, where electrostatic attraction, π-π electron donor-accepter interaction, and Lewis acid-base interaction mainly contribute to AO7 adsorption, and surface area (especially pore-filling) dominates MB adsorption. The N-doped biochar can be effectively regenerated and reused through direct combustion and desorption approaches.

  19. Adsorptive removal of methylene blue by agar: effects of NaCl and ethanol

    PubMed Central

    2012-01-01

    Adsorption of methylene blue (MB) on agar was investigated as a function of temperature (308-328 K), different concentrations of NaCl and HCl and various weight percentages of binary mixtures of ethanol with water. It was observed that the maximum experimental adsorption capacity, qm, exp, in water is up to 50 mg g-1 and decreases with increase in weight percentage of ethanol and NaCl and HCl concentration compared to that of water. Analysis of data using ARIAN model showed that MB adsorbs as monomer and dimer on the surface of agar. Binding constants of MB to agar were calculated using the Temkin isotherm. The process is exothermic in water and other solutions. The mean adsorption energy (E) value indicated binding of MB to agar is chemical adsorption. Kinetics of this interaction obeys from the pseudo-second-order model and diffusion of the MB molecules into the agar is the main rate-controlling step. PMID:22339759

  20. Facile synthesis of hydroxy-modified MOF-5 for improving the adsorption capacity of hydrogen by lithium doping.

    PubMed

    Kubo, Masaru; Hagi, Hayato; Shimojima, Atsushi; Okubo, Tatsuya

    2013-11-01

    A facile synthesis of partially hydroxy-modified MOF-5 and its improved H2-adsorption capacity by lithium doping are reported. The reaction of Zn(NO3)2·6H2O with a mixture of terephthalic acid (H2BDC) and 2-hydroxyterephthalic acid (H2BDC-OH) in DMF gave hydroxy-modified MOF-5 (MOF-5-OH-x), in which the molar fraction (x) of BDC-OH(2-) was up to 0.54 of the whole ligand. The MOF-5-OH-x frameworks had high BET surface areas (about 3300 m(2) g(-1)), which were comparable to that of MOF-5. We suggest that the MOF-5-OH-x frameworks are formed by the secondary growth of BDC(2-)-rich MOF-5 seed crystals, which are nucleated during the early stage of the reaction. Subsequent Li doping into MOF-5-OH-x results in increased H2 uptake at 77 K and 0.1 MPa from 1.23 to 1.39 wt.% and an increased isosteric heat of H2 adsorption from 5.1-4.2 kJ mol(-1) to 5.5-4.4 kJ mol(-1).

  1. 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.

  2. Dendritic silica nanomaterials (KCC-1) with fibrous pore structure possess high DNA adsorption capacity and effectively deliver genes in vitro.

    PubMed

    Huang, Xiaoxi; Tao, Zhimin; Praskavich, John C; Goswami, Anandarup; Al-Sharab, Jafar F; Minko, Tamara; Polshettiwar, Vivek; Asefa, Tewodros

    2014-09-16

    The pore size and pore structure of nanoporous materials can affect the materials' physical properties, as well as potential applications in different areas, including catalysis, drug delivery, and biomolecular therapeutics. KCC-1, one of the newest members of silica nanomaterials, possesses fibrous, large pore, dendritic pore networks with wide pore entrances, large pore size distribution, spacious pore volume and large surface area--structural features that are conducive for adsorption and release of large guest molecules and biomacromolecules (e.g., proteins and DNAs). Here, we report the results of our comparative studies of adsorption of salmon DNA in a series of KCC-1-based nanomaterials that are functionalized with different organoamine groups on different parts of their surfaces (channel walls, external surfaces or both). For comparison the results of our studies of adsorption of salmon DNA in similarly functionalized, MCM-41 mesoporous silica nanomaterials with cylindrical pores, some of the most studied silica nanomaterials for drug/gene delivery, are also included. Our results indicate that, despite their relatively lower specific surface area, the KCC-1-based nanomaterials show high adsorption capacity for DNA than the corresponding MCM-41-based nanomaterials, most likely because of KCC-1's large pores, wide pore mouths, fibrous pore network, and thereby more accessible and amenable structure for DNA molecules to diffuse through. Conversely, the MCM-41-based nanomaterials adsorb much less DNA, presumably because their outer surfaces/cylindrical channel pore entrances can get blocked by the DNA molecules, making the inner parts of the materials inaccessible. Moreover, experiments involving fluorescent dye-tagged DNAs suggest that the amine-grafted KCC-1 materials are better suited for delivering the DNAs adsorbed on their surfaces into cellular environments than their MCM-41 counterparts. Finally, cellular toxicity tests show that the KCC-1-based

  3. [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.

  4. 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

  5. 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.

  6. 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

    2016-06-05

    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.

  7. 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

  8. Determination of Adsorption Capacity and Kinetics of Amidoxime-Based Uranium Adsorbent Braided Material in Unfiltered Seawater Using a Flume Exposure System

    SciTech Connect

    Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.; Park, Jiyeon; Bonheyo, George T.; Jeters, Robert T.; Schlafer, Nicholas J.; Wood, Jordana R.

    2015-08-31

    PNNL has developed a recirculating flume system for exposing braided adsorbent material to natural seawater under realistic temperature and flow-rate exposure conditions. The flumes are constructed of transparent acrylic material they allow external light to pass into the flumes and permit photosynthetic growth of naturally present marine organisms (biofouling). Because the system consists of two flumes, replicate experiments can be conducted in which one of the flumes can be manipulated relative to the other. For example, one flume can be darkened to eliminate light exposure by placing a black tarp over the flume such that dark/light experiments can be conducted. Alternatively, two different braided adsorbents can be exposed simultaneously with no potential cross contamination issues. This report describes the first use of the PNNL flume system to study the impact of biofouling on adsorbent capacity. Experiments were conducted with the ORNL AI8 braided adsorbent material in light exposed and darkened flumes for a 42 day exposure experiment. The major objective of this effort is to develop a system for the exposure of braided adsorbent material to unfiltered seawater and to demonstrate the system by evaluating the performance of adsorption material when it is exposed to natural marine biofouling as it would be when the technology is used in the marine environment. Exposures of amidoxime-based polymeric braid adsorbents prepared by Oak Ridge Natural Laboratory (ORNL) were exposed to ambient seawater at 20°C in a flume system. Adsorption kinetics and adsorption capacity were assessed using time series determinations of uranium adsorption and one-site ligand saturation modeling. Biofouling in sunlight surface seawater has the potential to significantly add substantial biogenic mass to adsorption material when it is exposed for periods greater than 21 days. The observed biomass increase in the light flume was approximately 80 % of the adsorbent mass after 42 days. The

  9. Superb adsorption capacity of hierarchical calcined Ni/Mg/Al layered double hydroxides for Congo red and Cr(VI) ions.

    PubMed

    Lei, Chunsheng; Zhu, Xiaofeng; Zhu, Bicheng; Jiang, Chuanjia; Le, Yao; Yu, Jiaguo

    2017-01-05

    The preparation of hierarchical porous materials as catalysts and sorbents has attracted much attention in the field of environmental pollution control. Herein, Ni/Mg/Al layered double hydroxides (NMA-LDHs) hierarchical flower-like hollow microspheres were synthesized by a hydrothermal method. After the NMA-LDHs was calcined at 600°C, NMA-LDHs transformed into Ni/Mg/Al layered double oxides (NMA-LDOs), which maintained the hierarchical flower-like hollow structure. The crystal phase, morphology, and microstructure of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy elemental mapping, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption methods. Both the calcined and non-calcined NMA-LDHs were examined for their performance to remove Congo red (CR) and hexavalent chromium (Cr(VI)) ions in aqueous solution. The maximum monolayer adsorption capacities of CR and Cr(VI) ions over the NMA-LDOs sample were 1250 and 103.4mg/g at 30°C, respectively. Thermodynamic studies indicated that the adsorption process was endothermic in nature. In addition, the addition of coexisting anions negatively influenced the adsorption capacity of Cr(VI) ions, in the following order: CO3(2-)>SO4(2-)>H2PO4(-)>Cl(-). This work will provide new insight into the design and fabrication of advanced adsorption materials for water pollutant removal.

  10. Affinity adsorption of lysozyme on a macroligand prepared with Cibacron Blue 3GA attached to yeast cells.

    PubMed

    del Pilar Ferraris, María; Barrera, Guillermo I; Padilla, A Pérez; Rodríguez, Jorge A

    2011-09-15

    The objective of this study was the development of affinity adsorbent particles with the appropriate characteristics to be applied in protein purification using the affinity ultrafiltration method. To prepare affinity macroligands Cibacron Blue 3GA, as a ligand molecule, was immobilized by covalent bonding onto yeast cell walls, the support material or matrix. The maximum attachment of the ligand to the matrix was 212 μmol/g (ligand dry weight/yeast dry weight). Lysozyme was selected as the protein model for the adsorption studies. Its adsorption onto the matrix without ligand and matrix with attached ligand were investigated batch-wise. The adsorption equilibrium isotherms appeared to follow a typical Langmuir isotherm. The maximum adsorption capacity (q(m)) of the Cell-Cibacron macroligand for lysozyme was 110 mg/ml of wet macroligand. The adsorbent was also employed for the separation of lysozyme from hen egg white. High purity lysozyme was obtained.

  11. A study of the alumina-silica gel adsorbent for the removal of silicic acid from geothermal water: increase in adsorption capacity of the adsorbent due to formation of amorphous aluminosilicate by adsorption of silicic acid.

    PubMed

    Yokoyama, Takushi; Ueda, Akira; Kato, Koichi; Mogi, Katsumi; Matsuo, Shorin

    2002-08-01

    Two kinds of adsorbents (Si adsorbent and Al adsorbent) for the removal of silicic acid from geothermal water to retard the formation of silica scales were prepared using silicic acid contained in geothermal water. The Si adsorbent was prepared by evaporating geothermal water, and the Al adsorbent was prepared by evaporating geothermal water after the addition of aluminum chloride. The specific surface area of the Si adsorbent was small and it's adsorption capacity of silicic acid was low. Although the specific surface area of the Al adsorbent was also small, it was significantly increased by the adsorption of silicic acid and it's adsorption capacity was high. Based on the change in the local structure of aluminum ion by the adsorption of silicic acid, the Al adsorbent was considered to be silica particles covered with crystalline aluminum hydroxide. Moreover, it was concluded that the increase in the specific surface area of the Al adsorbent and the decrease in the zeta potential were due to the formation of an amorphous aluminosilicate with a large surface area and a negative charge (one 4-coordinated Al) by the reaction between aluminum ions and silicic acids.

  12. Q(M) and the depolarization index scalar metrics.

    PubMed

    Espinosa-Luna, Rafael; Bernabeu, Eusebio; Atondo-Rubio, Gelacio

    2008-04-01

    A depolarization scalar metric for Mueller matrices, named Q(M), is derived from the degree of polarization. Q(M) has been recently reported, and it has been deduced from the nine bilinear constraints between the sixteen elements of the Mueller-Jones matrix. We discuss the relations between Q(M) and the depolarization index.

  13. Fourier transform infra-red (FTIR) spectroscopy investigation, dose effect, kinetics and adsorption capacity of phosphate from aqueous solution onto laterite and sandstone.

    PubMed

    Coulibaly, Lassina Sandotin; Akpo, Sylvain Kouakou; Yvon, Jacques; Coulibaly, Lacina

    2016-12-01

    Environmental pollution by phosphate in developing countries is growing with extensive and diffuse pollution. Solving these problem with intensive technologies is very expensive. Using natural sorbent such as laterite and sandstone could be a solution. The main objective of the study is to evaluate the P-removal efficiency of these materials under various solution properties. Laterite and sandstone used mainly contain very high levels of finely grained iron and aluminum oxy-hydroxides and diverse dioctahedral clays. Phosphate adsorption tests were carried out using crushed laterite and sandstone. Optimal doses and pH effects on phosphate adsorption were studied with a potassium hydrogeno-phosphate solution of 5 mg/L at 30 °C. The main results were that the optimal dosage is 15 and 20 mg/L respectively for laterite and sandstone. The phosphate adsorptions efficiency of laterite and sandstone are pH-dependent, they increase when the pH grows up to the Point of Zero Charge (PZC) and slowly decrease beyond. The adsorption capacities of the materials also increase proportionally with the initial phosphate concentration. The pseudo-second-order successfully described the kinetics of the phosphate adsorption on the two adsorbents. With this model, the adsorption capacity values are obtained, which give an idea of the maximum phosphate uptake that the laterite and sandstone could achieve. The changes on the FTIR spectra of raw materials and phosphate adsorbed material confirm the mechanism of chemisorptions. Considering the above, laterite and sandstone could be used as efficient and cheap adsorbent for the removal of phosphate in aqueous solution.

  14. 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.

  15. Collagen/cellulose hydrogel beads reconstituted from ionic liquid solution for Cu(II) adsorption.

    PubMed

    Wang, Jilei; Wei, Ligang; Ma, Yingchong; Li, Kunlan; Li, Minghui; Yu, Yachen; Wang, Lei; Qiu, Huihui

    2013-10-15

    A novel adsorbent, biodegradable collagen/cellulose hydrogel beads (CCHBs), was prepared by reconstitution from a 1-butyl, 3-methylimidazolium chloride ([C4mim]Cl) solution. The adsorption properties of the CCHBs for Cu(II) ion removal from aqueous solutions were investigated and compared with those of cellulose hydrogel beads (CHBs). The CCHBs have a three-dimensional macroporous structure whose amino groups are believed to be the main active binding sites of Cu(II) ions. The equilibrium adsorption capacity (qe) of the CCHBs is greatly influenced by the collagen/cellulose mass ratio, and steeply increases until the collagen/cellulose mass ratio exceeds 2/1. The maximum adsorption is obtained at pH 6. The qe of Cu(II) ions increases with increased initial concentration of the solution. Based on Langmuir isotherms, the maximum adsorption capacity (qm) of CCHB3 (collagen/cellulose mass ratio of 3/1) is 1.06 mmol/g. The CCHBs maintain good adsorption properties after the fourth cycle of adsorption-desorption.

  16. Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

    PubMed

    Cataldo, Salvatore; Gianguzza, Antonio; Milea, Demetrio; Muratore, Nicola; Pettignano, Alberto

    2016-11-01

    The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL(-1). Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (qm) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., qm=15.7 and 10.5mgg(-1) at I=0.25molL(-1), for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion.

  17. Adsorption of methylene blue on an agro-waste oiltea shell with and without fungal treatment

    NASA Astrophysics Data System (ADS)

    Liu, Jiayang; Li, Enzhong; You, Xiaojuan; Hu, Changwei; Huang, Qingguo

    2016-12-01

    A lignocellulosic waste oiltea shell (OTS) was evaluated as an inexpensive sorbent to remove methylene blue (MB) from aqueous solution. Fungal treatment of OTS increased the MB adsorption by modifying the physicochemical properties of OTS and simultaneously produced laccase as a beneficial co-product. Without fungal treatment, the maximum amount of adsorption (qm) of MB by OTS was 64.4 mg/g, whereas the treatment with fungus Pycnoporus sp. and Trametes versicolor increased qm up to 72.5 mg/g and 85.7 mg/g, respectively. This is because of the improved surface area and pore sizes as well as altered chemical compositions. The equilibrium sorption data for OTS both with and without treatment fitted to the Langmuir model, and the sorption rate data well fitted to the pseudo second-order kinetic model. The changes in free energy (ΔG°) and separation factor (RL) indicated that the sorption was spontaneous and favorable. Scanning electron microscopy and Fourier transform infrared spectroscopy showed the changes in the surface morphology and functional groups of OTS after fungal treatment. The agro-waste OTS could be utilized as a low-cost adsorbent for efficient dye removal, and fungal treatment can serve as a mild and clean technique to increase the adsorptive capacity of OTS.

  18. Adsorption of methylene blue on an agro-waste oiltea shell with and without fungal treatment

    PubMed Central

    Liu, Jiayang; Li, Enzhong; You, Xiaojuan; Hu, Changwei; Huang, Qingguo

    2016-01-01

    A lignocellulosic waste oiltea shell (OTS) was evaluated as an inexpensive sorbent to remove methylene blue (MB) from aqueous solution. Fungal treatment of OTS increased the MB adsorption by modifying the physicochemical properties of OTS and simultaneously produced laccase as a beneficial co-product. Without fungal treatment, the maximum amount of adsorption (qm) of MB by OTS was 64.4 mg/g, whereas the treatment with fungus Pycnoporus sp. and Trametes versicolor increased qm up to 72.5 mg/g and 85.7 mg/g, respectively. This is because of the improved surface area and pore sizes as well as altered chemical compositions. The equilibrium sorption data for OTS both with and without treatment fitted to the Langmuir model, and the sorption rate data well fitted to the pseudo second-order kinetic model. The changes in free energy (ΔG°) and separation factor (RL) indicated that the sorption was spontaneous and favorable. Scanning electron microscopy and Fourier transform infrared spectroscopy showed the changes in the surface morphology and functional groups of OTS after fungal treatment. The agro-waste OTS could be utilized as a low-cost adsorbent for efficient dye removal, and fungal treatment can serve as a mild and clean technique to increase the adsorptive capacity of OTS. PMID:27917929

  19. Preparation and characterization of a hierarchical porous char from sewage sludge with superior adsorption capacity for toluene by a new two-step pore-fabricating process.

    PubMed

    Kong, Lingjun; Xiong, Ya; Tian, Shuanghong; Luo, Rongshu; He, Chun; Huang, Haibao

    2013-10-01

    A kind of hierarchical porous char (SCCA/Zn) was prepared from sewage sludge by a new two-step pore-fabricating process coupling citric acid (CA) with ZnCl2 in a pyrolysis process. The char was characterized by element analysis, N2-adsorption and mercury intrusion measurement etc. It is found that coupling CA and ZnCl2 can synergistically fabricate pores in the pyrolysis process, resulting in a hierarchical porous char, SCCA/Zn, with the largest SBET of 867.6 m(2) g(-1) due to the fact that the former contributes to the fabrication of macro-pores, which provides more space for fabricating meso- and micro-pores by ZnCl2 activation. Although the SBET of SCCA/Zn was 15% less than that of activated carbon fiber (ACF, SBET=999.5 m(2) g(-1)), SCCA/Zn had a higher toluene adsorption capacity (0.83 g g(-1)) than ACF. The inconsistence between their SBET and adsorption capacity can be ascribed to the strong hydrophobic property of SCCA/Zn.

  20. Discriminating Between qm and SED with Spin

    NASA Astrophysics Data System (ADS)

    Cavalleri, G.; Tonni, E.

    The complete prediction of diffraction for electrons passing through two slits is obtained by stochastic electrodynamics (SED) implemented by spin. The positions of the maxima and minima of the diffraction pattern turn out to be equal to those given by quantum mechanics (QM). However, when the transversal width Δy of the electron beam is much smaller than the size b of a slit, no diffraction should be present according to QM while a part of the diffraction pattern dependent on the position of the beam should appear according to SED plus spin. A relevant experiment is proposed to discriminate between the two theories. A second proposed experiment regards the form of the diffraction pattern. The intensities of the minima should be almost zero if the wall containing the slit is made of metal but appreciably different from zero if the wall is made of a dielectric. For a dielectric constant ≃ 2 the even maxima should be less than the minima.

  1. 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.

  2. 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.

  3. Comparative adsorption of Cu(II), Zn(II), and Pb(II) ions in aqueous solution on the crosslinked chitosan with epichlorohydrin.

    PubMed

    Chen, Arh-Hwang; Liu, Sheng-Chang; Chen, Chia-Yuan; Chen, Chia-Yun

    2008-06-15

    The crosslinked chitosans synthesized by the homogeneous reaction of chitosan in aqueous acetic acid solution with epichlorohydrin were used to investigate the adsorptions of three metals of Cu(II), Zn(II), and Pb(II) ions in an aqueous solution. The crosslinked chitosan characterized by 13CNMR, SEM, and elemental analysis, and the effects of pH and anion on the adsorption capacity were carried out. The dynamical study demonstrated that the adsorption process was followed the second-order kinetic equation. The results obtained from the equilibrium isotherms adsorption studies of three metals of Cu(II), Zn(II), and Pb(II) ions by being analyzed in three adsorption models, namely, Langmuir, Freundlich, and Dubinnin-Radushkevich isotherm equations, indicated to be well fitted to the Langmuir isotherm equation under the concentration range studied, by comparing the linear correlation coefficients. The order of the adsorption capacity (Qm) for three metal ions was as follows: Cu2+>Pb2+>Zn2+. This technique for syntheses of the crosslinked chitosans with epichlorohydrin via the homogeneous reaction in aqueous acetic acid solution showed that the adsorptions of three metal ions in aqueous solution were followed the monolayer coverage of the adsorbents through physical adsorption phenomena.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. Image compression with QM-AYA adaptive binary arithmetic coder

    NASA Astrophysics Data System (ADS)

    Cheng, Joe-Ming; Langdon, Glen G., Jr.

    1993-01-01

    The Q-coder has been reported in the literature, and is a renorm-driven binary adaptive arithmetic coder. A similar renorm-driven coder, the QM coder, uses the same approach with an initial attack to more rapidly estimate the statistics in the beginning, and with a different state table. The QM coder is the adaptive binary arithmetic coder employed in the JBIG and JPEG image compression algorithms. The QM-AYA arithmetic coder is similar to the QM coder, with a different state table, that offers balanced improvements to the QM probability estimation for the less skewed distributions. The QM-AYA performs better when the probability estimate is near 0.5 for each binary symbol. An approach for constructing effective index change tables for Q-coder type adaptation is discussed.

  10. 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.

  11. 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

  12. How Large Should the QM Region Be in QM/MM Calculations? The Case of Catechol O-Methyltransferase.

    PubMed

    Kulik, Heather J; Zhang, Jianyu; Klinman, Judith P; Martínez, Todd J

    2016-11-10

    Hybrid quantum mechanical-molecular mechanical (QM/MM) simulations are widely used in studies of enzymatic catalysis. Until recently, it has been cost prohibitive to determine the asymptotic limit of key energetic and structural properties with respect to increasingly large QM regions. Leveraging recent advances in electronic structure efficiency and accuracy, we investigate catalytic properties in catechol O-methyltransferase, a prototypical methyltransferase critical to human health. Using QM regions ranging in size from reactants-only (64 atoms) to nearly one-third of the entire protein (940 atoms), we show that properties such as the activation energy approach within chemical accuracy of the large-QM asymptotic limits rather slowly, requiring approximately 500-600 atoms if the QM residues are chosen simply by distance from the substrate. This slow approach to asymptotic limit is due to charge transfer from protein residues to the reacting substrates. Our large QM/MM calculations enable identification of charge separation for fragments in the transition state as a key component of enzymatic methyl transfer rate enhancement. We introduce charge shift analysis that reveals the minimum number of protein residues (approximately 11-16 residues or 200-300 atoms for COMT) needed for quantitative agreement with large-QM simulations. The identified residues are not those that would be typically selected using criteria such as chemical intuition or proximity. These results provide a recipe for a more careful determination of QM region sizes in future QM/MM studies of enzymes.

  13. How Large Should the QM Region Be in QM/MM Calculations? The Case of Catechol O-Methyltransferase

    PubMed Central

    2016-01-01

    Hybrid quantum mechanical–molecular mechanical (QM/MM) simulations are widely used in studies of enzymatic catalysis. Until recently, it has been cost prohibitive to determine the asymptotic limit of key energetic and structural properties with respect to increasingly large QM regions. Leveraging recent advances in electronic structure efficiency and accuracy, we investigate catalytic properties in catechol O-methyltransferase, a prototypical methyltransferase critical to human health. Using QM regions ranging in size from reactants-only (64 atoms) to nearly one-third of the entire protein (940 atoms), we show that properties such as the activation energy approach within chemical accuracy of the large-QM asymptotic limits rather slowly, requiring approximately 500–600 atoms if the QM residues are chosen simply by distance from the substrate. This slow approach to asymptotic limit is due to charge transfer from protein residues to the reacting substrates. Our large QM/MM calculations enable identification of charge separation for fragments in the transition state as a key component of enzymatic methyl transfer rate enhancement. We introduce charge shift analysis that reveals the minimum number of protein residues (approximately 11–16 residues or 200–300 atoms for COMT) needed for quantitative agreement with large-QM simulations. The identified residues are not those that would be typically selected using criteria such as chemical intuition or proximity. These results provide a recipe for a more careful determination of QM region sizes in future QM/MM studies of enzymes. PMID:27704827

  14. 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.

  15. 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

  16. 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.

  17. Effect of immobilized amine density on cadmium(II) adsorption capacities for ethanediamine-modified magnetic poly-(glycidyl methacrylate) microspheres

    NASA Astrophysics Data System (ADS)

    Dong, Tingting; Yang, Liangrong; Pan, Feng; Xing, Huifang; Wang, Li; Yu, Jiemiao; Qu, Hongnan; Rong, Meng; Liu, Huizhou

    2017-04-01

    A series of ethanediamine (EDA) - modified magnetic poly-(glycidyl methacrylate) (m-PGMA-EDA)microspheres with different amine density were synthesized and their cadmium saturation adsorption capacities were examined. The results showed that the cadmium saturation adsorption capacity increased with the immobilized amine density. However, they did not show strong positive linear correlation in the whole range of amine density examined. The molar ratio of amine groups to the adsorbed cadmium decreased with the increase of amine density and eventually reached a minimum value about 4. It suggested that low immobilized amine density led to low coordination efficiency of the amine. It is hypothesized that the immobilized amine groups needed to be physically close enough to form stable amine-metal complex. When the amine density reached to a critical value 1.25 m mol m-2, stable amine-cadmium complex (4:1 N/Cd) was proposed to form. To illustrate the coordination mechanism (structure and number) of amine and Cd, FT-IR spectra of m-PGMA-EDA and m-PGMA-EDA-Cd , and X-ray photoelectron spectroscopy (XPS) of PGMA-EDA and PGMA-EDA-Cd were examined and analyzed.

  18. Granular activated carbon adsorption of organic micro-pollutants in drinking water and treated wastewater--Aligning breakthrough curves and capacities.

    PubMed

    Zietzschmann, Frederik; Stützer, Christian; Jekel, Martin

    2016-04-01

    Small-scale granular activated carbon (GAC) tests for the adsorption of organic micro-pollutants (OMP) were conducted with drinking water and wastewater treatment plant (WWTP) effluent. In both waters, three influent OMP concentration levels were tested. As long as the influent OMP concentrations are below certain thresholds, the relative breakthrough behavior is not impacted in the respective water. Accordingly, the GAC capacity for OMP is directly proportional to the influent OMP concentration in the corresponding water. The differences between the OMP breakthrough curves in drinking water and WWTP effluent can be attributed to the concentrations of the low molecular weight acid and neutral (LMW) organics of the waters. Presenting the relative OMP concentrations (c/c0) over the specific throughput of the LMW organics (mg LMW organics/g GAC), the OMP breakthrough curves in drinking water and WWTP effluent superimpose each other. This superimposition can be further increased if the UV absorbance at 254 nm (UV254) of the LMW organics is considered. In contrast, using the specific throughput of the dissolved organic carbon (DOC) did not suffice to obtain superimposed breakthrough curves. Thus, the LMW organics are the major water constituent impacting OMP adsorption onto GAC. The results demonstrate that knowing the influent OMP and LMW organics concentrations (and UV254) of different waters, the OMP breakthroughs and GAC capacities corresponding to any water can be applied to all other waters.

  19. Effect of Heat Treatment on the Nitrogen Content and Its Role on the Carbon Dioxide Adsorption Capacity of Highly Ordered Mesoporous Carbon Nitride.

    PubMed

    Lakhi, Kripal S; Park, Dae-Hwan; Joseph, Stalin; Talapaneni, Siddulu N; Ravon, Ugo; Al-Bahily, Khalid; Vinu, Ajayan

    2017-03-02

    Mesoporous carbon nitrides (MCNs) with rod-shaped morphology and tunable nitrogen contents have been synthesized through a calcination-free method by using ethanol-washed mesoporous SBA-15 as templates at different carbonization temperatures. Carbon tetrachloride and ethylenediamine were used as the sources of carbon and nitrogen, respectively. The resulting MCN materials were characterized with low- and high-angle powder XRD, nitrogen adsorption, high-resolution (HR) SEM, HR-TEM, elemental analysis, X-ray photoelectron spectroscopy, and X-ray absorption near-edge structure techniques. The carbonization temperature plays a critical role in controlling not only the crystallinity, but also the nitrogen content and textural parameters of the samples, including specific surface area and specific pore volume. The nitrogen content of MCN decreases with a concomitant increase in specific surface area and specific pore volume, as well as the crystallinity of the samples, as the carbonization temperature is increased. The results also reveal that the structural order of the materials is retained, even after heat treatment at temperatures up to 900 °C with a significant reduction of the nitrogen content, but the structure is partially damaged at 1000 °C. The carbon dioxide adsorption capacity of these materials is not only dependent on the textural parameters, but also on the nitrogen content. The MCN prepared at 900 °C, which has an optimum BET surface area and nitrogen content, registers a carbon dioxide adsorption capacity of 20.1 mmol g(-1) at 273 K and 30 bar, which is much higher than that of mesoporous silica, MCN-1, activated carbon, and multiwalled carbon nanotubes.

  20. QM/MM methods for studying enzymatic reactions of glycosyltransferases.

    PubMed

    Tvaroška, Igor

    2015-01-01

    Hybrid quantum mechanics and molecular mechanics (QM/MM) methods have become a powerful tool to provide an accurate and effective description of complex biological systems. The QM treatment of the electronic structure of an active site region and the rest of the enzyme by molecular mechanics allows enzymatic reaction to being modeled with including the impact of environment. Different reaction pathways of the enzymatic mechanism can be tested--transition states (TS) and intermediates characterized using QM/MM methods, leading to significant advances in understanding enzymatic reactions. This chapter discusses the ideas and the setting up of the structural and computational models for calculations with QM/MM software. The use of QM/MM methodology is also illustrated using the case of the inverting glycosyltransferase GnT-I.

  1. The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam Basin in China

    NASA Astrophysics Data System (ADS)

    Wang, Lu; Yu, Qingchun

    2016-11-01

    This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (<4 nm) and larger pores (>10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.

  2. The Effect of Oxidation on the Surface Chemistry of Sulfur-Containing Carbons and their Arsine Adsorption Capacity

    DTIC Science & Technology

    2010-01-01

    hydrogen sulfide . Carbon 2004;42(3):469–76. Fig. 6 – Water adsorption isotherms of the samples studied. 1786 C A R B O N 4 8 ( 2 0 1 0 ) 1 7 7 9 –1 7 8...that oxygen- and sulfur-containing groups participate in arsine oxida- tion to arsenic tri- and pentoxide and/or in the formation of arsenic sulfides ...technological difficulties, arsine is also a powerful toxin susceptible to oxidation with a strong exothermic effect. Of all the methods to separate

  3. ``QM/Me'' - a novel embedding approach for adsorbate dynamics on metal surfaces

    NASA Astrophysics Data System (ADS)

    Meyer, Jörg; Reuter, Karsten

    2010-03-01

    The dissociative adsorption of oxygen molecules on metal surfaces is a commonly known, highly exothermic reaction and in its slow or fast form of great importance for corrosion or oxidation catalysis, respectively. However, knowledge about atomistic details of the heat dissipation, a central conceptual concern, is very limited at best. Even on the level of Born-Oppenheimer potential energy surfaces, accurate dynamical ab-initio descriptions of such reactions are quite challenging from a computational point of view: Modeling the excitations of substrate phonons within periodic boundary conditions requires huge supercells, whereas traditional ``QM/MM'' embedding schemes would need unfeasibly large metal clusters. In the novel ``QM/Me'' approach presented here, the adsorbate- interaction is obtained from periodic first-principles calculations in convenient supercells and combined with the description of a 'bath-like' substrate based on classical potentials, which are parametrized to seamlessly fit the first-principles data. We apply our approach to the dissociative adsorption of O2 and H2 on Pd(100) using density-functional theory and a modified embedded atom potential. In both cases, a dominant fraction of the released chemisorption energy is dissipated into the bulk already on a femtosecond time scale. Implications for the adsorbate dynamics will be discussed.

  4. New V(IV)-based metal-organic framework having framework flexibility and high CO2 adsorption capacity.

    PubMed

    Liu, Ying-Ya; Couck, Sarah; Vandichel, Matthias; Grzywa, Maciej; Leus, Karen; Biswas, Shyam; Volkmer, Dirk; Gascon, Jorge; Kapteijn, Freek; Denayer, Joeri F M; Waroquier, Michel; Van Speybroeck, Veronique; Van Der Voort, Pascal

    2013-01-07

    A vanadium based metal-organic framework (MOF), VO(BPDC) (BPDC(2-) = biphenyl-4,4'-dicarboxylate), adopting an expanded MIL-47 structure type, has been synthesized via solvothermal and microwave methods. Its structural and gas/vapor sorption properties have been studied. This compound displays a distinct breathing effect toward certain adsorptives at workable temperatures. The sorption isotherms of CO(2) and CH(4) indicate a different sorption behavior at specific temperatures. In situ synchrotron X-ray powder diffraction measurements and molecular simulations have been utilized to characterize the structural transition. The experimental measurements clearly suggest the existence of both narrow pore and large pore forms. A free energy profile along the pore angle was computationally determined for the empty host framework. Apart from a regular large pore and a regular narrow pore form, an overstretched narrow pore form has also been found. Additionally, a variety of spectroscopic techniques combined with N(2) adsorption/desorption isotherms measured at 77 K demonstrate that the existence of the mixed oxidation states V(III)/V(IV) in the titled MOF structure compared to pure V(IV) increases the difficulty in triggering the flexibility of the framework.

  5. 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.

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

    PubMed

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

    2012-11-13

    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.

  7. 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.

  8. Polymer modified biomass of baker's yeast for enhancement adsorption of methylene blue, rhodamine B and basic magenta.

    PubMed

    Yu, Jun-Xia; Li, Bu-Hai; Sun, Xiao-Mei; Yuan, Jun; Chi, Ru-An

    2009-09-15

    In this study, poly (methacrylic acid) modified biomass was prepared to improve the adsorption capacities for three dyes: methylene blue (MB), rhodamine B (RB) and basic magenta (BM). FTIR and potentiometric titration demonstrated that a large number of carboxyl groups were introduced on the biomass surface, and the concentration of the functional group was calculated to be 1.4 mmol g(-1) by using the first and second derivative method. According to the Langmuir equation, the maximum uptake capacities (q(m)) for MB, RB and BM were 869.6, 267.4 and 719.4 mg g(-1), which were 17-, 11- and 12-fold of that obtained on the unmodified biomass, respectively. Adsorption kinetics study showed that the completion of the adsorption process needed only 70 min, which is faster than that occur with the common sorbent such as activated carbon and resin. Temperature and ionic strength experiment showed that they both had effect on the adsorption capacity of the modified biomass. Good result was obtained when the modified biomass was used to treat dye wastewater.

  9. 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.

  10. QM:QM electronic embedding using Mulliken atomic charges: energies and analytic gradients in an ONIOM framework.

    PubMed

    Hratchian, Hrant P; Parandekar, Priya V; Raghavachari, Krishnan; Frisch, Michael J; Vreven, Thom

    2008-01-21

    An accurate first-principles treatment of chemical reactions for large systems remains a significant challenge facing electronic structure theory. Hybrid models, such as quantum mechanics:molecular mechanics (QM:MM) and quantum mechanics:quantum mechanics (QM:QM) schemes, provide a promising avenue for such studies. For many chemistries, including important reactions in materials science, molecular mechanics or semiempirical methods may not be appropriate, or parameters may not be available (e.g., surface chemistry of compound semiconductors such as indium phosphide or catalytic chemistry of transition metal oxides). In such cases, QM:QM schemes are of particular interest. In this work, a QM:QM electronic embedding model within the ONIOM (our own N-layer integrated molecular orbital molecular mechanics) extrapolation framework is presented. To define the embedding potential, we choose the real-system low-level Mulliken atomic charges. This results in a set of well-defined and unique embedding charges. However, the parametric dependence of the charges on molecular geometry complicates the energy gradient that is necessary for the efficient exploration of potential energy surfaces. We derive an efficient form for the forces where a single set of self-consistent field response equations is solved. Initial tests of the method and key algorithmic issues are discussed.

  11. 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.

  12. Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2'-dipyridylamine: Central composite design optimization.

    PubMed

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

    2016-09-01

    In present work, a graphene oxide chemically modified with 2,2'-dipyridylamine (GO-DPA), was synthesized by simple, fast and low-cost process for the simultaneous adsorption of four toxic heavy metals, Pb(II), Cd(II), Ni(II) and Cu(II), from aqueous solutions. The synthesized adsorbent was characterized by FT-IR, XRD, XPS, SEM and AFM measurements. The effects of variables such as pH solution, initial ion concentrations, adsorbent dosage and sonicating time were investigated on adsorption efficiency by rotatable central composite design. The optimum conditions, specified as 8mg of adsorbent, 20mgL(-1) of each ion at pH 5 and short time of 4min led to the achievement of a high adsorption capacities. Ultrasonic power had important role in shortening the adsorption time of ions by enhancing the dispersion of adsorbent in solution. The adsorption kinetic studies and equilibrium isotherms for evaluating the mechanism of adsorption process showed a good fit to the pseudo-second order and Langmuir model, respectively. The maximum adsorption capacities (Qm) of this adsorbent were 369.749, 257.201, 180.893 and 358.824mgg(-1) for lead, cadmium, nickel and copper ions, respectively. The removal performance of adsorbent on the real wastewater samples also showed the feasibility of adsorbent for applying in industrial purposes.

  13. 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.

  14. [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).

  15. [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.

  16. QM/MM free energy simulations: recent progress and challenges.

    PubMed

    Lu, Xiya; Fang, Dong; Ito, Shingo; Okamoto, Yuko; Ovchinnikov, Victor; Cui, Qiang

    Due to the higher computational cost relative to pure molecular mechanical (MM) simulations, hybrid quantum mechanical/molecular mechanical (QM/MM) free energy simulations particularly require a careful consideration of balancing computational cost and accuracy. Here we review several recent developments in free energy methods most relevant to QM/MM simulations and discuss several topics motivated by these developments using simple but informative examples that involve processes in water. For chemical reactions, we highlight the value of invoking enhanced sampling technique (e.g., replica-exchange) in umbrella sampling calculations and the value of including collective environmental variables (e.g., hydration level) in metadynamics simulations; we also illustrate the sensitivity of string calculations, especially free energy along the path, to various parameters in the computation. Alchemical free energy simulations with a specific thermodynamic cycle are used to probe the effect of including the first solvation shell into the QM region when computing solvation free energies. For cases where high-level QM/MM potential functions are needed, we analyze two different approaches: the QM/MM-MFEP method of Yang and co-workers and perturbative correction to low-level QM/MM free energy results. For the examples analyzed here, both approaches seem productive although care needs to be exercised when analyzing the perturbative corrections.

  17. Toluene, Methanol and Benzaldehyde Removal from Gas Streams by Adsorption onto Natural Clay and Faujasite-Y type Zeolite.

    PubMed

    Zaitan, Hicham; Mohamed, Elham F; Valdés, Héctor; Nawdali, Mostafa; Rafqah, Salah; Manero, Marie Hélène

    2016-12-01

    A great number of pollution problems come as a result of the emission of Volatile Organic Compounds (VOCs) into the environment and their control becomes a serious challenge for the global chemical industry. Adsorption is a widely used technique for the removal of VOCs due to its high efficiency, low cost, and convenient operation. In this study, the feasibility to use a locally available clay, as adsorbent material to control VOCs emissions is evaluated. Natural clay is characterised by different physical-chemical methods and adsorptive interaction features between VOCs and natural clay are identified. Toluene (T), methanol (M) and benzaldehyde (B) are used here as representatives of three different kinds of VOCs. Adsorption isotherms onto natural clay and faujasite-Y type zeolite (Fau Y) are obtained at room temperature. According to Langmuir model data, maximum adsorption capacities (qm) of Fez natural clay and zeolite toward methanol (M), toluene (T) and benzaldehyde (B) at 300 K are 8, 0.89 and 3.1 mmol g-1, and 15, 1.91 and 13.9 mmol g-1 respectively. In addition, the effect of temperature on the adsorption of toluene onto natural clay is evaluated in the range from 300 to 323K. An increase on temperature reduces the adsorption capacity of natural clay toward toluene, indicating that an exothermic physical adsorption process takes place. The enthalpy of adsorption of toluene onto Fez natural clay was found to be -54 kJ mol-1. A preliminary cost analysis shows that natural clay could be used as an alternative low cost adsorbent in the control of VOCs from contaminated gas streams with a cost of US$ 0.02 kg-1 compared to Fau Y zeolite with US$ 10 kg-1.

  18. 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.

  19. Polarizable density embedding: a new QM/QM/MM-based computational strategy.

    PubMed

    Olsen, Jógvan Magnus Haugaard; Steinmann, Casper; Ruud, Kenneth; Kongsted, Jacob

    2015-05-28

    We present a new QM/QM/MM-based model for calculating molecular properties and excited states of solute-solvent systems. We denote this new approach the polarizable density embedding (PDE) model, and it represents an extension of our previously developed polarizable embedding (PE) strategy. The PDE model is a focused computational approach in which a core region of the system studied is represented by a quantum-chemical method, whereas the environment is divided into two other regions: an inner and an outer region. Molecules belonging to the inner region are described by their exact densities, whereas molecules in the outer region are treated using a multipole expansion. In addition, all molecules in the environment are assigned distributed polarizabilities in order to account for induction effects. The joint effects of the inner and outer regions on the quantum-mechanical core part of the system is formulated using an embedding potential. The PDE model is illustrated for a set of dimers (interaction energy calculations) as well as for the calculation of electronic excitation energies, showing promising results.

  20. The Exosporium of Bacillus megaterium QM B1551 Is Permeable to the Red Fluorescence Protein of the Coral Discosoma sp.

    PubMed

    Lanzilli, Mariamichela; Donadio, Giuliana; Addevico, Roberta; Saggese, Anella; Cangiano, Giuseppina; Baccigalupi, Loredana; Christie, Graham; Ricca, Ezio; Isticato, Rachele

    2016-01-01

    Bacterial spores spontaneously interact and tightly bind heterologous proteins. A variety of antigens and enzymes have been efficiently displayed on spores of Bacillus subtilis, the model system for spore formers. Adsorption on B. subtilis spores has then been proposed as a non-recombinant approach for the development of mucosal vaccine/drug delivery vehicles, biocatalysts, bioremediation, and diagnostic tools. We used spores of B. megaterium QM B1551 to evaluate their efficiency as an adsorption platform. Spores of B. megaterium are significantly larger than those of B. subtilis and of other Bacillus species and are surrounded by the exosporium, an outermost surface layer present only in some Bacillus species and lacking in B. subtilis. Strain QM B1551 of B. megaterium and a derivative strain totally lacking the exosporium were used to localize the adsorbed monomeric Red Fluorescent Protein (mRFP) of the coral Discosoma sp., used as a model heterologous protein. Our results indicate that spores of B. megaterium adsorb mRFP more efficiently than B. subtilis spores, that the exosporium is essential for mRFP adsorption, and that most of the adsorbed mRFP molecules are not exposed on the spore surface but rather localized in the space between the outer coat and the exosporium.

  1. The Exosporium of Bacillus megaterium QM B1551 Is Permeable to the Red Fluorescence Protein of the Coral Discosoma sp.

    PubMed Central

    Lanzilli, Mariamichela; Donadio, Giuliana; Addevico, Roberta; Saggese, Anella; Cangiano, Giuseppina; Baccigalupi, Loredana; Christie, Graham; Ricca, Ezio; Isticato, Rachele

    2016-01-01

    Bacterial spores spontaneously interact and tightly bind heterologous proteins. A variety of antigens and enzymes have been efficiently displayed on spores of Bacillus subtilis, the model system for spore formers. Adsorption on B. subtilis spores has then been proposed as a non-recombinant approach for the development of mucosal vaccine/drug delivery vehicles, biocatalysts, bioremediation, and diagnostic tools. We used spores of B. megaterium QM B1551 to evaluate their efficiency as an adsorption platform. Spores of B. megaterium are significantly larger than those of B. subtilis and of other Bacillus species and are surrounded by the exosporium, an outermost surface layer present only in some Bacillus species and lacking in B. subtilis. Strain QM B1551 of B. megaterium and a derivative strain totally lacking the exosporium were used to localize the adsorbed monomeric Red Fluorescent Protein (mRFP) of the coral Discosoma sp., used as a model heterologous protein. Our results indicate that spores of B. megaterium adsorb mRFP more efficiently than B. subtilis spores, that the exosporium is essential for mRFP adsorption, and that most of the adsorbed mRFP molecules are not exposed on the spore surface but rather localized in the space between the outer coat and the exosporium. PMID:27867376

  2. An efficient removal of RB5 from aqueous solution by adsorption onto nano-ZnO/Chitosan composite beads.

    PubMed

    Çınar, Seda; Kaynar, Ümit H; Aydemir, Tülin; Çam Kaynar, Sermin; Ayvacıklı, Mehmet

    2017-03-01

    In this study, the removal of Reactive Black 5 (RB-5) by nano-ZnO/Chitosan composite beads (nano-ZnO/CT-CB) from aqueous solution was investigated. ZnO nanoparticles were prepared by the via the microwave-assisted combustion technique. And then nano-ZnO/Chitosan composite beads were prepared by polymerization in the presence of nano-ZnO and chitosan. Characterization of composite beads were conducted using SEM, TEM, FTIR, TGA and XRD. Several important parameters influencing the removal of RB 5 such as contact time, pH and temperature were investigated systematically by batch experiments. At optimum conditions of pH 4 and adsorbent concentration of 0.2g, dye removal efficiency was found 76%. Langmuir, Freundlich and Temkin adsorption models were used to describe adsorption isotherms and constants. The maximum adsorption capacity (qm) by Langmuir isotherm has been found to be 189.44mg/g. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (32.7kJ/mol) indicated that the adsorption is an endothermic process. The obtained results showed that the tested adsorbents are efficient and alternate low-cost adsorbent for removal of dyes from aqueous media.

  3. 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

  4. 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.

  5. Adsorption study of an organo-arsenical with chitosan-based sorbents.

    PubMed

    Poon, Louis; Younus, Shaguftah; Wilson, Lee D

    2014-04-15

    In this study, chitosan-based copolymers were prepared at various weight ratios of chitosan (C) to glutaraldehyde (G): 1:1 (CG11), 2:1 (CG21), and 3:1 (CG31). The sorption properties of these copolymers were investigated with roxarsone in simulated aquatic conditions at pH 7 in phosphate buffer, similar to that found in poultry litter leachate. The relative sorption capacity (Q(m); mmol/g) of the sorbents are listed in parentheses in descending order: CG11 (1.80)>CG31 (0.945)>CG21 (0.802)>chitosan (0.416). The sorptive properties of the copolymers are comparable to granular activated carbon (GAC), a standard carbonaceous sorbent material, where Q(m)=2.36 mmol/g. The adsorption properties of phenolic adsorbates such as o-nitrophenol, p-nitrophenol, and roxarsone with the CG copolymers and GAC were investigated at various pH and compared with phosphate and carbonate buffer systems.

  6. 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

  7. Enhancement of the adsorption capacity of the light-weight expanded clay aggregate surface for the metronidazole antibiotic by coating with MgO nanoparticles: Studies on the kinetic, isotherm, and effects of environmental parameters.

    PubMed

    Kalhori, Ebrahim Mohammadi; Al-Musawi, Tariq J; Ghahramani, Esmaeil; Kazemian, Hossein; Zarrabi, Mansur

    2017-02-09

    The synthesized MgO nanoparticles were used to coat the light-weight expanded clay aggregates (LECA) and as a metronidazole (MNZ) adsorbent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier-transformed infrared (FTIR) techniques were employed to study the surface morphology and characteristics of the adsorbents. MgO/LECA clearly revealed the advantages of the nanocomposite particles, showing high specific surface area (76.12 m(2)/g), significant adsorption sites and functional groups. Between pH 5 and 9, the MNZ sorption was not significantly affected. Kinetic studies revealed that the MNZ adsorption closely followed the Avrami model, with no dominant process controlling the sorption rate. The study of the effects of foreign ions revealed that the addition of carbonate raised the MNZ removal efficiency of LECA by 8% and the total removal of MNZ by MgO/LECA. Furthermore, nitrate and hardness only marginally influenced the MNZ removal efficiency and their effects can be ranked in the order of carbonate>nitrate>hardness. The isotherm adsorption of MNZ was best fitted with the Langmuir model enlighten the monolayer MNZ adsorption on the homogeneous LECA and MgO/LECA surfaces. The maximum adsorption capacity under optimum conditions was enhanced from 56.31 to 84.55 mg/g for LECA and MgO/LECA, respectively. These findings demonstrated that the MgO/LECA nanocomposite showed potential as an efficient adsorbent for MNZ removal.

  8. 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…

  9. Combining quantum wavepacket ab initio molecular dynamics with QM/MM and QM/QM techniques: Implementation blending ONIOM and empirical valence bond theory.

    PubMed

    Sumner, Isaiah; Iyengar, Srinivasan S

    2008-08-07

    We discuss hybrid quantum-mechanics/molecular-mechanics (QM/MM) and quantum mechanics/quantum mechanics (QM/QM) generalizations to our recently developed quantum wavepacket ab initio molecular dynamics methodology for simultaneous dynamics of electrons and nuclei. The approach is a synergy between a quantum wavepacket dynamics, ab initio molecular dynamics, and the ONIOM scheme. We utilize this method to include nuclear quantum effects arising from a portion of the system along with a simultaneous description of the electronic structure. The generalizations provided here make the approach a potentially viable alternative for large systems. The quantum wavepacket dynamics is performed on a grid using a banded, sparse, and Toeplitz representation of the discrete free propagator, known as the "distributed approximating functional." Grid-based potential surfaces for wavepacket dynamics are constructed using an empirical valence bond generalization of ONIOM and further computational gains are achieved through the use of our recently introduced time-dependent deterministic sampling technique. The ab initio molecular dynamics is achieved using Born-Oppenheimer dynamics. All components of the methodology, namely, quantum dynamics and ONIOM molecular dynamics, are harnessed together using a time-dependent Hartree-like procedure. We benchmark the approach through the study of structural and vibrational properties of molecular, hydrogen bonded clusters inclusive of electronic, dynamical, temperature, and critical quantum nuclear effects. The vibrational properties are constructed through a velocity/flux correlation function formalism introduced by us in an earlier publication.

  10. How to Assess if QM Can Break Down Barriers

    ERIC Educational Resources Information Center

    Kaelin, Roy A.

    2016-01-01

    Requiring savvy, online courses can present a perceived barrier to adult learners for a variety of reasons, but ease of access due to inadequate navigability should not be one of those barriers. Re-tooling online courses to standards of Quality Matters (QM) can lessen that barrier to access, making adult learners more participatory. Internal…

  11. 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.

  12. 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.

  13. 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

    2015-11-07

    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.

  14. 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.

  15. Tests of an adaptive QM/MM calculation on free energy profiles of chemical reactions in solution.

    PubMed

    Várnai, Csilla; Bernstein, Noam; Mones, Letif; Csányi, Gábor

    2013-10-10

    We present reaction free energy calculations using the adaptive buffered force mixing quantum mechanics/molecular mechanics (bf-QM/MM) method. The bf-QM/MM method combines nonadaptive electrostatic embedding QM/MM calculations with extended and reduced QM regions to calculate accurate forces on all atoms, which can be used in free energy calculation methods that require only the forces and not the energy. We calculate the free energy profiles of two reactions in aqueous solution: the nucleophilic substitution reaction of methyl chloride with a chloride anion and the deprotonation reaction of the tyrosine side chain. We validate the bf-QM/MM method against a full QM simulation, and show that it correctly reproduces both geometrical properties and free energy profiles of the QM model, while the electrostatic embedding QM/MM method using a static QM region comprising only the solute is unable to do so. The bf-QM/MM method is not explicitly dependent on the details of the QM and MM methods, so long as it is possible to compute QM forces in a small region and MM forces in the rest of the system, as in a conventional QM/MM calculation. It is simple, with only a few parameters needed to control the QM calculation sizes, and allows (but does not require) a varying and adapting QM region which is necessary for simulating solutions.

  16. Accuracy of buffered-force QM/MM simulations of silica

    SciTech Connect

    Peguiron, Anke; Moras, Gianpietro; Colombi Ciacchi, Lucio; De Vita, Alessandro; Kermode, James R.

    2015-02-14

    We report comparisons between energy-based quantum mechanics/molecular mechanics (QM/MM) and buffered force-based QM/MM simulations in silica. Local quantities—such as density of states, charges, forces, and geometries—calculated with both QM/MM approaches are compared to the results of full QM simulations. We find the length scale over which forces computed using a finite QM region converge to reference values obtained in full quantum-mechanical calculations is ∼10 Å rather than the ∼5 Å previously reported for covalent materials such as silicon. Electrostatic embedding of the QM region in the surrounding classical point charges gives only a minor contribution to the force convergence. While the energy-based approach provides accurate results in geometry optimizations of point defects, we find that the removal of large force errors at the QM/MM boundary provided by the buffered force-based scheme is necessary for accurate constrained geometry optimizations where Si–O bonds are elongated and for finite-temperature molecular dynamics simulations of crack propagation. Moreover, the buffered approach allows for more flexibility, since special-purpose QM/MM coupling terms that link QM and MM atoms are not required and the region that is treated at the QM level can be adaptively redefined during the course of a dynamical simulation.

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

    PubMed

    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

    2016-10-01

    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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. New insights in the catalytic mechanism of tyrosine ammonia-lyase given by QM/MM and QM cluster models.

    PubMed

    Pinto, Gaspar P; Ribeiro, António J M; Ramos, Maria J; Fernandes, Pedro A; Toscano, Marirosa; Russo, Nino

    2015-09-15

    Tyrosine ammonia lyase (TAL) catalyzes the deamination of tyrosine to p-coumaric acid in purple phototropic bacteria and Actinomycetales. The enzyme is used in bioengineering and has the potential to be used industrially. It belongs to a family of enzymes that uses a 4-methylidene-imidazole-5-one (MIO) cofactor to catalyze the deamination amino acids. In the present work, we used a QM/MM and a QM cluster models of TAL to explore two putative reaction paths for its catalytic mechanism. Part of the N-MIO mechanism was previously studied by computational methods. We improved on previous studies by using a larger, more complete model of the enzyme, and by describing the complete reaction path. The activation energy for this mechanism, in agreement with the previous study, is 28.5 kcal/mol. We also found another reaction path that has overall better kinetics and reaches the products in a single reaction step. The barrier for this Single-Step mechanism is 16.6 kcal/mol, which agrees very well with the experimental kcat of 16.0 kcal/mol. The geometrical parameters obtained for the cluster and QM/MM models are very similar, despite differences in the relative energies. This means that both approaches are capable of describing the correct catalytic path of TAL.

  3. 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

    2014-04-08

    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

  4. 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

    2011-04-05

    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.

  5. 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

  6. QM-6 test firing at Wasatch Operations, Morton Thiokol, Utah

    NASA Technical Reports Server (NTRS)

    1988-01-01

    The third redesigned Space Shuttle solid rocket motor (SRM), designated qualification motor 6 (QM-6), is test fired. Five motor firings are required prior to resumption of Shuttle flights. This test, part of the Shuttle motor redesign program, was conducted by Morton Thiokol, NASA's prime contractor for the SRM, at its Wasatch Facility near Brigham City, Utah. The Marshall Space Flight Center (MSFC) in Huntsville, Alabama manages the motor program for NASA. NOTE: S88-34564 through S88-34566 are 35mm CN; S88-34567 is 120 CN.

  7. Effect of functionalized groups on gas-adsorption properties: syntheses of functionalized microporous metal-organic frameworks and their high gas-storage capacity.

    PubMed

    Wang, Yanlong; Tan, Chunhong; Sun, Zhihao; Xue, Zhenzhen; Zhu, Qilong; Shen, Chaojun; Wen, Yuehong; Hu, Shengmin; Wang, Yong; Sheng, Tianlu; Wu, Xintao

    2014-01-27

    The microporous metal-organic framework (MMOF) Zn4O(L1)2⋅9 DMF⋅9 H2O (1-H) and its functionalized derivatives Zn4O(L1-CH3)2⋅9 DMF⋅9 H2O (2-CH3) and Zn4O(L1-Cl)2⋅9 DMF⋅9 H2O (3-Cl) have been synthesized and characterized (H3L1=4-[N,N-bis(4-methylbenzoic acid)amino]benzoic acid, H3L1-CH3=4-[N,N-bis(4-methylbenzoic acid)amino]-2-methylbenzoic acid, H3L1-Cl=4-[N,N-bis(4-methylbenzoic acid)amino]-2-chlorobenzoic acid). Single-crystal X-ray diffraction analyses confirmed that the two functionalized MMOFs are isostructural to their parent MMOF, and are twofold interpenetrated three-dimensional (3D) microporous frameworks. All of the samples possess enduring porosity with Langmuir surface areas over 1950 cm(2) g(-1). Their pore volumes and surface areas decrease in the order 1-H>2-CH3 >3-Cl. Gas-adsorption studies show that the H2 uptakes of these samples are among the highest of the MMOFs (2.37 wt% for 3-Cl at 77 K and 1 bar), although their structures are interpenetrating. Furthermore, this work reveals that the adsorbate-adsorbent interaction plays a more important role in the gas-adsorption properties of these samples at low pressure, whereas the effects of the pore volumes and surface areas dominate the gas-adsorption properties at high pressure.

  8. 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.

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

    PubMed

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

    2015-07-05

    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.

  10. 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…

  11. 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.

  12. 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

  13. 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

  14. K4Nb6O17·4.5H2O: a novel dual functional material with quick photoreduction of Cr(VI) and high adsorptive capacity of Cr(III).

    PubMed

    Ma, Yuli; Liu, Xiaoqing; Li, Yang; Su, Yiguo; Chai, Zhanli; Wang, Xiaojing

    2014-08-30

    A series of orthorhombic phase K4Nb6O17·4.5H2O was synthesized via a hydrothermal approach. When presented in an acidic pH range, K4Nb6O17·4.5H2O showed a strong ability in quick reduction from Cr(VI) to Cr(III). The resulted Cr(III) ions were removed by an effective adsorption through simply adjusting the solution pH from strong acidity to near neutrality, owing to the sample's unique nano-sheet structure with a wide layer spacing. The Cr(III) ions adsorbed onto samples were released again for reusing by eluting with 1molL(-1) HCl solution, and K4Nb6O17·4.5H2O regenerated by immersing in a KOH solution. The reduction efficiency of Cr(VI) was still up to 98% after irradiation for 60min, and the removal efficiency of Cr(III) ions was as high as 83% even after five cycles. Therefore, K4Nb6O17·4.5H2O is clearly demonstrated to be an excellent dual functional material with quick photoreduction of Cr(VI) and high adsorptive capacity of Cr(III). The relevant materials reported herein might be found various environment-related applications.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. Developing adaptive QM/MM computer simulations for electrochemistry.

    PubMed

    Dohm, Sebastian; Spohr, Eckhard; Korth, Martin

    2017-01-05

    We report the development of adaptive QM/MM computer simulations for electrochemistry, providing public access to all sources via the free and open source software development model. We present a modular workflow-based MD simulation code as a platform for algorithms for partitioning space into different regions, which can be treated at different levels of theory on a per-timestep basis. Currently implemented algorithms focus on targeting molecules and their solvation layers relevant to electrochemistry. Instead of using built-in forcefields and quantum mechanical methods, the code features a universal interface, which allows for extension to a range of external forcefield programs and programs for quantum mechanical calculations, thus enabling the user to readily implement interfaces to those programs. The purpose of this article is to describe our codes and illustrate its usage. © 2016 Wiley Periodicals, Inc.

  20. 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.

  1. 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

  2. Acceleration of Ab Initio QM/MM Calculations under Periodic Boundary Conditions by Multiscale and Multiple Time Step Approaches.

    PubMed

    Nam, Kwangho

    2014-10-14

    Development of multiscale ab initio quantum mechanical and molecular mechanical (AI-QM/MM) method for periodic boundary molecular dynamics (MD) simulations and their acceleration by multiple time step approach are described. The developed method achieves accuracy and efficiency by integrating the AI-QM/MM level of theory and the previously developed semiempirical (SE) QM/MM-Ewald sum method [J. Chem. Theory Comput. 2005, 1, 2] extended to the smooth particle-mesh Ewald (PME) summation method. In the developed methods, the total energy of the simulated system is evaluated at the SE-QM/MM-PME level of theory to include long-range QM/MM electrostatic interactions, which is then corrected on the fly using the AI-QM/MM level of theory within the real space cutoff. The resulting energy expression enables decomposition of total forces applied to each atom into forces determined at the low-level SE-QM/MM method and correction forces at the AI-QM/MM level, to integrate the system using the reversible reference system propagator algorithm. The resulting method achieves a substantial speed-up of the entire calculation by minimizing the number of time-consuming energy and gradient evaluations at the AI-QM/MM level. Test calculations show that the developed multiple time step AI-QM/MM method yields MD trajectories and potential of mean force profiles comparable to single time step QM/MM results. The developed method, together with message passing interface (MPI) parallelization, accelerates the present AI-QM/MM MD simulations about 30-fold relative to the speed of single-core AI-QM/MM simulations for the molecular systems tested in the present work, making the method less than one order slower than the SE-QM/MM methods under periodic boundary conditions.

  3. 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

  4. 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.

  5. Solvents effects on the mechanism of cellulose hydrolysis: A QM/MM study.

    PubMed

    Loerbroks, Claudia; Heimermann, Andreas; Thiel, Walter

    2015-06-05

    This article reports a combined quantum mechanics/molecular mechanics (QM/MM) investigation on the acid hydrolysis of cellulose in water using two different models, cellobiose and a 40-unit cellulose chain. The explicitly treated solvent molecules strongly influence the conformations, intramolecular hydrogen bonds, and exoanomeric effects in these models. As these features are largely responsible for the barrier to cellulose hydrolysis, the present QM/MM results for the pathways and reaction intermediates in water are expected to be more realistic than those from a former density functional theory (DFT) study with implicit solvent (CPCM). However, in a qualitative sense, there is reasonable agreement between the DFT/CPCM and QM/MM predictions for the reaction mechanism. Differences arise mainly from specific solute-solvent hydrogen bonds that are only captured by QM/MM and not by DFT/CPCM.

  6. 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.

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

    PubMed

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

    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.

  8. 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.

  9. 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.

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

    PubMed

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

    2016-08-09

    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.

  11. 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

  12. Mapping protein electron transfer pathways with QM/MM methods

    PubMed Central

    Guallar, Victor; Wallrapp, Frank

    2008-01-01

    Mixed quantum mechanics/molecular mechanics (QM/MM) methods offer a valuable computational tool for understanding the electron transfer pathway in protein–substrate interactions and protein–protein complexes. These hybrid methods are capable of solving the Schrödinger equation on a small subset of the protein, the quantum region, describing its electronic structure under the polarization effects of the remainder of the protein. By selectively turning on and off different residues in the quantum region, we are able to obtain the electron pathway for short- and large-range interactions. Here, we summarize recent studies involving the protein–substrate interaction in cytochrome P450 camphor, ascorbate peroxidase and cytochrome c peroxidase, and propose a novel approach for the long-range protein–protein electron transfer. The results on ascorbate peroxidase and cytochrome c peroxidase reveal the importance of the propionate groups in the electron transfer pathway. The long-range protein–protein electron transfer has been studied on the cytochrome c peroxidase–cytochrome c complex. The results indicate the importance of Phe82 and Cys81 on cytochrome c, and of Asn196, Ala194, Ala176 and His175 on cytochrome c peroxidase. PMID:18445553

  13. 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.

  14. 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.

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

    SciTech Connect

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

    2015-02-03

    We present the implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER. 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.

  16. 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.

  17. 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

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

    DOE PAGES

    Mones, Letif; Jones, Andrew; Götz, Andreas W.; ...

    2015-02-03

    We present the implementation and validation of the adaptive buffered force (AdBF) quantum-mechanics/molecular-mechanics (QM/MM) method in two popular packages, CP2K and AMBER. 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 usingmore » 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.« less

  19. 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.

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

    PubMed

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

    2014-04-08

    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.

  1. 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.

  2. Toward QM/MM Simulation of Enzymatic Reactions with the Drude Oscillator Polarizable Force Field.

    PubMed

    Boulanger, Eliot; Thiel, Walter

    2014-04-08

    The polarization of the environment can influence the results from hybrid quantum mechanical/molecular mechanical (QM/MM) simulations of enzymatic reactions. In this article, we address several technical aspects in the development of polarizable QM/MM embedding using the Drude Oscillator (DO) force field. We propose a stable and converging update of the DO polarization state for geometry optimizations and a suitable treatment of the QM/MM-DO boundary when the QM and MM regions are separated by cutting through a covalent bond. We assess the performance of our approach by computing binding energies and geometries of three selected complexes relevant to biomolecular modeling, namely the water trimer, the N-methylacetamide dimer, and the cationic bis(benzene)sodium sandwich complex. Using a recently published MM-DO force field for proteins, we evaluate the effect of MM polarization on the QM/MM energy profiles of the enzymatic reactions catalyzed by chorismate mutase and by p-hydroxybenzoate hydroxylase. We find that inclusion of MM polarization affects the computed barriers by about 10%.

  3. 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

  4. 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.

  5. Analytical First and Second Derivatives for a Fully Polarizable QM/Classical Hamiltonian.

    PubMed

    Lipparini, Filippo; Cappelli, Chiara; Scalmani, Giovanni; De Mitri, Nicola; Barone, Vincenzo

    2012-11-13

    In this work, we present the derivation and implementation of analytical first and second derivatives for a fully polarizable QM/MM/PCM energy functional. First derivatives with respect to both QM- and MM-described nuclear coordinates and electric perturbations are derived and implemented, and some preliminary application is shown. Analytical second derivatives with respect to nuclear and electric perturbations are then derived, and some numerical test is presented both for a solvated system and for a cromophore embedded in a biological matrix.

  6. Multilayer adsorption on fractal surfaces.

    PubMed

    Vajda, Péter; Felinger, Attila

    2014-01-10

    Multilayer adsorption is often observed in liquid chromatography. The most frequently employed model for multilayer adsorption is the BET isotherm equation. In this study we introduce an interpretation of multilayer adsorption measured on liquid chromatographic stationary phases based on the fractal theory. The fractal BET isotherm model was successfully used to determine the apparent fractal dimension of the adsorbent surface. The nonlinear fitting of the fractal BET equation gives us the estimation of the adsorption equilibrium constants and the monolayer saturation capacity of the adsorbent as well. In our experiments, aniline and proline were used as test molecules on reversed phase and normal phase columns, respectively. Our results suggest an apparent fractal dimension 2.88-2.99 in the case of reversed phase adsorbents, in the contrast with a bare silica column with a fractal dimension of 2.54.

  7. Adsorption of acid dye onto organobentonite.

    PubMed

    Baskaralingam, P; Pulikesi, M; Elango, D; Ramamurthi, V; Sivanesan, S

    2006-02-06

    Removal of Acid Red 151 from aqueous solution at different dye concentrations, adsorbent doses and pH has been studied. The bentonite clay has been modified using cationic surfactants, which has been confirmed using XRD and FT-IR analyses. Experimental result has shown that the acidic pH favours the adsorption. The adsorption isotherms are described by means of Langmuir and Freundlich isotherms. The adsorption capacity has been found to be 357.14 and 416.66 mg g(-1) for the cetyldimethylbenzylammonium chloride-bentonite (CDBA-bent) and cetylpyridinium chloride-bentonite (CP-bent), respectively. Kinetic studies show that the adsorption followed second-order kinetics.

  8. Adsorption of selected volatile organic vapors on multiwall carbon nanotubes.

    PubMed

    Shih, Yang-hsin; Li, Mei-syue

    2008-06-15

    Carbon nanotubes are expected to play an important role in sensing, pollution treatment and separation techniques. This study examines the adsorption behaviors of volatile organic compounds (VOCs), n-hexane, benzene, trichloroethylene and acetone on two multiwall carbon nanotubes (MWCNTs), CNT1 and CNT2. Among these VOCs, acetone exhibits the highest adsorption capacity. The highest adsorption enthalpies and desorption energies of acetone were also observed. The strong chemical interactions between acetone and both MWCNTs may be the result from chemisorption on the topological defects. The adsorption heats of trichloroethylene, benzene, and n-hexane are indicative of physisorption on the surfaces of both MWCNTs. CNT2 presents a higher adsorption capacity than CNT1 due to the existence of an exterior amorphous carbon layer on CNT2. The amorphous carbon enhances the adsorption capacity of organic chemicals on carbon nanotubes. The morphological and structure order of carbon nanotubes are the primary affects on the adsorption process of organic chemicals.

  9. Adsorption of crude oil on anhydrous and hydrophobized vermiculite.

    PubMed

    da Silva, Umberto G; de F Melo, Marcus A; da Silva, Adaílton F; de Farias, Robson F

    2003-04-15

    This publication reports the adsorption of crude oil on vermiculite samples, expanded and hydrophobized with carnauba (Copernícia Cerífera) wax. The adsorption studies were performed by using columns filled with the vermiculite matrices and by dispersion of the vermiculite samples in an oil-water (50 ppm of oil) emulsion. The hydrate vermiculite exhibits a very low adsorption capacity against crude oil. On the other hand, anhydrous (expanded) and hydrophobized matrices show a high adsorption capacity. The 10% hydrophobized matrix show a 50% increased adsorption capacity, in comparison with the expanded one. For adsorption performed in the water-oil emulsion, saturation of the solid hydrophobized matrix is achieved after 60 min. The hydrophobized samples exhibit adsorption factors in the 0.7-1.0 range.

  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. Multiple-steering QM-MM calculation of the free energy profile in chorismate mutase.

    PubMed

    Crespo, Alejandro; Martí, Marcelo A; Estrin, Darío A; Roitberg, Adrian E

    2005-05-18

    A novel technique for computing free energy profiles in enzymatic reactions using the multiple steering molecular dynamics approach in the context of an efficient QM-MM density functional scheme is presented. The conversion reaction of chorismate to prephenate catalyzed by the Bacillus subtilis enzyme chorismate mutase has been chosen as an illustrative example.

  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. 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).

  14. 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

  15. 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

  16. In vitro adsorption of tilidine HCl by activated charcoal.

    PubMed

    Cordonnier, J A; Van den Heede, M A; Heyndrickx, A M

    In vitro studies were carried out in order to determine the adsorption of tilidine HCl, a narcotic analgesic, by activated charcoal (max. adsorption capacity 185.5 mg/g of charcoal). The path of the adsorption isotherms at pH 1.2 and 7.5 suggests that the in vivo adsorption of tilidine HCl may be increased when the drug passes from the stomach to the intestine, unless the intestinal content exerts a displacing effect. Nevertheless, the adsorption was dependent on the quantity of activated charcoal used, becoming more complete when the quantity of activated charcoal was increased. The effects of additives on the adsorption capacity of activated charcoal were also investigated in vitro. Ethanol, sorbitol and sucrose significantly reduced drug adsorption, while cacao powder, milk and starch had no effect on tilidine adsorption. At an acid pH, Federa Activated Charcoal significantly adsorbed more drug than either Norit A or Activated Charcoal Merck.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. Binding free energy calculation with QM/MM hybrid methods for Abl-Kinase inhibitor.

    PubMed

    Dubey, Kshatresh Dutta; Ojha, Rajendra Prasad

    2011-01-01

    We report a Quantum mechanics/Molecular Mechanics-Poisson-Boltzmann/ Surface Area (QM/MM-PB/SA) method to calculate the binding free energy of c-Abl human tyrosine kinase by combining the QM and MM principles where the ligand is treated quantum mechanically and the rest of the receptor by classical molecular mechanics. To study the role of entropy and the flexibility of the protein ligand complex in a solvated environment, molecular dynamics calculations are performed using a hybrid QM/MM approach. This work shows that the results of the QM/MM approach are strongly correlated with the binding affinity. The QM/MM interaction energy in our reported study confirms the importance of electronic and polarization contributions, which are often neglected in classical MM-PB/SA calculations. Moreover, a comparison of semi-empirical methods like DFTB-SCC, PM3, MNDO, MNDO-PDDG, and PDDG-PM3 is also performed. The results of the study show that the implementation of a DFTB-SCC semi-empirical Hamiltonian that is derived from DFT gives better results than other methods. We have performed such studies using the AMBER molecular dynamic package for the first time. The calculated binding free energy is also in agreement with the experimentally determined binding affinity for c-Abl tyrosine kinase complex with Imatinib.Electronic supplementary material The online version of this article (doi:10.1007/s10867-010-9199-z) contains supplementary material, which is available to authorized users.

  2. Unbiased QM/MM approach using accurate multipoles from a linear scaling DFT calculation with a systematic basis set

    NASA Astrophysics Data System (ADS)

    Mohr, Stephan; Genovese, Luigi; Ratcliff, Laura; Masella, Michel

    The quantum mechanics/molecular mechanis (QM/MM) method is a popular approach that allows to perform atomistic simulations using different levels of accuracy. Since only the essential part of the simulation domain is treated using a highly precise (but also expensive) QM method, whereas the remaining parts are handled using a less accurate level of theory, this approach allows to considerably extend the total system size that can be simulated without a notable loss of accuracy. In order to couple the QM and MM regions we use an approximation of the electrostatic potential based on a multipole expansion. The multipoles of the QM region are determined based on the results of a linear scaling Density Functional Theory (DFT) calculation using a set of adaptive, localized basis functions, as implemented within the BigDFT software package. As this determination comes at virtually no extra cost compared to the QM calculation, the coupling between QM and MM region can be done very efficiently. In this presentation I will demonstrate the accuracy of both the linear scaling DFT approach itself as well as of the approximation of the electrostatic potential based on the multipole expansion, and show some first QM/MM applications using the aforementioned approach.

  3. Tomato QM-like protein protects Saccharomyces cerevisiae cells against oxidative stress by regulating intracellular proline levels.

    PubMed

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

    2006-06-01

    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.

  4. Challenges and Solutions in Optimizing Execution Performance of a Clinical Decision Support-Based Quality Measurement (CDS-QM) Framework.

    PubMed

    Tippetts, Tyler J; Warner, Phillip B; Kukhareva, Polina V; Shields, David E; Staes, Catherine J; Kawamoto, Kensaku

    2015-01-01

    Given the close relationship between clinical decision support (CDS) and quality measurement (QM), it has been proposed that a standards-based CDS Web service could be leveraged to enable QM. Benefits of such a CDS-QM framework include semantic consistency and implementation efficiency. However, earlier research has identified execution performance as a critical barrier when CDS-QM is applied to large populations. Here, we describe challenges encountered and solutions devised to optimize CDS-QM execution performance. Through these optimizations, the CDS-QM execution time was optimized approximately three orders of magnitude, such that approximately 370,000 patient records can now be evaluated for 22 quality measure groups in less than 5 hours (approximately 2 milliseconds per measure group per patient). Several key optimization methods were identified, with the most impact achieved through population-based retrieval of relevant data, multi-step data staging, and parallel processing. These optimizations have enabled CDS-QM to be operationally deployed at an enterprise level.

  5. Electronic Absorption Spectra from MM and ab initio QM/MM Molecular Dynamics: Environmental Effects on the Absorption Spectrum of Photoactive Yellow Protein

    PubMed Central

    Isborn, Christine M.; Götz, Andreas W.; Clark, Matthew A.; Walker, Ross C.; Martínez, Todd J.

    2012-01-01

    We describe a new interface of the GPU parallelized TeraChem electronic structure package and the Amber molecular dynamics package for quantum mechanical (QM) and mixed QM and molecular mechanical (MM) molecular dynamics simulations. This QM/MM interface is used for computation of the absorption spectra of the photoactive yellow protein (PYP) chromophore in vacuum, aqueous solution, and protein environments. The computed excitation energies of PYP require a very large QM region (hundreds of atoms) covalently bonded to the chromophore in order to achieve agreement with calculations that treat the entire protein quantum mechanically. We also show that 40 or more surrounding water molecules must be included in the QM region in order to obtain converged excitation energies of the solvated PYP chromophore. These results indicate that large QM regions (with hundreds of atoms) are a necessity in QM/MM calculations. PMID:23476156

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

    NASA Astrophysics Data System (ADS)

    Ishida, Toyokazu

    2008-09-01

    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.

  7. 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.

  8. 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.

  9. 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.

  10. Functionalized SBA-15 materials for bilirubin adsorption

    NASA Astrophysics Data System (ADS)

    Tang, Tao; Zhao, Yanling; Xu, Yao; Wu, Dong; Xu, Jun; Deng, Feng

    2011-05-01

    To investigate the driving force for bilirubin adsorption on mesoporous materials, a comparative study was carried out between pure siliceous SBA-15 and three functionalized SBA-15 mesoporous materials: CH 3-SBA-15 (MS), NH 2-SBA-15 (AS), and CH 3/NH 2-SBA-15 (AMS) that were synthesized by one-pot method. The obtained materials exhibited large surface areas (553-810 m 2/g) and pore size (6.6-7.1 nm) demonstrated by XRD and N 2-ad/desorption analysis. The SEM images showed that the materials had similar fiberlike morphology. The functionalization extent was calculated according to 29Si MAS NMR spectra and it was close to the designed value (10%). The synthesized mesoporous materials were used as bilirubin adsorbents and showed higher bilirubin adsorption capacities than the commercial active carbon. The adsorption capacities of amine functionalized samples AMS and AS were larger than those of pure siliceous SBA-15 and MS, indicating that electrostatic interaction was the dominant driving force for bilirubin adsorption on mesoporous materials. Increasing the ionic strength of bilirubin solution by adding NaCl would decrease the bilirubin adsorption capacity of mesoporous material, which further demonstrated that the electrostatic interaction was the dominant driving force for bilirubin adsorption. In addition, the hydrophobic interaction provided by methyl groups could promote the bilirubin adsorption.

  11. 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.

  12. Carbon dioxide adsorption in graphene sheets

    NASA Astrophysics Data System (ADS)

    Mishra, Ashish Kumar; Ramaprabhu, Sundara

    2011-09-01

    Control over the CO2 emission via automobiles and industrial exhaust in atmosphere, is one of the major concerns to render environmental friendly milieu. Adsorption can be considered to be one of the more promising methods, offering potential energy savings compared to absorbent systems. Different carbon nanostructures (activated carbon and carbon nanotubes) have attracted attention as CO2 adsorbents due to their unique surface morphology. In the present work, we have demonstrated the CO2 adsorption capacity of graphene, prepared via hydrogen induced exfoliation of graphitic oxide at moderate temperatures. The CO2 adsorption study was performed using high pressure Sieverts apparatus and capacity was calculated by gas equation using van der Waals corrections. Physical adsorption of CO2 molecules in graphene was confirmed by FTIR study. Synthesis of graphene sheets via hydrogen exfoliation is possible at large scale and lower cost and higher adsorption capacity of as prepared graphene compared to other carbon nanostructures suggests its possible use as CO2 adsorbent for industrial application. Maximum adsorption capacity of 21.6 mmole/g was observed at 11 bar pressure and room temperature (25 °C).

  13. Parametric study of a silica gel-water adsorption refrigeration cycle -- The influence of thermal capacitance and heat exchanger UA-values on cooling capacity, power density, and COP

    SciTech Connect

    Boelman, E.C.; Saha, B.B.; Kashiwagi, Takao

    1997-12-31

    The influence of heat exchanger UA-values (adsorber/desorber, evaporator, and condenser) is investigated for an adsorption chiller, with consideration given to the thermal capacitance of the adsorber/desorber by means of a lumped-parameter cycle simulation model developed by the authors and co-workers for the single-stage silica gel-water adsorption chiller. The closed-cycle-type chiller, for use in air conditioning, is driven by low-grade waste heat (85 C [185 F]) and cooled by water at 31 C (88 F) and operates on relatively short cycle times (420 seconds adsorption/desorption; 30 second adsorber/desorber sensible cooling and heating). The results showed cycle performance to be considerably affected by the thermal capacitance and UA-value of the adsorber/desorber, which is attributed to the severe sensible cooling/heating requirements resulting from batched cycle operation. The model is also sensitive to the evaporator UA-value--but to a lesser extent. The condenser UA-value is the least sensitive parameter due to the working pair adsorption behavior in the temperature range defined for desorption and condensation.

  14. Adsorption of carbon black using carboxymethyl chitosan in deinking process

    NASA Astrophysics Data System (ADS)

    Muryeti, Budimulyani, Estuti; Sinurat, Ellya

    2017-03-01

    The study about synthesis, characterization, and application carboxymethyl chitosan as adsorbent in deinking process was conducted. Adsorption of carbon black onto carboxymethyl chitosan has been investigated in a batch system. This research was conducted to obtain the adsorption capacity of carboxymethyl chitosan. The experiments were carried out to study the effect of carbon black concentration, contact time and dosage of carboxymethyl chitosan to the adsorption capacity of carboxymethyl chitosan. The optimum condition of carbon black adsorption was achieved at contact time of 60 min and weight doses of 1.0 g. The adsorption capacity of carboxymethyl chitosan was 14.34 mg/g and the adsorption effectivity was 70.54%. The result indicates that carboxymethyl chitosan could be used as adsorbent of carbon black in deinking process.

  15. [Adsorption dynamics and breakthrough characteristics based on the fluidization condition].

    PubMed

    Wang, Jun; Wang, Yao; Huang, Xing; Yuan, Yi-Long; Chen, Rui-Hui; Zhou, Hang; Zhou, Dan-Dan

    2014-02-01

    Few studies on the adsorption dynamics and breakthrough characteristics based on the fluidization condition have been reported. In a fluidized bed adsorption reactor with phenol as the adsorbate and granular activated carbon as the adsorbent, the adsorption efficiency, adsorption dynamic characteristics, adsorption breakthrough curves and adsorption capacities were studied and compared with those of a fixed bed operated under the same conditions. The results showed that the adsorption efficiencies exceeded 93% in 5 min in both the fluidized conditions and fixed conditions at the superficial velocities of 8 mm x s(-1) and 13 mm x s(-1). Meanwhile, the above adsorption reactions fitted to Pseudo-second-order with linear correlation coefficients greater than 0.999. The adsorption capacity of fluidized conditions was 8.77 mg x g(-1) and 24.70 mg x g(-1) at the superficial velocities of 6 mm x s(-1) and 8 mm x s(-1). Generally, the fluidized bed reactor showed a higher adsorption efficiency and greater adsorption capacity than the fixed bed reactor.

  16. A QM/MM study of absorption spectra of uracil derivatives in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nakayama, Akira

    2016-12-01

    The absorption spectra of three representative uracil derivatives (uracil, thymine, and 5-fluorouracil) in aqueous solution are investigated by the QM/MM approach, where the CASPT2 method is employed to evaluate the excitation energies. The computed absorption spectra are in good agreement with the experimental results, and in particular, the relative values of the absorption maximum between these derivatives are well reproduced in the simulations.

  17. 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...

  18. Full QM Calculation of RNA Energy Using Electrostatically Embedded Generalized Molecular Fractionation with Conjugate Caps Method.

    PubMed

    Jin, Xinsheng; Zhang, John Z H; He, Xiao

    2017-03-30

    In this study, the electrostatically embedded generalized molecular fractionation with conjugate caps (concaps) method (EE-GMFCC) was employed for efficient linear-scaling quantum mechanical (QM) calculation of total energies of RNAs. In the EE-GMFCC approach, the total energy of RNA is calculated by taking a proper combination of the QM energy of each nucleotide-centric fragment with large caps or small caps (termed EE-GMFCC-LC and EE-GMFCC-SC, respectively) deducted by the energies of concaps. The two-body QM interaction energy between non-neighboring ribonucleotides which are spatially in close contact are also taken into account for the energy calculation. Numerical studies were carried out to calculate the total energies of a number of RNAs using the EE-GMFCC-LC and EE-GMFCC-SC methods at levels of the Hartree-Fock (HF) method, density functional theory (DFT), and second-order many-body perturbation theory (MP2), respectively. The results show that the efficiency of the EE-GMFCC-SC method is about 3 times faster than the EE-GMFCC-LC method with minimal accuracy sacrifice. The EE-GMFCC-SC method is also applied for relative energy calculations of 20 different conformers of two RNA systems using HF and DFT, respectively. Both single-point and relative energy calculations demonstrate that the EE-GMFCC method has deviations from the full system results of only a few kcal/mol.

  19. 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.

  20. Does the DFT Self-Interaction Error Affect Energies Calculated in Proteins with Large QM Systems?

    PubMed

    Fouda, Adam; Ryde, Ulf

    2016-11-08

    We have examined how the self-interaction error in density-functional theory (DFT) calculations affects energies calculated on large systems (600-1000 atoms) involving several charged groups. We employ 18 different quantum mechanical (QM) methods, including Hartree-Fock, as well as pure, hybrid, and range-separated DFT methods. They are used to calculate reaction and activation energies for three different protein models in vacuum, in a point-charge surrounding, or with a continuum-solvent model. We show that pure DFT functionals give rise to a significant delocalization of the charges in charged groups in the protein, typically by ∼0.1 e, as evidenced from the Mulliken charges. This has a clear effect on how the surroundings affect calculated reaction and activation energies, indicating that these methods should be avoided for DFT calculations on large systems. Fortunately, methods such as CAM-B3LYP, BHLYP, and M06-2X give results that agree within a few kilojoules per mole, especially when the calculations are performed in a point-charge surrounding. Therefore, we recommend these methods to estimate the effect of the surroundings with large QM systems (but other QM methods may be used to study the intrinsic reaction and activation energies).

  1. Improved Sugar Puckering Profiles for Nicotinamide Ribonucleoside for Hybrid QM/MM Simulations.

    PubMed

    Pshetitsky, Yaron; Eitan, Reuven; Verner, Gilit; Kohen, Amnon; Major, Dan Thomas

    2016-10-11

    The coenzyme nicotinamide adenine dinucleotide (NAD(+)) and its reduced form (NADH) play ubiquitous roles as oxidizing and reducing agents in nature. The binding, and possibly the chemical redox step, of NAD(+)/NADH may be influenced by the cofactor conformational distribution and, in particular, by the ribose puckering of its nicotinamide-ribonucleoside (NR) moiety. In many hybrid quantum mechanics-molecular mechanics (QM/MM) studies of NAD(+)/NADH dependent enzymes, the QM region is treated by semiempirical (SE) methods. Recent work suggests that SE methods do not adequately describe the ring puckering in sugar molecules. In the present work we adopt an efficient and practical strategy to correct for this deficiency for NAD(+)/NADH. We have implemented a cost-effective correction to a SE Hamiltonian by adding a correction potential, which is defined as the difference between an accurate benchmark density functional theory (DFT) potential energy surface (PES) and the SE PES. In practice, this is implemented via a B-spline interpolation scheme for the grid-based potential energy difference surface. We find that the puckering population distributions obtained from free energy QM(SE)/MM simulations are in good agreement with DFT and in fair accord with experimental results. The corrected PES should facilitate a more accurate description of the ribose puckering in the NAD(+)/NADH cofactor in simulations of biological systems.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Competitive adsorption of VOCcs and BOM: Oxic and anoxic environments

    SciTech Connect

    Sorial, G.A.; Papadimas, S.P.; Suidan, M.T.; Speth, T.F.

    1994-01-01

    The effect of the presence of molecular oxygen on the adsorption of volatile organic compounds (VOCs) in distilled Milli-Q water and in water supplemented with background organic matter (BOM) is evaluated. Experiments are conducted under conditions where molecular oxygen is present in the test environment (oxic adsorption), and where oxygen is absent from the test environment (anoxic adsorption). Adsorption isotherms for tetrachloroethylene (PCE) and trichloroethylene (TCE) in Milli-Q water showed no impact of the presence of oxygen on their adsorption behavior, while adsorption isotherms for cis-1,2-dichloroethylene (DCE) showed higher capacities under toxic conditions. The Ideal Adsorbed Solution Theory (IAST) successfully predicted the VOCs anoxic adsorption isotherms in BOM. However, the IAST model did not predict the VOCs oxic adsorption isotherms in BOM.

  7. 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.

  8. Factors affecting drug adsorption on beta zeolites.

    PubMed

    Pasti, Luisa; Sarti, Elena; Cavazzini, Alberto; Marchetti, Nicola; Dondi, Francesco; Martucci, Annalisa

    2013-05-01

    The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO2/Al2O3 ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X-ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.

  9. Development of linear scaling QM/MM methods using BRABO/CHARMM

    NASA Astrophysics Data System (ADS)

    Swerts, Benjamin

    As we focus on the quantum mechanical (QM) description of large molecular systems in our research group, the goal of my research was extending the size-limit of molecular systems through the use of QM/MM. In this type of calculation, a small region of the system is described by quantum mechanics while the remaining bulk is described by molecular mechanics (MM). As a first step, the BRABO program package was interfaced with the MM program CHARMM, which is optimised for biomolecules. In the simplest implementation of QM/MM, the QM and MM regions are comprised of entire molecules and consequently interact only through nonbonded interactions: electrostatics and Van der Waals interactions. On this basis, two models for the description of molecular crystals were developed. With BRABO it was possible to do cluster calculations with the Point Charge (PC) and Supermolecule (SM) models. In the cluster model, a central molecule is surrounded by identical molecules arranged according to its space group symmetry. In the PC model, the surrounding molecules are represented by ab initio charges placed on the atomic positions. In the SM model, the nearest neighbours are also included in the wavefunction. The two new QM/MM models are based thereon and named the Extended Point Charge (PCX) and Extended Supermolecule (SMX) models. The main differences lie in the addition of classical Van der Waals interactions between the central molecule and the neighbours, and the different type of electrostatics: fixed force field charges versus geometry dependent ab initio charges. The PCX and SMX models were tested on a number of organic crystals, including formamide oxime, alpha-glycine, and the yellow form of dimethyl 3,6-dichloro-2,5-dihydroxyterephthalate. It was concluded that the PCX and SMX models can give a significant improvement over the ab initio cluster models. With the PCX model, results of SM quality can be obtained at PC cost. With the SMX model, increased accuracy can be obtained

  10. 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.

  11. QM/MM modelling of ketosteroid isomerase reactivity indicates that active site closure is integral to catalysis.

    PubMed

    van der Kamp, Marc W; Chaudret, Robin; Mulholland, Adrian J

    2013-07-01

    Ketosteroid isomerase (Δ⁵-3-keto steroid isomerase or steroid Δ-isomerase) is a highly efficient enzyme at the centre of current debates on enzyme catalysis. We have modelled the reaction mechanism of the isomerization of 3-oxo-Δ⁵-steroids into their Δ⁴-conjugated isomers using high-level combined quantum mechanics/molecular mechanics (QM/MM) methods, and semi-empirical QM/MM molecular dynamics simulations. Energy profiles were obtained at various levels of QM theory (AM1, B3LYP and SCS-MP2). The high-level QM/MM profile is consistent with experimental data. QM/MM dynamics simulations indicate that active site closure and desolvation of the catalytic Asp38 occur before or during formation of dienolate intermediates. These changes have a significant effect on the reaction barrier. A low barrier to reaction is found only when the active site is closed, poising it for catalysis. This conformational change is thus integral to the whole process. The effects on the barrier are apparently largely due to changes in solvation. The combination of high-level QM/MM energy profiles and QM/MM dynamics simulation shows that the reaction involves active site closure, desolvation of the catalytic base, efficient isomerization and re-opening of the active site. These changes highlight the transition between the ligand binding/releasing form and the catalytic form of the enzyme. The results demonstrate that electrostatic interactions (as a consequence of pre-organization of the active site) are crucial for stabilization during the chemical reaction step, but closure of the active site is essential for efficient catalysis to occur.

  12. Characterization of gene expression of QM from Caragana jubata, a plant species that grows under extreme cold.

    PubMed

    Bhardwaj, Pardeep Kumar; Ahuja, Paramvir Singh; Kumar, Sanjay

    2010-02-01

    Caragana [Caragana jubata (Pall.) Poir] is a temperate plant that thrives well under extremes of cold in high altitude of Himalaya and hence the plant is expected to be a source of genes that might play an important role in tolerance to low temperature (LT). In order to identify LT inducible gene(s), differential display of mRNA (DD) was performed using the apical buds growing under snow as well as growing in the near vicinity without snow, and a LT inducible QM gene (CjQM) homologue was identified. Realizing the importance of QM gene (which encodes human Wilms' tumor suppressor QM protein) in aggregation of 40 and 60S ribosomal subunit and that not much has been reported on this gene in plant systems in relation to its relationship with LT, full length cDNA of CjQM was cloned through rapid amplification of cDNA ends. The gene (977 bp), encoded by small gene family, had an open reading frame of 651 bp and was found to be intronless. The gene exhibited up-regulation within 20 min of exposure to LT and abscisic acid (ABA), but no significant change in gene expression was observed in response to drought stress (DS), salicylic acid (SA) and methyl jasmonate (MJ) application. Up-regulation of CjQM was obtained in the tissues growing in situ under snow. Non-responsiveness of CjQM towards DS, SA and MJ, but up-regulation in response to LT and ABA suggested a specific regulation of the gene in Caragana under varied cues.

  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. Polychelated cryogels: hemoglobin adsorption from human blood.

    PubMed

    Erol, Kadir

    2017-02-01

    The separation and purification methods are extremely important for the hemoglobin (Hb) which is a crucial biomolecule. The adsorption technique is popular among these methods and the cryogels have been used quite much due to their macropores and interconnected flow channels. In this study, the Hb adsorption onto the Cu(II) immobilized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA)-Cu(II), cryogels was investigated under different conditions (pH, interaction time, initial Hb concentration, temperature and ionic strength) to optimize adsorption conditions. The swelling test, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), surface area (BET), elemental and ICP-OES analysis were performed for the characterization of cryogels. Polyethyleneimine (PEI) molecule was used as a Cu(II)-chelating ligand. The Hb adsorption capacity of cryogels was determined as 193.8 mg Hb/g cryogel. The isolation of Hb from human blood was also studied under optimum adsorption conditions determined and the Hb (124.5 mg/g cryogel) was isolated. The adsorption model was investigated in the light of Langmuir and Freundlich adsorption isotherm models and it was determined to be more appropriate to the Langmuir adsorption isotherm model.

  15. Phosphoryl functionalized mesoporous silica for uranium adsorption

    NASA Astrophysics Data System (ADS)

    Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

    2017-04-01

    Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N2 adsorption-desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG0, ΔH0 and ΔS0) confirmed that the adsorption process was endothermic and spontaneous.

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

    SciTech Connect

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

    2014-10-16

    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. Here, 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.

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

    DOE PAGES

    Sodt, Alexander J.; Mei, Ye; Konig, Gerhard; ...

    2014-10-16

    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 completelymore » avoided at each configuration. Here, 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.« less

  18. Intersystem Crossing Enables 4-Thiothymidine to Act as a Photosensitizer in Photodynamic Therapy: An Ab Initio QM/MM Study.

    PubMed

    Cui, Ganglong; Thiel, Walter

    2014-08-07

    Motivated by its potential use as a photosensitizer in photodynamic therapy, we report the first ab initio quantum mechanics/molecular mechanics (QM/MM) study of 4-thiothymidine in aqueous solution. The core chromophore 4-thiothymine was described using the multiconfigurational CASSCF and CASPT2 QM methods, while the ribose and the solvent water molecules were treated at the MM level (CHARMM and TIP3P, respectively). The minima of the five lowest electronic states (S0, S1, S2, T1, and T2) and six minimum-energy intersections were fully optimized at the QM(CASSCF)/MM level, and their energies were further refined by single-point QM(CASPT2)/MM and CASPT2 calculations. The relevant spin-orbit couplings were also computed. We find that (1) there are three efficient photophysical pathways that account for the experimentally observed ultrafast formation of the lowest triplet state with a quantum yield of nearly unity, (2) the striking qualitative differences in the photophysical behavior of 4-thiothymine and thymine originate from the different electronic structure of their S1 states, and (3) environmental effects play an important role. The present QM/MM calculations provide mechanistic insight that may guide the design of improved photosensitizers for photodynamic therapy.

  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. 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.

  1. 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.

  2. 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.

  3. SIM.QM-S2 supplemental: Trace elements in drinking water

    NASA Astrophysics Data System (ADS)

    Willie, Scott

    2012-01-01

    In order to address laboratory capability for the determination of trace elements in drinking water and to support corresponding CMC submissions for several SIM members, the exercise SIM.QM-S2 was planned in 2008 and authorized as a supplementary comparison at the April 2010 meeting of the Inorganic Analysis Working Group (IAWG) of the Consultative Committee for Amount of Substance-Metrology in Chemistry (CCQM). Laboratories participating in SIM.QM-S2 generally agree within stated uncertainties with the reference value. This analysis is relatively easy as the matrix is simple and the mass fractions are above ICP-MS detection limits for cadmium, lead and nickel, and with that for calcium also well above the detection limit for ICP-OES and FAAS. The calcium results for all but two laboratories are traceable to the same NIST SRM used to spike the solution, resulting in a comparison of preparation of calibration solutions rather than a matrix sample. Core capability forms submitted by the SIM.QM-S2 participants generally agreed that this exercise demonstrated a low level of difficulty. It would be expected that potential CMC claims as a result of this study could not be extended beyond similar water samples with a simple matrix. 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 SIM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

  4. Exploring SCC-DFTB paths for mapping QM/MM reaction mechanisms.

    PubMed

    Woodcock, H Lee; Hodoscek, Milan; Brooks, Bernard R

    2007-07-05

    A new first-order procedure for locating transition structures (TS) that employs hybrid quantum mechanical/molecular mechanical (QM/MM) potentials has been developed. This new technique (RPATh+RESD) combines the replica path method (RPATh) and standard reaction coordinate driving (RCD) techniques in an approach that both efficiently determines reaction barriers and successfully eliminates two key weaknesses of RCD calculations (i.e., hysteresis/discontinuities in the path and the sequential nature of the RCD procedure). In addition, we have extended CHARMM's QM/MM reaction pathway methods, the RPATh and nudged elastic band (NEB) methods, to incorporate SCC-DFTB wave functions. This newly added functionality has been applied to the chorismate mutase-catalyzed interconversion of chorismate to prephenate, which is a key step in the shikimate pathway of bacteria, fungi, and other higher plants. The RPATh+RESD barrier height (DeltaE=5.7 kcal/mol) is in good agreement with previous results from full-energy surface mapping studies (Zhang, X.; Zhang, X.; Bruice, T. C. Biochemistry 2005, 44, 10443-10448). Full reaction paths were independently mapped with RPATh and NEB methods and showed good agreement with the final transition state from the RPATh+RESD "gold standard" and previous high-level QM/MM transition states (Woodcock, H. L.; Hodoscek, M.; Gilbert, T. B.; Gill, P. M. W.; Schaefer, H. F.; Brooks, B. R. J. Comput. Chem. 2007, 28, 1485-1502). The SCC-DFTB TS geometry most closely approximates the MP2/6-31+G(d) QM/MM result. However, the barrier height is underestimated and possibly points to an area for improvement in SCC-DFTB parametrization. In addition, the steepest descents (SD) minimizer for the NEB method was modified to uncouple the in-path and off-path degrees of freedom during the minimization, which significantly improved performance. The convergence behavior of the RPATh and NEB was examined for SCC-DFTB wave functions, and it was determined that, in general

  5. 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.

  6. 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...

  7. 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.

  8. 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.

  9. 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.

  10. 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

    2016-07-05

    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.

  11. Ionic Adsorption and Desorption of CNT Nanoropes

    PubMed Central

    Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

    2016-01-01

    A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment. PMID:28335306

  12. Plasmid-encoded genes influence exosporium assembly and morphology in Bacillus megaterium QM B1551 spores.

    PubMed

    Manetsberger, Julia; Hall, Elizabeth A H; Christie, Graham

    2015-09-01

    Spores of Bacillus megaterium QM B1551 are encased in a morphologically distinctive exosporium. We demonstrate here that genes encoded on the indigenous pBM500 and pBM600 plasmids are required for exosporium assembly and or stability in spores of this strain. Bioinformatic analyses identified genes encoding orthologues of the B. cereus-family exosporium nap and basal layer proteins within the B. megaterium genome. Transcriptional analyses, supported by electron and fluorescent microscopy, indicate that the pole-localized nap, identified here for the first time in B. megaterium QM B1551 spores, is comprised of the BclA1 protein. The role of the BxpB protein, which forms the basal layer of the exosporium in B. cereus spores, is less clear since spores of a null mutant strain display an apparently normal morphology. Retention of the localized nap in bxpB null spores suggests that B. megaterium employs an alternative mechanism to that used by B. cereus spores in anchoring the nap to the spore surface.

  13. 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.

  14. Plasmid-encoded genes influence exosporium assembly and morphology in Bacillus megaterium QM B1551 spores

    PubMed Central

    Manetsberger, Julia; Hall, Elizabeth A. H.; Christie, Graham

    2015-01-01

    Spores of Bacillus megaterium QM B1551 are encased in a morphologically distinctive exosporium. We demonstrate here that genes encoded on the indigenous pBM500 and pBM600 plasmids are required for exosporium assembly and or stability in spores of this strain. Bioinformatic analyses identified genes encoding orthologues of the B. cereus-family exosporium nap and basal layer proteins within the B. megaterium genome. Transcriptional analyses, supported by electron and fluorescent microscopy, indicate that the pole-localized nap, identified here for the first time in B. megaterium QM B1551 spores, is comprised of the BclA1 protein. The role of the BxpB protein, which forms the basal layer of the exosporium in B. cereus spores, is less clear since spores of a null mutant strain display an apparently normal morphology. Retention of the localized nap in bxpB null spores suggests that B. megaterium employs an alternative mechanism to that used by B. cereus spores in anchoring the nap to the spore surface. PMID:26316548

  15. QM/MM Simulation on P450 BM3 Enzyme Catalysis Mechanism

    PubMed Central

    Tian, Li; Friesner, Richard A.

    2009-01-01

    Using a structure generated by induced fit modeling of the protein-ligand complex, the reaction path for hydrogen atom abstraction in P450 BM3 is studied by means of mixed QM/MM methods to determine the structures and energetics along the reaction path. The IFD structure is suitable for hydrogen atom abstraction at the ω-1 position. The electronic structures obtained are similar to those observed in P450 cam. We show that the barrier for the hydrogen abstraction step from QM/MM modeling is 13.3 kcal/mol in quartet and 15.6 kcal/mol in doublet. Although there is some strain energy present in the ligand, the activation barrier is not dramatically affected. A crystal water molecule, HOH502, plays a role as catalyst and decreases the activation barrier by about 2 kcal/mol and reaction energy by about 3-4 kcal/mol. In order to achieve reactive chemistry at the remaining experimentally observed positions in the hydrocarbon tail of the ligand, other structures would have to be utilized as a starting point for the reaction. Finally, the present results still leave open the question of whether DFT methods provide an accurate computation of the barrier height in the P450 hydrogen atom abstraction reaction. PMID:20046929

  16. ℏ derived from cosmology and origin of special relativity and QM.

    NASA Astrophysics Data System (ADS)

    Cavalleri, G.

    1997-09-01

    Electrons are assumed to have the speed c of light and an e.m. self-reaction perpendicular to the velocity so that they perform a circular motion (spin or real zitterbewegung) that generates the zero-point field, hence special relativity. The spin angular frequency ωs = c/Rs, where Rs is the radius of the spin orbit, is obtained from the Hubble constant H and the average density N of electrons in the universe by equating the powers Pradiated = Pabsorbed. Used in the reverse way the new relationship leads to values of H and of Ωb = ρmb/qme (where ρmb is the average baryonic mass density of the universe and ρme the critical mass density) in agreement with recent observations. Quantum mechanics (QM) is derived as well, although the Schrödinger equation is found to be an approximate regime equation not valid for scattering. Even for diffraction of electrons there are different predictions between QM and the proposed stochastic electrodynamics implemented by spin. A relevant experiment to discriminate between the two theories is proposed.

  17. 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.

  18. Molecular characterization, immune responsive expression and functional analysis of QM, a putative tumor suppressor gene from the Pacific white shrimp, Litopenaeus vannamei.

    PubMed

    Liu, Yongjie; Qian, Zhaoying; Qu, Rongfeng; Wang, Xianzong; He, Shulin; Hou, Fujun; Liu, Qiao; Mi, Xiao; Liu, Xiaolin

    2014-03-01

    The QM, firstly identified as a putative tumor suppressor gene from human, has been confirmed to possess varieties of functions in a range of organisms. In the present study, the cDNA that encodes a 220-amino-acid QM protein with calculated molecular mass of 25.5 kDa and isoelectric point of 10.07 was characterized from the Pacific white shrimp Litopenaeus vannamei. Analysis of the deduced amino acid sequence of LvQM revealed that it contained a series of conserved functional motifs. Quantitative real-time PCR (qRT-PCR) results showed that the transcript of LvQM was extensively distributed in the tissues under investigation and most highly expressed in gill. After challenged with Vibrio anguillarum, the LvQM transcripts were significantly increased (P < 0.05) both in hepatopancreas and hemocytes in the early experimental phase. When LvQM was knocked down by RNA interference (RNAi), the transcript of prophenoloxidase (proPO) and the phenoloxidase activity (PO) in shrimp hemolymph were dramatically decreased, while the mortality was significantly increased. Furthermore, the recombinant LvQM protein (rLvQM) was successfully expressed in Escherichia coli BL21 (DE3)-pLysS. Injecting the purified rLvQM mixed with V. anguillarum markedly increased the clearance rate of bacteria and PO activity in the shrimp hemolymph. Hence, we conclude that LvQM was involved in the host defense of L. vannamei, probably as a positive regulator to phenoloxidase activity.

  19. Adsorption of malathion on thermally treated egg shell material.

    PubMed

    Elwakeel, Khalid Z; Yousif, Ahmed M

    2010-01-01

    Thermally treated egg shell materials were prepared at different temperatures. The samples were investigated by means of FT-IR and thermogravimetric analysis (TGA). The adsorption behaviour of malathion on egg shell and its thermally treated samples was studied using batch method and gave uptake capacities up to 0.964 mmol/g. Adsorption kinetics as well as the adsorption isotherms were discussed. Regeneration of the loaded adsorbent beads towards the successive cycles was also clarified. The adsorption of malathion is maintained until the third cycle without a significant activity loss.

  20. 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.

  1. 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

  2. [Dynamics of soil phosphorus adsorption-desorption in maize/soybean relay intercropping system in purple hilly area].

    PubMed

    Xu, Min; Song, Chun; Dai, Wei; Xiao, Xia; Mao, Lu; Wang, Xiao-chun; Yang, Wen-yu

    2015-07-01

    Field plot experiment was carried out to study the effect of phosphorus application on soil phosphorus adsorption-desorption characteristics under three cropping patterns including maize/soybean relay intercropping (M/S), maize monoculture (M), and soybean monoculture (S). Results showed that without phosphorus fertilization, the system crop yield under M/S was increased by 9.8% and 79. 1% compared with that of M and S, respectively, and the land equivalent ratio (LER) was 1.58. With phosphate fertilizer application, the system crop yield under M/S was increased by 10.4% and 80.3% compared with that of M and S, respectively, and the LER was 1.62. The system crop yields under M/S, M and S with phosphate fertilizer application were increased by 12.7%, 12. 2% and 17. 6%, respectively, compared with that without phosphorus fertilization. Among three cropping patterns, the soil buffer capacity (SBC) values were in the order of M/S>M >S regardless of phosphate fertilizer applied or not. The SBC values of M/S, M and S without phosphate fertilizer application were reduced by 19.6%, 30.3% and 12.0% compared with phosphate fertilizer application treatments, respectively. The soil desorption per absorption (b) values of the three cropping patterns with phosphate fertilizer application were in the order of M/S>M>S, and the b values increased by 10.9%, 39.1% and -9.6%, respectively, compared with non phosphate fertilizer application. The soil phosphorus maximum absorption (Qm) and soil phosphorus desorption rate also showed the same trend.

  3. 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

  4. 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

  5. Porous cellulose spheres: Preparation, modification and adsorption properties.

    PubMed

    Ma, Xiaofei; Liu, Congzhi; Anderson, Debbie P; Chang, Peter R

    2016-12-01

    Porous cellulose spheres (PCS) were fabricated by precipitating the spheres from a cellulose ionic liquid solution, followed by freezing, solvent exchange, and drying. PCS had low crystallinity and a large surface area that facilitated modification with trisodium trimetaphosphate (STMP) to introduce phosphate ester groups into the porous structure of the heterogeneous system. The STMP-modified PCS (SPCS) were used to remove heavy metal ions from aqueous solution. With increasing STMP dosage, the adsorption capacity of SPCS obviously improved due to chelation between Pb(2+) and phosphate ester groups. The kinetic adsorption and isotherm data matched the pseudo-second order model and the Langmuir model well. The maximum adsorption capacity reached 150.6 mg g(-1) for SPCS. SPCS were competitive with other absorbents because the phosphate ester groups and porous structure contributed to Pb(2+) adsorption. Moreover, SPCS can be regenerated with ethylenediamine tetraacetic acid disodium salt (EDTA) solution for repetitious adsorption of Pb(2+).

  6. 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.

  7. Adsorption of trichlorophenol on zeolite and adsorbent regeneration with ozone.

    PubMed

    Zhang, Yongjun; Mancke, Raoul Georg; Sabelfeld, Marina; Geißen, Sven-Uwe

    2014-04-30

    A FAU-type zeolite was studied as an adsorbent to remove 2,4,6-trichlorophenol (TCP), a frequently detected recalcitrant pollutant in water bodies. Both adsorption isotherm and kinetics were studied with TCP concentrations from 10 to 100mg/L. It was observed that TCP was effectively adsorbed onto the zeolite with a high adsorption capacity and a high kinetic rate. Freundlich model and pseudo-second-order kinetics were successfully applied to describe the experimental data. The influence of solution pH was also studied. Furthermore, ozone was applied to regenerate the loaded zeolite. It was found that an effective adsorption of TCP was kept for at least 8 cycles of adsorption and regeneration. The ozonation also increased the BET specific surface of zeolite by over 60% and consequently enhanced the adsorption capacity.

  8. Blind prediction of distribution in the SAMPL5 challenge with QM based protomer and p K a corrections

    NASA Astrophysics Data System (ADS)

    Pickard, Frank C.; König, Gerhard; Tofoleanu, Florentina; Lee, Juyong; Simmonett, Andrew C.; Shao, Yihan; Ponder, Jay W.; Brooks, Bernard R.

    2016-11-01

    The computation of distribution coefficients between polar and apolar phases requires both an accurate characterization of transfer free energies between phases and proper accounting of ionization and protomerization. We present a protocol for accurately predicting partition coefficients between two immiscible phases, and then apply it to 53 drug-like molecules in the SAMPL5 blind prediction challenge. Our results combine implicit solvent QM calculations with classical MD simulations using the non-Boltzmann Bennett free energy estimator. The OLYP/DZP/SMD method yields predictions that have a small deviation from experiment (RMSD = 2.3 log D units), relative to other participants in the challenge. Our free energy corrections based on QM protomer and {{p}}K_{{a}} calculations increase the correlation between predicted and experimental distribution coefficients, for all methods used. Unfortunately, these corrections are overly hydrophilic, and fail to account for additional effects such as aggregation, water dragging and the presence of polar impurities in the apolar phase. We show that, although expensive, QM-NBB free energy calculations offer an accurate and robust method that is superior to standard MM and QM techniques alone.

  9. Optimization of cutting schemes for the evaluation of molecular electrostatic potentials in proteins via Moving-Domain QM/MM.

    PubMed

    Menikarachchi, Lochana C; Gascón, José A

    2008-06-01

    This work presents new developments of the moving-domain QM/MM (MoD-QM/MM) method for modeling protein electrostatic potentials. The underlying goal of the method is to map the electronic density of a specific protein configuration into a point-charge distribution. Important modifications of the general strategy of the MoD-QM/MM method involve new partitioning and fitting schemes and the incorporation of dynamic effects via a single-step free energy perturbation approach (FEP). Selection of moderately sized QM domains partitioned between C (alpha) and C (from C=O), with incorporation of delocalization of electrons over neighboring domains, results in a marked improvement of the calculated molecular electrostatic potential (MEP). More importantly, we show that the evaluation of the electrostatic potential can be carried out on a dynamic framework by evaluating the free energy difference between a non-polarized MEP and a polarized MEP. A simplified form of the potassium ion channel protein Gramicidin-A from Bacillus brevis is used as the model system for the calculation of MEP.

  10. Conformational effects in enzyme catalysis: QM/MM free energy calculation of the 'NAC' contribution in chorismate mutase.

    PubMed

    Ranaghan, Kara E; Mulholland, Adrian J

    2004-05-21

    The controversial 'near attack conformation'(NAC) effect in the important model enzyme chorismate mutase is calculated to be 3.8-4.6 kcal mol(-1) by QM/MM free energy perturbation molecular dynamics methods, showing that the NAC effect by itself does not account for catalysis in this enzyme.

  11. Amino acid availability regulates S6K1 and protein synthesis in avian insulin-insensitive QM7 myoblasts.

    PubMed

    Tesseraud, Sophie; Bigot, Karine; Taouis, Mohammed

    2003-04-10

    The regulation of S6K1 by nutritional status and insulin has been recently reported in vivo in chicken muscle despite the relative insulin resistance of this tissue as estimated by phosphatidylinositol 3-kinase (PI3-kinase) activity. The present work aimed to study the impact of amino acids on S6K1 activity in quail muscle (QM7) myoblasts. Firstly, we characterized S6K1 in QM7 cells and demonstrated the absence of insulin receptors in these cells. Secondly, we showed that amino acids in the absence of insulin induced S6K1 phosphorylation on Thr389 and concomitantly increased its enzymatic activity. Amino acid-induced S6K1 activation was inhibited by LY294002 (PI3-kinase inhibitor) and rapamycin (inhibitor of the mammalian target of rapamycin, mTOR), suggesting the involvement of an avian homolog of mTOR. The availability of individual amino acids (methionine or leucine) regulated S6K1 phosphorylation on Thr389 and QM7 protein synthesis. In conclusion, amino acids regulate S6K1 phosphorylation and activity in QM7 cells through the mTOR/PI3-kinase pathway in an insulin-independent manner.

  12. Computational study of Au_4 cluster on a carbon nanotube with and without defects using QM/MM methodology.

    PubMed

    Barraza-Jimenez, Diana; Galvan, D H; Posada-Amarillas, Alvaro; Flores-Hidalgo, Manuel Alberto; Glossman-Mitnik, Daniel; Jose-Yacaman, Miguel

    2012-11-01

    We use ONIOM (QM/MM) methodology to carry out geometry calculations in a 4-atom nanocluster supported by an (8, 8) armchair carbon nanotube with and without defects employing LSDA/SDD for the QM system and UFF for MM. In two particular cases, defects were added in the carbon nanotube wall. These defects are a double oxygenated vacancy (Vac₂O₂) and a double vacancy but without oxygen which creates two pentagons and an octagon. Our results show how geometries using QM/MM and energies calculations carried out with QM, change on both the gold nanocluster and the carbon nanotube. In addition, an application of ONIOM methodology in a comparative study to predict behavior of structures as hybrid materials based in carbon nanotubes combined with gold nanoclusters is shown. In this work we examine geometry changes on both the gold nanocluster and the carbon nanotube. A comparison is made with the binding energy resulting values as well as with the orbital energies such as the frontier orbitals HOMO and LUMO.

  13. 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.

  14. 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.

  15. 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...

  16. Phosphorus recovery using pelletized adsorptive materials ...

    EPA Pesticide Factsheets

    Phosphorous (P) is one of the essential nutrients for growth and is generally the most limiting nutrient since, it cannot be fixed from the atmosphere. Methods for recovering phosphorous from water systems already exist, but advances are being made to find a more economic, efficient, effective and easy to use method that can allow for reuse of the recovered P. One area of study is in adsorption, which involves finding the best material for adsorption of phosphorous from water and for releasing it back into the environment through desorption or leaching. The goal of this research was to first optimize the capacity for a pelletized adsorptive material that was synthesized with varying amounts of a binder material from 0-20 % and then to study recovering the phosphate for reuse. The pelletized materials were studied through kinetics experiments as well as isotherm experiments to gain insight into the adsorption capacity and mechanism. Following successful adsorption, a simple leaching study was conducted to see how much phosphate would be released back into water without any added desorption aid. Desorption was then studied by changing the pH of solution. Presenting my thesis work with a poster at ACS.

  17. Sulfate adsorption in Michigan forest soils

    SciTech Connect

    MacDonald, N.W.

    1987-01-01

    The occurrence of acidic atmospheric deposition raised concerns over adverse cation leaching effects on Michigan forest soils with low cation exchange capacities. Leaching effects of acid deposition depend on mobility of sulfate in the soil. Little was known, however, concerning the ability of these soils to adsorb sulfate. The objectives of this study were to determine the ability of representative Michigan forest soils to adsorb sulfate, to relate sulfate adsorption to soil properties, and to develop equations to predict sulfate adsorption in similar forest soils. Frigid zone soil series studied were Grayling (Typic Udipsamments), Rubicon (Entic Haplorthods), Kalkaska (Typic Haplorthods), and Montcalm (Eutric Glossoboralfs). Mesic zone series studied were Spinks (Psammentic Hapludals) and Oshtemo (Typic Hapludalfs). Six randomly located pedons of each series were sampled. Sulfate adsorption was determined by shaking 10 gram soil samples for 24 hours in 50 mL 0.01 M CaCl/sub 2/ solution containing 10 mg SO/sub 4/-S L/sup -1/. Solution filtrates were turbidimetrically analyzed for SO/sub 4/-S and adsorption was calculated from reduction in SO/sub 4/-S concentration. Bw, Bs, and Bh horizons of frigid zone soils and E and Bt horizons of mesic zone soils had the highest sulfate adsorbing abilities. No significant differences were found between series in total sulfate adsorptive capacity.

  18. Adsorption of ammonia by sulfuric acid treated zirconium hydroxide.

    PubMed

    Glover, T Grant; Peterson, Gregory W; DeCoste, Jared B; Browe, Matthew A

    2012-07-17

    The adsorption of ammonia on Zr(OH)(4), as well as Zr(OH)(4) treated with sulfuric acid, were examined. The results show that treating Zr(OH)(4) with sulfuric acid leads to the formation of a sulfate on the surface of the material, and that the sulfate contributes to the ammonia adsorption capacity through the formation of an ammonium sulfates species. Calcination of Zr(OH)(4) decreases the ammonia adsorption capacity of the material and limits the formation of sulfate species. NMR and FTIR spectroscopy results are presented that show the presence of two distinct ammonium species on the surface of the material. The adsorption capacity of the materials is shown to be a complex phenomenon that is impacted by the surface area, the sulfur content, and the pH of the material. The results illustrate that Zr(OH)(4), which is known to adsorb acidic gases, can be modified and used to adsorb basic gases.

  19. 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.

  20. Three dimensional MOF-sponge for fast dynamic adsorption.

    PubMed

    Li, Huizeng; Li, Mingzhu; Li, Wenbo; Yang, Qiang; Li, Yanan; Gu, Zhenkun; Song, Yanlin

    2017-02-22

    Nowadays, environmental pollution is a big problem. Metal organic frameworks (MOFs) provide a novel strategy for exhaust gases adsorption and toxic pollutants removal. We proposed a facile and versatile method to prepare a highly efficient three dimensional MOF-sponge by coating MOF crystals on polyurethane sponge surface, mimicking the porous structure of the marine animal, sponge. Owing to combination of the spatial structure of the commercial sponge and the excellent adsorption capacity of MOF coatings, the MOF-sponge possessed good permeability and high dynamic adsorption capacity. Dynamic adsorption ability of the prepared Cu3(BTC)2-sponge was demonstrated by flowing gas-mixtures of NH3/N2 and an aquatic solution of Rhodamine B through it, with a capacity of 101.6 mg g(-1) and 8.8 mg g(-1) for NH3 and Rhodamine B, respectively.

  1. Equilibrium and kinetic adsorption study of the adsorptive removal of Cr(VI) using modified wheat residue.

    PubMed

    Chen, Suhong; Yue, Qinyan; Gao, Baoyu; Xu, Xing

    2010-09-01

    A new adsorbent modified from wheat residue was synthesized after reaction with epichlorohydrin and triethylamine by using the modifying agents of diethylenetriamine in the presence of organic medium of N,N-dimethylformamide. The performance of the modified wheat straw (MWS) was characterized by Fourier transform infrared spectroscopy and point of zero charge analysis. The adsorption was investigated in a batch adsorption system, including both equilibrium adsorption isotherms and kinetics. Results showed that MWR had great anion-adsorbing capacity, due to the existence of a large number of introduced amino groups, and the value of pH(PZC) was around 5.0. Equilibrium data were analyzed using the Langmuir, Freundlich, and Temkin isotherm models and were found to be best represented by the Freundlich isotherm model. Evaluation of the adsorption process identified its endothermic nature. The maximum adsorption capacity of MWS for the removal of Cr(VI) was 322.58mg/g at 328K, indicating that MWS has high chromium removal efficiency, compared to other adsorbents reported. The kinetics of adsorption followed the pseudo-second-order kinetic equation. The mechanism of adsorption was investigated using the intraparticle diffusion model. Thermodynamic parameters (free energy change, enthalpy change, and entropy change) revealed that the adsorption of Cr(VI) onto MWS was endothermic and spontaneous; additionally, the adsorption can be characterized as an ion-exchange process. The results suggest that MWS is an inexpensive and efficient adsorbent for removing Cr(VI) ions from aqueous solution.

  2. Adsorption studies of methylene blue dye on tunisian activated lignin

    NASA Astrophysics Data System (ADS)

    Kriaa, A.; Hamdi, N.; Srasra, E.

    2011-02-01

    Activated carbon prepared from natural lignin, providing from a geological deposit, was used as the adsorbent for the removal of methylene blue (MB) dye from aqueous solutions. Batch adsorption studies were conducted to evaluate various experimental parameters like pH and contact time for the removal of this dye. Effective pH for MB removal was 11. Kinetic study showed that the adsorption of dye was gradual process. Quasi equilibrium reached in 4 h. Pseudo-first-order, pseudo-second-order were used to fit the experimental data. Pseudo-second-order rate equation was able to provide realistic description of adsorption kinetics. The experimental isotherms data were also modelled by the Langmuir and Freundlich equation of adsorption. Equilibrium data fitted well with the Langmuir model with maximum monolayer adsorption capacity of 147 mg/g. Activated lignin was shown to be a promising material for adsorption of MB from aqueous solutions.

  3. Report of the key comparison APMP.QM-K19. APMP comparison on pH measurement of borate buffer

    NASA Astrophysics Data System (ADS)

    Hioki, Akiharu; Asakai, Toshiaki; Maksimov, Igor; Suzuki, Toshihiro; Miura, Tsutomu; Obromsook, Krairerk; Tangpaisarnkul, Nongluck; Rodruangthum, Patumporn; Wong, Siu-Kay; Lam, Wai-Hing; Zakaria, Osman; Anuar Mohd. Amin, Khirul; Thanh, Ngo Huy; Máriássy, Michal; Vyskocil, Leos; Hankova, Zuzana; Fisicaro, Paola; Stoica, Daniela; Singh, Nahar; Soni, Daya; Ticona Canaza, Galia; Kutovoy, Viatcheslav; Barbieri Gonzaga, Fabiano; Dias, Júlio Cesar; Vospelova, Alena; Bakovets, Nickolay; Zhanasbayeva, Bibinur

    2015-01-01

    The APMP.QM-K19 was organised by TCQM of APMP to test the abilities of the national metrology institutes in the APMP region to measure a pH value of a borate buffer. This APMP comparison on pH measurement was proposed by the National Metrology Institute of Japan (NMIJ) and the National Institute of Metrology (Thailand) (NIMT) at the APMP-TCQM meeting held 26-27 November 2012. After approval by TCQM, the comparison has been conducted by NMIJ and NIMT. The comparison is a key comparison following CCQM-K19 and CCQM-K19.1. The comparison material was a borate buffer of pH around 9.2 and the measurement temperatures were 15 °C, 25 °C and 37 °C. This is the second APMP key comparison on pH measurement and the fourth APMP comparison on pH measurement following APMP.QM-P06 (two phosphate buffers) in 2004, APMP.QM-P09 (a phthalate buffer) in 2006 and APMP.QM-K9/APMP.QM-P16 (a phosphate buffer) in 2010-2011. The results can be used further by any participant to support its CMC claim at least for a borate buffer. That claim will concern the pH method employed by the participant during this comparison and will cover the used temperature(s) or the full temperature range between 15°C and 37 °C for the participant which measured pH values at the three temperatures. 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 CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  4. 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...

  5. 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

  6. Predominance of gluconate formation from glucose during germination of Bacillus megaterium QM B1551 spores.

    PubMed Central

    Otani, M; Ihara, N; Umezawa, C; Sano, K

    1986-01-01

    Metabolic pathways of glucose during germination of Bacillus megaterium QM B1551 spores were studied by using specifically labeled glucose and gluconate. The Embden-Meyerhof pathway, the pentose cycle, and the direct oxidation route of glucose to gluconate (the gluconate pathway) were all operative at this stage; among those, gluconate accumulation was most predominant, especially in the early stage. Potassium fluoride, an enolase inhibitor, abolished the catabolism by the Embden-Meyerhof pathway totally without affecting gluconate accumulation. Under these conditions glucose was exclusively oxidized to gluconate. Gluconate thus accumulated could be metabolized further via phosphorylation by gluconate kinase. Remarkable gluconate accumulation was also demonstrated in several other spores requiring alanine as an effective germinant. NADH formed by the direct glucose oxidation may serve as a initial ATP source to phosphorylate glucose in germinating spores. PMID:3013833

  7. 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.

  8. A QM/MM study of the 5‧-AMP DNA hydrolysis of aprataxin

    NASA Astrophysics Data System (ADS)

    Hanaoka, Kyohei; Tanaka, Wataru; Kayanuma, Megumi; Shoji, Mitsuo

    2015-07-01

    Aprataxin is a DNA repair enzyme that hydrolyzes the abnormal 5‧-AMP termini of broken DNAs. Based on quantum mechanical/molecular mechanical (QM/MM) calculations, we found that the catalytic reaction proceeds in three steps; substrate protonation, DNA deadenylation and histidine-AMP intermediate hydrolysis. The calculated activation energies for the second and third reactions are 19.0 and 10.5 kcal mol-1, which can be attributed to a penta-coordinated AMP-phosphoryl formation and closing of a water molecule, respectively. We also found that a histidine-AMP intermediate is hydrolyzed easily in the third step when a water molecule closes within 3 Å to the phosphorus nucleus.

  9. 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.

  10. 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

  11. 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.

  12. Q/M distribution in pulsed corona powder coating spray cone

    SciTech Connect

    Inculet, I.I.; Castle, G.S.P.

    1995-12-31

    The advantages of using a high voltage pulsed corona superimposed on a lower voltage DC bias electrostatic field have been well-documented for the case of electrostatic precipitation of high resistivity dusts. The high voltage, short pulses achieve adequate charge-to-mass ratios, while reducing the total ionic current landing on the dust layer and thus minimizing the deleterious back corona effects. To throw further light on this corona charging process, which up to the present has not been put to wide use by the electrostatic painting industry, the authors present a preliminary experimental study applied to powder coating. Measurements are presented for the Q/M ratios of the charged powder fractions collected in an ensemble of 5 double Faraday pails mounted in a cross behind the target plane. The results indicate, in average, a substantial increase in the charge-to-mass ratio of powder, combined with a reduction of the total ionic current which bombards the painting target.

  13. Genome sequences of the biotechnologically important Bacillus megaterium strains QM B1551 and DSM319.

    PubMed

    Eppinger, Mark; Bunk, Boyke; Johns, Mitrick A; Edirisinghe, Janaka N; Kutumbaka, Kirthi K; Koenig, Sara S K; Creasy, Heather Huot; Rosovitz, M J; Riley, David R; Daugherty, Sean; Martin, Madeleine; Elbourne, Liam D H; Paulsen, Ian; Biedendieck, Rebekka; Braun, Christopher; Grayburn, Scott; Dhingra, Sourabh; Lukyanchuk, Vitaliy; Ball, Barbara; Ul-Qamar, Riaz; Seibel, Jürgen; Bremer, Erhard; Jahn, Dieter; Ravel, Jacques; Vary, Patricia S

    2011-08-01

    Bacillus megaterium is deep-rooted in the Bacillus phylogeny, making it an evolutionarily key species and of particular importance in understanding genome evolution, dynamics, and plasticity in the bacilli. B. megaterium is a commercially available, nonpathogenic host for the biotechnological production of several substances, including vitamin B(12), penicillin acylase, and amylases. Here, we report the analysis of the first complete genome sequences of two important B. megaterium strains, the plasmidless strain DSM319 and QM B1551, which harbors seven indigenous plasmids. The 5.1-Mbp chromosome carries approximately 5,300 genes, while QM B1551 plasmids represent a combined 417 kb and 523 genes, one of the largest plasmid arrays sequenced in a single bacterial strain. We have documented extensive gene transfer between the plasmids and the chromosome. Each strain carries roughly 300 strain-specific chromosomal genes that account for differences in their experimentally confirmed phenotypes. B. megaterium is able to synthesize vitamin B(12) through an oxygen-independent adenosylcobalamin pathway, which together with other key energetic and metabolic pathways has now been fully reconstructed. Other novel genes include a second ftsZ gene, which may be responsible for the large cell size of members of this species, as well as genes for gas vesicles, a second β-galactosidase gene, and most but not all of the genes needed for genetic competence. Comprehensive analyses of the global Bacillus gene pool showed that only an asymmetric region around the origin of replication was syntenic across the genus. This appears to be a characteristic feature of the Bacillus spp. genome architecture and may be key to their sporulating lifestyle.

  14. 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.

  15. 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.

  16. Accurate Evaluation of the Dispersion Energy in the Simulation of Gas Adsorption into Porous Zeolites.

    PubMed

    Fraccarollo, Alberto; Canti, Lorenzo; Marchese, Leonardo; Cossi, Maurizio

    2017-03-07

    The force fields used to simulate the gas adsorption in porous materials are strongly dominated by the van der Waals (vdW) terms. Here we discuss the delicate problem to estimate these terms accurately, analyzing the effect of different models. To this end, we simulated the physisorption of CH4, CO2, and Ar into various Al-free microporous zeolites (ITQ-29, SSZ-13, and silicalite-1), comparing the theoretical results with accurate experimental isotherms. The vdW terms in the force fields were parametrized against the free gas densities and high-level quantum mechanical (QM) calculations, comparing different methods to evaluate the dispersion energies. In particular, MP2 and DFT with semiempirical corrections, with suitable basis sets, were chosen to approximate the best QM calculations; either Lennard-Jones or Morse expressions were used to include the vdW terms in the force fields. The comparison of the simulated and experimental isotherms revealed that a strong interplay exists between the definition of the dispersion energies and the functional form used in the force field; these results are fairly general and reproducible, at least for the systems considered here. On this basis, the reliability of different models can be discussed, and a recipe can be provided to obtain accurate simulated adsorption isotherms.

  17. 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.

  18. Adsorption of ammonium on biochar prepared from giant reed.

    PubMed

    Hou, Jie; Huang, Lei; Yang, Zhimin; Zhao, Yaqi; Deng, Chaoren; Chen, Yucheng; Li, Xin

    2016-10-01

    Giant reed was used as precursor for making biochar in order for the adsorption of NH4 (+)-N from aqueous solution. And the adsorption of the product to NH4 (+)-N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K2O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH4 (+)-N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH4 (+)-N from slightly polluted wastewater.

  19. Adsorption Behavior of Pb(II) Onto Potassium Polytitanate Nanofibres.

    PubMed

    Shahid, Mohammad; Tiling, Leonard D; El Saliby, Ibrahim; McDonagh, Andrew; Kim, Jong-Beom; Kim, Jong-Ho; Shon, Ho Kyong

    2016-02-01

    Potassium polytitanate nanofibres prepared by a hydrothermal method were investigated for their possible application in removing toxic metals from aqueous solution. Particular attention was paid to employing the titanate as a novel effective adsorbent for the removal of Pb(II). Batch adsorption experiments demonstrated that the adsorption was influenced by various conditions such as solution pH, adsorbent dosage and initial Pb(II) concentration. The results showed that the adsorption rate was faster in the first 5 min and equilibrium was achieved after 180 min. The maximum amount of adsorption was detected at pH 5. Potassium titanate showed much higher adsorption capacity compared to P25. The kinetic studies indicated that the adsorption of Pb(II) onto titanate best fit the pseudo-second-order kinetic model. FTIR spectra revealed that the hydroxyl groups in titanate were responsible for Pb(II) adsorption. The principal mechanism of the adsorption of Pb(II) in the present study is attributed to both ion exchange and oxygen bonding. The adsorption-desorption results demonstrated that the titanate could be readily regenerated after adsorption. Therefore, the present titanate exhibits great potential for the removal of Pb(II) from wastewater.

  20. 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.

  1. Study on the adsorption feature of rutin aqueous solution on macroporous adsorption resins.

    PubMed

    Chen, Zhenbin; Zhang, Anjie; Li, Jie; Dong, Fang; Di, Duolong; Wu, Youzhi

    2010-04-15

    The adsorption feature of different kinds of polystyrene-based macroporous adsorption resins (MARs) was investigated systemically at constant temperature employing Rutin as the adsorbate. Different from traditional adsorption patterns, Langmuir and Freundlich adsorption, and the results showed interesting aspects: (1) With the increase of the volume of the initial solution, the adsorption capacity increased to the maximum, and then decreased gradually. (2) Experimental results clearly verified the opinion that the adsorption process of MARs could be divided into three stages-macropores, mesopores, and micropores-by the capillary effects occurring at the two intersections, and the adsorption feature for every stage could be described well by the fourth type of Brunauer model. (3) The model that the inductive effect transmitted to the first layer could not interpret our experimental results reasonably. Thus, the model that the inductive effect passed on to a higher layer was proposed by investigating regression of the experimental results and the conclusion that the inductive effect transmitted to the third layer was drawn.

  2. 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

  3. 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.

  4. Arsenate adsorption onto iron oxide amended rice husk char.

    PubMed

    Cope, Christopher O; Webster, Damon S; Sabatini, David A

    2014-08-01

    In this study, rice husks were charred at 550 °C in a partially sealed ceramic vessel for 30minutes to create a high specific surface area (SSA) rice husk char (RHC). The RHC was then amended with iron oxides using dissolved ferric nitrate, Fe(NO3)3⋅9H2O, to provide a surface chemistry conducive to arsenic adsorption. The 550 °C iron oxide amended rice husk char's (550 IOA-RHC's) SSA was nearly 2.5 orders of magnitude higher and the arsenate adsorptive level was nearly 2 orders of magnitude higher than those reported for iron oxide amended sand, thus indicating a positive relationship between post-amendment SSA and arsenate adsorptive levels. Rice husks were then charred at temperatures ranging from 450 °C to 1050 °C to create an even higher SSA material, which might further increase arsenate adsorptive levels. The 950 °C RHC was chosen for amendment due to its high SSA and feasibility of being produced in the field. Once amended, the 950 °C iron oxide amended rice husk char (950 IOA-RHC) improved the arsenate adsorption capacity by thus confirming a positive relationship, though not a linear relationship, between post-amendment SSA and arsenic adsorptive capacity. Further study demonstrated that post-amendment mesoporous volume and mesoporous surface area appear to be better indicators of arsenic adsorptive capacity than SSA or iron content.

  5. Adsorption of Compounds that Mimic Urban Stormwater Dissolved Organic Nitrogen.

    PubMed

    Mohtadi, Mehrdad; James, Bruce R; Davis, Allen P

    2017-02-01

      Stormwater runoff carrying nitrogen can accelerate eutrophication. Bioretention facilities are among low impact development systems which are commonly used to manage urban stormwater quality and quantity. They are, however, not designed to remove dissolved organic nitrogen (DON) and may become a net DON exporter. Adsorption of seven organic nitrogenous compounds onto several adsorbents was examined. Batch adsorption study revealed that coal activated carbon (AC) exhibited the best performance in adsorption of the selected organic nitrogenous compounds. The highest adsorption capacity of coal AC was 0.4 mg N/g for pyrrole at an equilibrium concentration of 0.02 mg N/L, while adsorption was not detectable for urea at the same equilibrium concentration. The fastest compound to reach equilibrium adsorption capacity onto the coal AC was pyrrole (1 hour). The adsorption capacity of the coal AC for pyrrole and N-acetyl-d-glucosamine and 1-hour contact time is recommended for designing bioretention systems targeting organic nitrogenous compounds.

  6. 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.

  7. 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.

  8. 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.

  9. CO2 adsorption on chemically modified activated carbon.

    PubMed

    Caglayan, Burcu Selen; Aksoylu, A Erhan

    2013-05-15

    CO2 adsorption capacity of a commercial activated carbon was improved by using HNO3 oxidation, air oxidation, alkali impregnation and heat treatment under helium gas atmosphere. The surface functional groups produced were investigated by diffuse reflectance infrared Fourier transform spectrometer (DRIFTS). CO2 adsorption capacities of the samples were determined by gravimetric analyses for 25-200°C temperature range. DRIFTS studies revealed the formation of carboxylic acid groups on the HNO3 oxidized adsorbents. Increased aromatization and uniform distribution of the Na particles were observed on the samples prepared by Na2CO3 impregnation onto HNO3 oxidized AC support. The adsorption capacities of the nonimpregnated samples were increased by high temperature helium treatments or by increasing the adsorption temperature; both leading to decomposition of surface oxygen groups, forming sites that can easily adsorb CO2. The adsorption capacity loss due to cyclic adsorption/desorption procedures was overcome with further surface stabilization of Na2CO3 modified samples with high temperature He treatments. With Na2CO3 impregnation the mass uptakes of the adsorbents at 20 bars and 25 °C were improved by 8 and 7 folds and at 1 bar were increased 15 and 16 folds, on the average, compared to their air oxidized and nitric acid oxidized supports, respectively.

  10. 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.

  11. 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.

  12. Novel nano bearings constructed by physical adsorption

    PubMed Central

    Zhang, Yongbin

    2015-01-01

    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. PMID:26412488

  13. Adsorption behavior of EDTA-graphene oxide for Pb (II) removal.

    PubMed

    Madadrang, Clemonne J; Kim, Hyun Yun; Gao, Guihua; Wang, Ning; Zhu, Jun; Feng, Huan; Gorring, Matthew; Kasner, Marc L; Hou, Shifeng

    2012-03-01

    Chelating groups are successfully linked to graphene oxide (GO) surfaces through a silanization reaction between N-(trimethoxysilylpropyl) ethylenediamine triacetic acid (EDTA-silane) and hydroxyl groups on GO surface. EDTA-GO was found to be an ideal adsorbent for Pb(II) removal with a higher adsorption capacity. EDTA-modification enhances the adsorption capacity of GO because of the chelating ability of ethylene diamine triacetic acid. This study investigates the adsorption and desorption behaviors of heavy metal cations and the effects of solution conditions such as pH on Pb(II) removal. The adsorption capacity for Pb(II) removal was found to be 479 ± 46) mg/g at pH 6.8, and the adsorption process was completed within 20 min. The Langmuir adsorption model agrees well with the experimental data. The experimental results suggest that EDTA-GO can be reused after washed with HCl, suggesting potential applications in the environmental cleanup.

  14. Dynamic and static adsorption and desorption of Hg(II) ions on chitosan membranes and spheres.

    PubMed

    Vieira, Rodrigo S; Beppu, Marisa M

    2006-05-01

    The adsorption and desorption of Hg(II) ions was studied using static and dynamic methods, employing membranes and spheres of chitosan as the adsorbent. The quantity of adsorption was influenced by chitosan crosslinking and by the adsorbent shape. The Langmuir model was applied to fit the experimental equilibrium data. Glutaraldehyde-crosslinked membranes presented a lower desorption capacity, when compared to natural membranes, but could be regenerated for use in successive cycles. Dynamic adsorption experiments suggested that the adsorption capacity depended mainly on adsorbent geometry, due to differences between surface area to mass ratio and initial concentration of Hg(II) ions. The adsorption capacity determined by the dynamic method was 65% and 77% for membranes and spheres, respectively of the value obtained static method results. A process combining dynamic adsorption and static desorption can be used to concentrate the Hg(II) ions by a factor of nearly seven (7x), when compared to the initially treated volume.

  15. Adsorption of congo red by chitosan hydrogel beads impregnated with carbon nanotubes.

    PubMed

    Chatterjee, Sudipta; Lee, Min W; Woo, Seung H

    2010-03-01

    The adsorption performance of chitosan (CS) hydrogel beads was investigated after multiwalled carbon nanotubes (MWCNTs) impregnation for the removal of congo red (CR) as an anionic dye. The study of the adsorption capacity of CS/CNT beads as a function of the CNT concentration indicated that 0.01% CNT impregnation was the most useful for enhancing the adsorption capacity. The sulfur (%) in the CS/CNT beads measured by energy dispersive X-ray (EDX) was 2.5 times higher than that of normal CS beads after CR adsorption. Equilibrium adsorption isotherm data of the CS/CNT beads exhibited better fit to the Langmuir isotherm model than to the Freundlich isotherm model, and the heterogeneity factor (n) value of the CS/CNT beads calculated from the Sips isotherm model was close to unity (0.98). The maximum adsorption capacity of CS/CNT beads obtained from the Langmuir model was 450.4 mg g(-1).

  16. [Adsorption of perchlorate by calcined Mg/Zn/Al layered double hydroxides].

    PubMed

    Wang, Hong-Yu; Liu, Yan

    2014-07-01

    The adsorption capacity of perchlorate by Mg/Zn/Al layered double hydroxides was investigated. The samples were characterized by X-ray diffraction (XRD) and the adsorption isothermal model and dynamic model were discussed. The effect of calcination temperature, Mg/Zn/Al molar ratio, pH value of solution, adsorption time and dosage on the adsorption capacity of samples were studied. The experiment results showed that the removal ratio and adsorption capacity reached the highest and the pH value had good applicability when the molar ratio was Mg/Zn/Al = 2: 1 : 1. The adsorption of perchlorate basically conformed to the pseudo-second kinetics and Langmuir, Freundlich isotherm model.

  17. Adsorption of phenanthrene by quaternary ammonium surfactant modified peat and the mechanism involved.

    PubMed

    Zhou, Y B; Chen, L; Wang, X Q; Xu, Y X; Lu, J

    2012-01-01

    Removal of phenanthrene (PHE) from aqueous solution by adsorption onto quaternary ammonium surfactant modified peat was studied. The results show that surfactant modification enhanced the PHE adsorption capacity of peat. Low temperature and neutral pH favored PHE adsorption. Peat modified with long carbon chain surfactant performed better than peat modified with short carbon chain surfactant. The magnitude of PHE adsorption capacity followed the order of MP-HPB>MP-HTAB>MP-TBAB>RP, ranged from 924 to 1,228 μg g(-1). A negative trend between adsorption capacity (y) and (O+N)/C ratio of biosorbent (x) was observed (y = -1,369.6x + 2,176), which confirmed the negative effect of polarity on polycyclic aromatic hydrocarbon (PAH) removal. The study provides a guide to modify raw materials to enhance adsorption of hydrophobic organics.

  18. 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.

  19. 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.

  20. Comparison of Radii Sets, Entropy, QM Methods, and Sampling on MM-PBSA, MM-GBSA, and QM/MM-GBSA Ligand Binding Energies of F. tularensis Enoyl-ACP Reductase (FabI)

    PubMed Central

    Su, Pin-Chih; Tsai, Cheng-Chieh; Mehboob, Shahila; Hevener, Kirk E.; Johnson, Michael E.

    2015-01-01

    To validate a method for predicting the binding affinities of FabI inhibitors, three implicit solvent methods, MM-PBSA, MM-GBSA and QM/MM GBSA were carefully compared using sixteen benzimidazole inhibitors in complex with F. tularensis FabI. The data suggests that the prediction results are sensitive to radii sets, GB methods, QM Hamiltonians, sampling protocols, and simulation length, if only one simulation trajectory is used for each ligand. In this case, QM/MM-GBSA using 6 ns MD simulation trajectories together with GBneck2, PM3, and the mbondi2 radii set, generate the closest agreement with experimental values (r2= 0.88). However, if the three implicit solvent methods are averaged from six 1 ns MD simulations for each ligand (called “multiple independent sampling”), the prediction results are relatively insensitive to all the tested parameters. Moreover, MM/GBSA together with GBHCT and mbondi, using 600 frames extracted evenly from six 0.25 ns MD simulations, can also provide accurate prediction to experimental values (r2 = 0.84). Therefore, the multiple independent sampling method can be more efficient than a single, long simulation method. Since future scaffold expansions may significantly change the benzimidazole's physiochemical properties (charges, etc.) and possibly binding modes, which may affect the sensitivities of various parameters, the relatively insensitive “multiple independent sampling method” may avoid the need of an entirely new validation study. Moreover, due to large fluctuating entropy values, (QM/)MM-P(G)BSA were limited to inhibitors’ relative affinity prediction, but not the absolute affinity. The developed protocol will support an ongoing benzimidazole lead optimization program. PMID:26216222

  1. Comparison of monometal and multimetal adsorption in Mississippi River alluvial wetland sediment: batch and column experiments.

    PubMed

    Seo, Dong Cheol; Yu, Kewei; DeLaune, Ronald D

    2008-12-01

    Monometal and multimetal adsorption of selected heavy metals in a sediment from a coastal Louisiana forested swamp used for wastewater treatment was studied. Results from the batch experiments show that the maximum adsorption capacities of the metals by the sediment were in the order of Pb>Hg>Cr>CdCuZn>As based on monometal adsorption isotherm, and Hg>Cr>CuCd approximately Pb>As approximately Zn based on multimetal adsorption isotherm, respectively. Batch experimental data best fit the Langmuir model rather than the Freundlich isotherms. In the column experiments, the maximum adsorption capacities of the metals were in the order of Pb>Hg>Cr>Cd>Cu>Zn>As in monometal conditions, and Hg>Cr>Pb>CuZn approximately Cd>As in multimetal conditions. The metals became more mobile in multimetal than in monometal conditions. Results from both the batch and column experiments show that competitive adsorption among metals increases the mobility of these metals. Particularly, in this study, Pb in multimetal conditions lost it adsorption capacity most significantly. In both monometal and multimetal conditions, the maximum adsorption capacity of the metals in the column experiments was higher than that in the batch experiment indicating other metal retention mechanisms rather than adsorption may be involved. Therefore, both column and batch experiments are needed for estimating retention capacities and removal efficiencies of metals in sediments.

  2. Adsorption of deamidated antibody variants on macroporous and dextran-grafted cation exchangers: II. Adsorption kinetics.

    PubMed

    Tao, Yinying; Carta, Giorgio; Ferreira, Gisela; Robbins, David

    2011-03-18

    Single and multicomponent batch adsorption kinetics were obtained for deamidated mAb variants on two commercial cation exchangers, one with an open macroporous structure--UNOsphere S--and the other with charged dextran grafts--Capto S. The adsorption kinetics for the macroporous matrix was found to be controlled largely by pore diffusion. The effective diffusivity estimated from single component data was a fraction of the mAb free solution diffusivity, and its value could be used to accurately predict the adsorption kinetics for two- and three-component systems. In this case, when two or more variants were adsorbed simultaneously, both experimental and predicted results showed a temporary overshoot of the amount adsorbed above the equilibrium value for the more deamidated variant followed by a gradual approach to equilibrium. Adsorption rates on the dextran grafted material were much faster than those observed for the macroporous matrix for both single component and simultaneous adsorption cases. In this case, no significant overshoot was observed for the more deamidated forms. The Capto S adsorption kinetics could be described well by a diffusion model with an adsorbed phase driving force for single component adsorption and for the simultaneous adsorption of multiple variants. However, this model failed to predict the adsorption kinetics when more deamidated forms pre-adsorbed on the resin were displaced by less deamidated ones. In this case, the kinetics of the displacement process was much slower indicating that the pre-adsorbed components severely hindered transport of the more strongly bound variants. Overall, the results indicate that despite the lower capacity, the macroporous resin may be more efficient in process applications where displacement of one variant by another takes place as a result of the faster and more predictable kinetics.

  3. Adsorption of Gases on Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Mbaye, Mamadou Thiao

    2014-01-01

    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. Adsorption of arsenate on untreated dolomite powder.

    PubMed

    Ayoub, G M; Mehawej, M

    2007-09-05

    Raw dolomite powder was evaluated for its efficiency in adsorbing As(V) from water. An experimental setup comprised of a fluidized dolomite powder bed was used to assess the impact of various test variables on the efficiency of removal of As(V). Test influents including distilled water (DW), synthetic groundwater (SGW) and filtered sewage effluent (FSE) were employed to assess the effect of influent parameters on the adsorption process and the quality of the effluent generated. Dolomite exhibited good As(V) removal levels for distilled water (>92%) and synthetic ground water (>84%) influents at all initial As(V) concentrations tested (0.055-0.600 ppm). Breakthrough of dolomite bed occurred after 45 bed volumes for DW and 20 bed volumes for SGW influents with complete breakthrough taking place at more than 300 bed volumes. As(V) removal from FSE influents was relatively unsuccessful as compared to the DW and SGW influents. Partial removal in the order of 32% from filtered sewage effluent at initial concentration of 0.6 mg/L started at 75 bed volumes and gradually stopped at 165 bed volumes. Varying degrees of As(V) adsorption capacities were observed by the different test influents employed, which indicate that the adsorption of As(V) is adversely affected by competing species, mainly sulfates and phosphates present in the influent. The adsorptive behavior of dolomite was described by fitting data generated from the study into the Langmuir and Freundlich isotherm models. Both models described well the adsorption of dolomite. The average isotherm adsorptive capacity was determined at 5.02 mug/g. Regeneration of the dolomite bed can be achieved with the use of caustic soda solution at a pH of 10.5.

  5. 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.

  6. 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

  7. Mental capacity.

    PubMed

    Williams, Ruth

    2010-02-03

    Three short videos exploring some of the different principles in the Mental Capacity Act 2009 are available on Social Care TV, an online channel intended mainly for the social care sector, although the films are relevant to any professionals whose work is affected by the act. The dramas, which are set in a residential home, a person's own home and a residential school for young people with learning difficulties, concern thedecision-making process and can be viewed at www.scie.org.uk/socialcaretv/topic.asp?guid=377dbe1b-de0c-4d66-bb87-22a243542db2.

  8. 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.

  9. 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

    2016-08-09

    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.

  10. Energy analysis of four dimensional extended hyperbolic Scarf I plus three dimensional separable trigonometric noncentral potentials using SUSY QM approach

    NASA Astrophysics Data System (ADS)

    Suparmi, A.; Cari, C.; Deta, U. A.; Handhika, J.

    2016-11-01

    The non-relativistic energies and wave functions of extended hyperbolic Scarf I plus separable non-central shape invariant potential in four dimensions are investigated using Supersymmetric Quantum Mechanics (SUSY QM) Approach. The three dimensional separable non-central shape invariant angular potential consists of trigonometric Scarf II, Manning Rosen and Poschl-Teller potentials. The four dimensional Schrodinger equation with separable shape invariant non-central potential is reduced into four one dimensional Schrodinger equations through variable separation method. By using SUSY QM, the non-relativistic energies and radial wave functions are obtained from radial Schrodinger equation, the orbital quantum numbers and angular wave functions are obtained from angular Schrodinger equations. The extended potential means there is perturbation terms in potential and cause the decrease in energy spectra of Scarf I potential.

  11. 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].

  12. 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…

  13. 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.

  14. Adsorption of dyes on Sahara desert sand.

    PubMed

    Varlikli, Canan; Bekiari, Vlasoula; Kus, Mahmut; Boduroglu, Numan; Oner, Ilker; Lianos, Panagiotis; Lyberatos, Gerasimos; Icli, Siddik

    2009-10-15

    Sahara desert sand (SaDeS) was employed as a mineral sorbent for retaining organic dyes from aqueous solutions. Natural sand has demonstrated a strong affinity for organic dyes but significantly lost its adsorption capacity when it was washed with water. Therefore, characterization of both natural and water washed sand was performed by XRD, BET, SEM and FTIR techniques. It was found that water-soluble kyanite, which is detected in natural sand, is the dominant factor affecting adsorbance of cationic dyes. The sand adsorbs over 75% of cationic dyes but less than 21% for anionic ones. Among the dyes studied, Methylene Blue (MB) demonstrated the strongest affinity for Sahara desert sand (Q(e)=11.98 mg/g, for initial dye solution concentration 3.5 x 10(-5)mol/L). The effects of initial dye concentration, the amount of the adsorbent, the temperature and the pH of the solution on adsorption capacity were tested by using Methylene Blue as model dye. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were applied. It was concluded that adsorption of Methylene Blue on Sahara desert sand followed pseudo-second order kinetics. Gibbs free energy, enthalpy change and entropy change were calculated and found -6411 J/mol, -30360 J/mol and -76.58 J/mol K, respectively. These values indicate that the adsorption is an exothermic process and has a spontaneous nature at low temperatures.

  15. 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.

  16. A QM-MM interface between CHARMM and TURBOMOLE: implementation and application to systems in bulk phase and biologically active systems.

    PubMed

    Loferer, Markus J; Loeffler, Hannes H; Liedl, Klaus R

    2003-07-30

    The implementation of a hybrid QM-MM approach combining ab initio and density functional methods of TURBOMOLE with the molecular mechanics program package CHARMM is described. An interface has been created to allow data exchange between the two applications. With this method the efficient multiprocessor capabilities of TURBOMOLE can be utilized with CHARMM running as a single processor application. Therefore, features of nonparallel running code in CHARMM like the TRAVEL module for locating saddle points or VIBRAN for the calculation of second derivatives can be exploited by running the CPU intensive QM calculations in parallel. To test the methodology, several small systems are studied with both Hartree-Fock and density functional methods and varying QM-MM boundaries. Also, the computationally efficient RI-J method has been examined for use in QM-MM applications. A B(12) cofactor containing cobalt has been studied, to examine systems with a large QM region and transition metals. All tested methods perform satisfactory in comparison with pure quantum calculations. Additionally, algorithms for the characterization of saddle points have been tested for their potential use in QM-MM problems. The TRAVEL module of CHARMM has been applied to the Menshutkin reaction in the condensed phase, and a saddle point was located. This saddle point was verified by calculation of a steepest descent path connecting educt, transition state, and product, and by calculation of vibrational modes.

  17. 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

    2016-03-03

    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.

  18. Irreversible adsorption/desorption of PAHs in sediment/water

    SciTech Connect

    Fu, G.; Kan, A.T.; Tomson, M.B.

    1996-10-01

    Successive adsorption isotherm of phenanthrene on soil corresponds to a constant partition of phenanthrene between the bulk solution and solid phase. This shows that the hydrophobic reaction is a dominant mechanism in adsorption process. However, desorption of PAHs appears irreversibility. Cyclic and multiple adsorption and desorption experiments indicated that there is an irreversibly adsorbed intrinsic capacity in the interaction of PAHs (naphthalene and phenanthrene) and soil in aqueous solution. This irreversible fraction for PAHs (naphthalene and phenanthrene) is about 1000-5000 {mu}g/g normalized on the basis of soil organic carbon. The desorption of PAHs from soil appears biphasic when the total adsorbed capacity is greater than the intrinsic irreversibly adsorbed value. In phase, the partitioning coefficient of desorption of PAHs is similar to that of adsorption. However, the other mechanism may be responsible to control the release of PAHs in phase 2.

  19. A review on chitosan-based adsorptive membranes.

    PubMed

    Salehi, Ehsan; Daraei, Parisa; Arabi Shamsabadi, Ahmad

    2016-11-05

    Membrane adsorbents have emerged as powerful and attractive tools for the removal of hazardous materials such as dyes and heavy metal ions, mainly in trace amounts, from water resources. Among membrane adsorbents, those prepared from or modified with chitosan biopolymer and its derivatives are cases of interest because of chitosan advantages including biocompatibility, biodegradability, nontoxicity, reactivity, film and fiber forming capacity and favorable hydrophilicity. This review is oriented to provide a framework for better insight into fabrication methods and applications of chitosan-based adsorptive membranes. Critical aspects including thermokinetic analyses of adsorption and regeneration capacity of the membrane adsorbents have been also overviewed. Future of chitosan-based adsorptive membranes might include efforts for the improvement of mechanical stability and reusability and also most targeted application of appropriate copolymers as well as nanostructures in preparing high performance adsorptive membranes.

  20. Adsorption behaviour of dibutyl phthalate on marine sediments.

    PubMed

    Xu, Xiang-Rong; Li, Xiao-Yan

    2008-01-01

    Laboratory experiments were carried out to investigate the adsorption behaviour of dibutyl phthalate (DBP) on marine sediments collected from five different sites in Victoria Harbour, Hong Kong. DBP adsorption can be well described by the Langmuir isotherm. The maximum DBP adsorption capacity (Q(max)) of the marine sediments ranges from 53 to 79 mg g(-1), which has a positive correlation with their organic content. Around 90% of the organic can be removed from the sediments with treatment by H(2)O(2) oxidation, and the Q(max) then decreases to a range between 13 and 22 mg g(-1). The black carbon content of the sediments has a much greater DBP adsorption capacity than does the natural organic matter of the sediments. The amount of DBP adsorbed on the sediments increases as the salinity of the marine water increases.

  1. 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

  2. Adsorption behavior of heavy metals on biomaterials.

    PubMed

    Minamisawa, Mayumi; Minamisawa, Hiroaki; Yoshida, Shoichiro; Takai, Nobuharu

    2004-09-08

    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.

  3. DNA adsorption by indium tin oxide nanoparticles.

    PubMed

    Liu, Biwu; Liu, Juewen

    2015-01-01

    The high conductivity and optical transparency of indium tin oxide (ITO) has made it a popular material in the electronic industry. Recently, its application in biosensors is also explored. To understand its biointerface chemistry, we herein investigate its interaction with fluorescently labeled single-stranded oligonucleotides using ITO nanoparticles (NPs). The fluorescence of DNA is efficiently quenched after adsorption, and the interaction between DNA and ITO NPs is strongly dependent on the surface charge of ITO. At low pH, the ITO surface is positively charged to afford a high DNA adsorption capacity. Adsorption is also influenced by the sequence and length of DNA. For its components, In2O3 adsorbs DNA more strongly while SnO2 repels DNA at neutral pH. The DNA adsorption property of ITO is an averaging result from both components. DNA adsorption is confirmed to be mainly by the phosphate backbone via displacement experiments using free phosphate or DNA bases. Last, DNA-induced DNA desorption by forming duplex DNA is demonstrated on ITO, while the same reaction is more difficult to achieve on other metal oxides including CeO2, TiO2, and Fe3O4 because these particles adsorb DNA more tightly.

  4. Study on Adsorption of Cu(II) on Chitosan Nanofiber Membranes

    NASA Astrophysics Data System (ADS)

    Cao, Jianhua; Li, Dongzhou; Liang, Weihua; Wu, Dayong

    2014-12-01

    Chitosan nanofiber membranes by electrospinning technique were used to remove Cu(II) from aqueous solution. The adsorption kinetics, equilibrium isotherms, and pH effect were investigated in batch experiments. The Langmuir isotherm and pseudo second-order kinetic models agree well with the experimental data. The chitosan nanofiber membranes are effective for Cu(II) adsorption at pH6. Results showed that the maximum adsorption capacity of the chitosan nanofiber membranes with Cu(II) is 118.62 mg g-1. The chitosan nanofiber membranes can be used as an effective adsorbent for the removal of Cu(II) in aqueous solution due to high adsorption capacity.

  5. Competitive adsorption of VOCs and BOM: The role of molecular oxygen

    SciTech Connect

    Sorial, G.A.; Cerminara, P.; Papadimas, S.P.; Suidan, M.T. . Dept. of Civil and Environmental Engineering); Speth, T.F. )

    1994-03-01

    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 capacity was likely due to conglomeration of BOM on the carbon surface, which reduced the available surface area for the target volatile organic chemical (VOC). Adsorption isotherms conducted with constant initial concentration ratios of VOC to BOM showed similar behavior. The ideal adsorbed solution theory (IAST) was found to accurately describe anoxic adsorption isotherms for VOCs in water containing BOM but failed to predict this competition for data collected under oxic conditions.

  6. Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin.

    PubMed

    Hu, Qinhai; Meng, Yuanyuan; Sun, Tongxi; Mahmood, Qaisar; Wu, Donglei; Zhu, Jianhang; Lu, George

    2011-01-30

    The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293K. Various thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis.

  7. Bile salt adsorption ability of dietary fiber from named varieties of carrot at different developmental ages.

    PubMed

    Robertson, J A; Eastwood, M A; Yeoman, M M

    1980-06-01

    The adsorption of bile salts to fiber has been measured using fiber prepared from different varieties of carrot at different developmental ages. We investigated the carrot varieties Altrinchan and Chantenay and used the bile salts deoxycholate and glycocholate. The method used to measure adsorption distinguished between true adsorption and apparent adsorption due to bile salts trapped within the interstices of the fiber matrix. Adsorption ability was influenced by the developmental age of the carrot but not by variety. Adsorption ability was at a maximum when the carrot fresh weight was at a maximum. The adsorption ability measured was true adsorption and was not dependent on the water holding capacity of the fiber. Deoxycholate was better adsorbed than glycocholate and the results suggest that the developmental age of a fiber source could be important when formulating diets designed to influence bile salt metabolism.

  8. Investigation of dye adsorption onto activated carbon from the shells of Macoré fruit.

    PubMed

    Aboua, Kouassi Narcisse; Yobouet, Yao Augustin; Yao, Kouassi Benjamin; Goné, Droh Lanciné; Trokourey, Albert

    2015-06-01

    The activated carbon obtained from the shells of Macoré fruit was used as an adsorbent for the removal of dyes such as methylene blue (MB) and methyl orange (MO) from synthetic contaminated aqueous solutions. It holds that the adsorption is more favourable at acidic pH, with an optimum adsorption at pH = 2. At this pH, the adsorption rate is more than 98% for the two dyes. The sorption capacity was enhanced by increasing the amount of activated carbon. Above room temperature, the adsorption rates remain constant at a value of approximately 99%. The study of the adsorption kinetics indicates that the adsorption on the studied dyes follows second-order kinetics. The isotherm adsorption data were found to be described by both Langmuir and Freundlich. In addition, the thermodynamic studies revealed that the adsorption process is a favourable, endothermic and spontaneous phenomenon.

  9. Adsorption of 2,4,6-trinitrotoluene on carboxylated porous polystyrene microspheres

    NASA Astrophysics Data System (ADS)

    Ye, Zhengfang; Meng, Qingqiang; Lu, Shengtao

    2012-02-01

    Large-pore-size (150 nm) polystyrene (PSt) microspheres were carboxylated with phthalic anhydride (PA) through Friedel-Crafts acetylation to study the adsorption of 2,4,6-trinitrotoluene (TNT) on this material from aqueous solution. The scanning electron microscope (SEM) images and mercury porosimetry measurements (MPM) of the microspheres showed that the pore structure was unchanged during the reaction. High adsorption capacity (11.2 mg g-1 of suction-dried adsorbent) and adsorption rate (33.9 mg g-1 h-1) for TNT were observed during the study. As shown by the adsorption isotherm, the adsorption of TNT on PA-PSt can be described by the Freundlich adsorption equation, indicating heterogeneous adsorption process. On-column adsorption of TNT on PA-PSt and elution indicated that TNT can be completely removed from aqueous solution and condensed into acetone.

  10. Application of activated carbon derived from scrap tires for adsorption of Rhodamine B.

    PubMed

    Li, Li; Liu, Shuangxi; Zhu, Tan

    2010-01-01

    Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char (APTC) for Rhodamine B (RhB). Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little effect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.

  11. 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.

  12. Adsorption of trihalomethanes from water with carbon nanotubes.

    PubMed

    Lu, Chungsying; Chung, Yao-Lei; Chang, Kuan-Foo

    2005-03-01

    Commercial carbon nanotubes (CNTs) were purified by acid solution and were employed as adsorbents to study adsorption of trihalomethanes (THMs) from water. The properties of CNTs such as purity, structure and nature of the surface were greatly improved after acid treatment which made CNTs become more hydrophilic and suitable for adsorption of low molecular weight and relatively polar THM molecules. The adsorption of THMs onto CNTs fluctuates very little in the pH range 3-7, but decreases with pH value as pH exceeds 7. A comparative study between CNTs and powdered activated carbon (PAC) for adsorption of THMs from water was also conducted. The short time needed to reach equilibrium as well as the high adsorption capacity of CHCl3, which accounts for a significant portion of THMs in the chlorinated drinking water, suggests that CNTs possess highly potential applications for THMs removal from water.

  13. Methane Adsorption on Graphitic Nanostructures: Every Molecule Counts

    PubMed Central

    2012-01-01

    Bundles of single-walled nanotubes are promising candidates for storage of hydrogen, methane, and other hydrogen-rich molecules, but experiments are hindered by nonuniformity of the tubes. We overcome the problem by investigating methane adsorption on aggregates of fullerenes containing up to six C60; the systems feature adsorption sites similar to those of nanotube bundles. Four different types of adsorption sites are distinguished, namely, registered sites above the carbon hexagons and pentagons, groove sites between adjacent fullerenes, dimple sites between three adjacent fullerenes, and exterior sites. The nature and adsorption energies of the sites in C60 aggregates are determined by density functional theory and molecular dynamics (MD) simulations. Excellent agreement between experiment and theory is obtained for the adsorption capacity in these sites. PMID:23378887

  14. Reuse of Solid Waste in Adsorption of the Textile Dye

    NASA Astrophysics Data System (ADS)

    Meziti, Chafika; Boukerroui, Abdelhamid

    This work presents the study of the reuse of a regenerated spent bleaching earth (RSBE). The RSBE material was tested in the removal of a basic textile dye presents in aqueous solution. The effect of physicochemical parameters such as stirring speed, initial concentration, contact time and temperature have been invested and thermodynamic nature of the adsorption process was determined by calculating the ΔH°, ΔS° and ΔG° values The results obtained show that the adsorption mechanism was described by the Langmuir model and the adsorption capacity, qmax (72.41 to 82.37 mg.g-1), increases with temperature (20-50 °C). The thermodynamic parameters show a presence of a strong affinity between two phases (liquid-solid) and an endothermic equilibrium adsorption process. However, the phenomenon of the adsorption kinetic follows the pseudo second order kinetic model.

  15. Adsorption of organic phenols onto hexadecyltrimethylammonium-treated montmorillonite

    SciTech Connect

    Kim, Young S.; Song, Dong I.; Jeon, Young W.; Choi, Sang J.

    1996-12-01

    Montmorillonite used as an adsorbent was organically modified by using a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the removal capacity of organic phenol contaminants dissolved in an aqueous solution. This modification produces a change of the surface property of montmorillonite from hydrophilic to organophilic. The single- and multicomponent competitive adsorptions were performed in a batch reactor to investigate the removal of three toxic organic phenols, 2-chlorophenol, 3-cyanophenol, and 4-nitrophenol, on the modified HDTMA-montmorillonite. It was observed from the experimental results that the adsorption affinity for HDTMA-montmorillonite was 2-chlorophenol, 4-nitrophenol, 3-cyanophenol in decreasing order. Langmuir and the Redlich-Peterson models were used to analyze the single-component adsorption results, while the IAST and the LCM models predicted the multicomponent adsorption equilibria. These models yielded favorable representations of both individual and competitive adsorption behaviors.

  16. 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.

  17. Influence of multi-walled carbon nanotubes on textural and adsorption characteristics of in situ synthesized mesostructured silica.

    PubMed

    Karim, A H; Jalil, A A; Triwahyono, S; Kamarudin, N H N; Ripin, A

    2014-05-01

    Carbon nanotubes-mesostructured silica nanoparticles (CNT-MSN) composites were prepared by a simple one step method with various loading of CNT. Their surface properties were characterized by XRD, N2 physisorption, TEM and FTIR, while the adsorption performance of the CNT-MSN composites were evaluated on the adsorption of methylene blue (MB) while varying the pH, adsorbent dosage, initial MB concentration, and temperature. The CNTs were found to improve the physicochemical properties of the MSN and led to an enhanced adsorptivity for MB. N2 physisorption measurements revealed the development of a bimodal pore structure that increased the pore size, pore volume and surface area. Accordingly, 0.05 g L(-1) CNT-MSN was able to adsorb 524 mg g(-1) (qm) of 60 mg L(-1) MB at pH 8 and 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, with the Langmuir model affording the best fit to the adsorption data. The adsorption kinetics were best described by the pseudo-first order model. These results indicate the potential of CNT-MSN composites as effective new adsorbents for dye adsorption.

  18. 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.

  19. 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.

  20. 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

  1. Insights into enzyme catalysis from QM/MM modelling: transition state stabilization in chorismate mutase

    NASA Astrophysics Data System (ADS)

    Ranaghan, Kara E.; Ridder, Lars; Szefczyk, Borys; Sokalski, W. Andrzej; Hermann, Johannes C.; Mulholland, Adrian J.

    Chorismate mutase provides an important test of theories of enzyme catalysis, and of modelling methods. The Claisen rearrangement of chorismate to prephenate in the enzyme has been modelled here by a combined quantum mechanics/molecular mechanics (QM/MM) method. Several pathways have been calculated. The sensitivity of the results to details of model preparation and pathway calculation is tested, and the results are compared in detail to previous similar studies and experiments. The potential energy barrier for the enzyme reaction is estimated at 24.5-31.6 kcal mol-1 (AM1/CHARMM), and 2.7-11.9 kcal mol-1 with corrections (e.g. B3LYP/6-31+G(d)). In agreement with previous studies, the present analysis of the calculated paths provides unequivocal evidence of significant transition state stabilization by the enzyme, indicating that this is central to catalysis by the enzyme. The active site is exquisitely complementary to the transition state, stabilizing it more than the substrate, so reducing the barrier to reaction. A number of similar pathways for reaction exist in the protein, as expected. Small structural differences give rise to differences in energetic contributions. Major electrostatic contributions to transition state stabilization come in all cases from Arg90, Arg7, one or two water molecules, and Glu78 (Glu78 destabilizes the transition state less than the substrate), while Arg63 contributes significantly in one model.

  2. QM/MM calculations of kinetic isotope effects in the chorismate mutase active site.

    PubMed

    Martí, Sergio; Moliner, Vincent; Tuñón, Iñaki; Williams, Ian H

    2003-02-07

    Kinetic isotope effects have been computed for the Claisen rearrangement of chorismate to prephenate in aqueous solution and in the active site of chorismate mutase from B. subtilus. These included primary 13C and 18O and secondary 3H effects for substitutions at the bond-making and bond-breaking positions. The initial structures of the putative stationary points on the potential energy surface, required for the calculations of isotope effects using the CAMVIB/CAMISO programs, have been selected from hybrid QM/MM molecular dynamical simulations using the DYNAMO program. Refinement of the reactant complex and transition-state structures has been carried out by means of AM1/CHARMM24/TIP3P calculations using the GRACE program, with full gradient relaxation of the position of > 5200 atoms for the enzymic simulations, and with a box containing 711 water molecules for the corresponding reaction in aqueous solution. Comparison of these results, and of gas phase calculations, with experimental data has shown that the chemical rearrangement is largely rate-determining for the enzyme mechanism. Inclusion of the chorismate conformational pre-equilibrium step in the modelled kinetic scheme leads to better agreement between recent experimental data and theoretical predictions. These results provide new information on an important enzymatic transformation, and the key factors responsible for the kinetics of its molecular mechanism are clarified. Treatment of the enzyme and/or solvent environment by means of a large and flexible model is absolutely essential for prediction of kinetic isotope effects.

  3. Trichloroethylene (TCE) adsorption using sustainable organic mulch.

    PubMed

    Wei, Zongsu; Seo, Youngwoo

    2010-09-15

    Soluble substrates (electron donors) have been commonly injected into chlorinated solvent contaminated plume to stimulate reductive dechlorination. Recently, different types of organic mulches with economic advantages and sustainable benefits have received much attention as new supporting materials that can provide long term sources of electron donors for chlorinated solvent bioremediation in engineered biowall systems. However, sorption capacities of organic mulches for chlorinated solvents have not been studied yet. In this study, the physiochemical properties of organic mulches (pine, hardwood and cypress mulches) were measured and their adsorption capacity as a potential media was elucidated. Single, binary and quaternary isotherm tests were conducted with trichloroethylene (TCE), tetrachloroethylene (PCE), trans-dichloroethylene (trans-DCE) and cis-dichloroethylene (cis-DCE). Among the three tested mulches, pine mulch showed the highest sorption capacity for the majority of the tested chemicals in single isotherm test. In binary or quaternary isotherm tests, competition among chemicals appears to diminish the differences in Q(e) for tested mulches. However, pine mulch also showed higher adsorption capacity for most chemicals when compared to hardwood and cypress mulches in the two isotherm tests. Based upon physicochemical properties of the three mulches, higher sorption capacity of pine mulch over hardwood and cypress mulches appears to be attributed to a higher organic carbon content and the lower polarity.

  4. Advances in principal factors influencing carbon dioxide adsorption on zeolites

    PubMed Central

    Bonenfant, Danielle; Kharoune, Mourad; Niquette, Patrick; Mimeault, Murielle; Hausler, Robert

    2008-01-01

    We report the advances in the principal structural and experimental factors that might influence the carbon dioxide (CO2) adsorption on natural and synthetic zeolites. The CO2 adsorption is principally govern by the inclusion of exchangeable cations (countercations) within the cavities of zeolites, which induce basicity and an electric field, two key parameters for CO2 adsorption. More specifically, these two parameters vary with diverse factors including the nature, distribution and number of exchangeable cations. The structure of framework also determines CO2 adsorption on zeolites by influencing the basicity and electric field in their cavities. In fact, the basicity and electric field usually vary inversely with the Si/Al ratio. Furthermore, the CO2 adsorption might be limited by the size of pores within zeolites and by the carbonates formation during the CO2 chemisorption. The polarity of molecules adsorbed on zeolites represents a very important factor that influences their interaction with the electric field. The adsorbates that have the most great quadrupole moment such as the CO2, might interact strongly with the electric field of zeolites and this favors their adsorption. The pressure, temperature and presence of water seem to be the most important experimental conditions that influence the adsorption of CO2. The CO2 adsorption increases with the gas phase pressure and decreases with the rise of temperature. The presence of water significantly decreases adsorption capacity of cationic zeolites by decreasing strength and heterogeneity of the electric field and by favoring the formation of bicarbonates. The optimization of the zeolites structural characteristics and the experimental conditions might enhance substantially their CO2 adsorption capacity and thereby might give rise to the excellent adsorbents that may be used to capturing the industrial emissions of CO2. PMID:27877925

  5. Adsorption behavior of the catechins and caffeine onto polyvinylpolypyrrolidone.

    PubMed

    Dong, Zhan-Bo; Liang, Yue-Rong; Fan, Fang-Yuan; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang

    2011-04-27

    Adsorbent is one of the most important factors for separation efficiency in fixed-bed purification techniques. The adsorption behavior of catechins and caffeine onto polyvinylpolypyrrolidone (PVPP) was investigated by static adsorption tests. The results showed that catechins rather than caffeine were preferred to adsorb onto PVPP since the adsorption selectivity coefficient of total catechins vs caffeine was around 22.5, and that adsorption of catechins could be described by the pseudo-second-order model. Adsorption amount of caffeine onto PVPP in green tea extracts solution was much higher than that in purified caffeine solution although the initial concentration of caffeine was similar in the two solutions, indicating the caffeine might be attached with catechins which were adsorbed by PVPP instead of being adsorbed by PVPP directly. The results also showed that the adsorption capacity of catechins and caffeine decreased with an increase in temperature, and that Freundlich and Langmuir models were both suitable for describing the isothermal adsorption of catechins, but not suitable for caffeine. The predicted maximum monolayer adsorption capacity of total catechins by PVPP was 671.77 mg g(-1) at 20 °C, which was significantly higher than that by other reported adsorbents. The thermodynamics analyses indicated that the adsorption of catechins onto PVPP was a spontaneous and exothermic physisorption process, revealing lower temperature was favorable for the adsorption of catechins. Elution tests showed that the desorption rates of catechins and caffeine were higher than 91% and 99% after two elution stages; in detail, almost all of the caffeine could be washed down at the water eluting stage, while catechins could be recovered at the dimethyl sulfoxide/ethanol solution eluting stage. Thus, the PVPP could be used as an excellent alternative adsorbent candidate for separating catechins from crude tea extracts, although some investigations, such as exploring the new

  6. Competitive adsorption of organic compounds by microbial biomass

    SciTech Connect

    Selvakumar, A.; Hsieh, H.N. )

    1988-01-01

    This study investigated the effect of competitive adsorption of liquid organic compounds on inactive microbial biomass in bisolute solution systems. Phenol-nitrophenol, phenol-chlorophenol, nitrophenol-chlorophenol, and chlorobenzene-ethylbenzene systems were selected for the analysis. The experimental results suggest that although the amount of each solute adsorbed on the biomass can be reduced significantly by the presence of a second solute, the combined adsorptive capacity was greater than that for either of the individual substances from its pure solution. The octanol/water partition coefficient(K{sub ow}) indicates the relative extent of adsorption better than the aqueous solubility(S).

  7. Adsorptive decolorization of methylene blue by crosslinked porous starch.

    PubMed

    Guo, Lei; Li, Guiying; Liu, Junshen; Meng, Yanfeng; Tang, Yanfeng

    2013-04-02

    Crosslinked porous starch (CPS) was prepared by two steps. Native starch was crosslinked with epichlorohydrin and then CPS was prepared by hydrolyzing the crosslinked starch with α-amylase. As a biodegradable and safe adsorbent, CPS was used to remove methylene blue (MB) from the aqueous solution based on its characterizations, including surface area, pore volume and scanning electron microscopy (SEM). The results indicate that the adsorption capacity of CPS is much higher than native starch and relatively higher than porous starch. The effects of the initial concentration of MB, the time and temperature on the adsorption capacity were investigated. The pseudo-first-order kinetic model provides a better correlation of the experimental data in comparison with the pseudo-second-order model. The equilibrium adsorption data are well described by the Langmuir isotherm model with a maximum adsorption capacity of 9.46mg g(-1). The adsorption of MB on CPS is endothermic and spontaneous in nature. The thermodynamics data are in good agreement with physical adsorption mechanism.

  8. Enhanced adsorption of quaternary amine using modified activated carbon.

    PubMed

    Prahas, Devarly; Wang, M J; Ismadji, Suryadi; Liu, J C

    2014-01-01

    This study examined different methodologies to modify activated carbon (AC) for the removal of quaternary amine, tetramethylammonium hydroxide (TMAH), from water. Commercial carbon (WAC) was treated by nitric acid oxidation (NA-WAC), silica impregnation (SM-WAC0.5), and oxygen plasma (P10-WAC), and their characteristics and adsorption capacity were compared. The Langmuir model fitted the equilibrium adsorption data well under different pH. The maximum adsorption capacity of WAC was 27.77 mg/g, while those of NA-WAC, SM-WAC 0.5, and P10-WAC were 37.46, 32.83 and 29.03 mg/g, respectively. Nitric acid oxidation was the most effective method for enhancing the adsorption capacity of TMAH. Higher pH was favorable for TMAH adsorption. Desorption study revealed that NA-WAC had no considerable reduction in performance even after five cycles of regeneration by 0.1 N hydrochloric acid. It was proposed that electrostatic interaction was the main mechanism of TMAH adsorption on activated carbon.

  9. Synthesis of magnetic wheat straw for arsenic adsorption.

    PubMed

    Tian, Ye; Wu, Min; Lin, Xiaobo; Huang, Pei; Huang, Yong

    2011-10-15

    Magnetic wheat straw (MWS) with different Fe(3)O(4) content was synthesized by using in-situ co-precipitation method. It was characterized by powder X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). This material can be used for arsenic adsorption from water, and can be easily separated by applied magnetic field. The introduction of wheat straw template highly enhanced the arsenic adsorption of Fe(3)O(4). Among three adsorption isotherm models examined, the data fitted Langmuir model better. Fe(3)O(4) content and initial pH value influenced its adsorption behavior. Higher Fe(3)O(4) content corresponded to a higher adsorption capacity. In the pH range of 3-11, As(V) adsorption was decreased with increasing of pH; As(III) adsorption had the highest capacity at pH 7-9. Moreover, by using 0.1 mol L(-1) NaOH aqueous solution, it could be regenerated. This work provided an efficient way for making use of agricultural waste.

  10. Adsorptive removal of α-endosulfan from water by hydrophobic zeolites. An isothermal study.

    PubMed

    Yonli, Arsène H; Batonneau-Gener, Isabelle; Koulidiati, Jean

    2012-02-15

    This paper deals with the removal of α-endosulfan from water over HY and steamed HBEA zeolites. Experiments were performed to understand the adsorption mechanisms of α-endosulfan on zeolites and to determine the most efficient adsorbent for the purification of water contaminated by this pesticide. The experiments exhibit that α-endosulfan was adsorbed in the micropores. In the case of HY zeolites an adsorption of α-endosulfan molecules on BrØnsted sites was pointed out, due to a preferential water adsorption in mesopores. Moreover a physisorption of α-endosulfan occurred in micropores. For steamed HBEA zeolites physisorption in micropores was pointed out as the adsorption mode. For both types of zeolites a decrease of the adsorption capacities was noticed when the acidity of zeolites increased. There was also a linear relation between the adsorption capacities of α-endosulfan and the hydrophobicity (HI) of the samples and by determining the values of HI for a type of zeolite it was possible to deduce the uptake of α-endosulfan. The HY(40) sample was the most efficient for the removal of α-endosulfan from water because of preferential adsorption of water molecules in mesopores and lower acidity. For this sample the adsorption capacity for α-endosulfan was about 833.33 mg/g where for the most effective HBEA sample (St700(3)) the adsorption capacity was about 793.65 mg/g.

  11. 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.

  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. 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.

  14. 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.

  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. 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.

  17. 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.

  18. 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...

  19. Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons.

    PubMed

    Dai, Xiaodong; Zou, Linda; Yan, Zifeng; Millikan, Mary

    2009-08-30

    This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N(2) adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO(2) particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

  20. 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

  1. 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.

  2. Final report of the key comparison APMP.QM-K91: APMP comparison on pH measurement of phthalate buffer

    NASA Astrophysics Data System (ADS)

    Hioki, Akiharu; Asakai, Toshiaki; Maksimov, Igor; Suzuki, Toshihiro; Miura, Tsutomu; Ketrin, Rosi; Nuryatini; Thanh, Ngo Huy; Truong Chinh, Nguyen; Vospelova, Alena; Bastkowski, Frank; Sander, Beatrice; Matzke, Jessica; Prokunin, Sergey; Frolov, Dmitry; Aprelev, Alexey; Dobrovolskiy, Vladimir; Uysal, Emrah; Liv, Lokman; Velina Lara-Manzano, Judith; Montero-Ruiz, Jazmin; Ortiz-Aparicio, JosÉ Luis; Ticona Canaza, Galia; Anuar Mohd Amin, Khirul; Abd Kadir, Haslina; Bakovets, Nickolay; Wong, Siu-Kay; Lam, Wai-Hing

    2017-01-01

    The APMP.QM-K91 was organised by TCQM of APMP to test the abilities of the national metrology institutes in the APMP region to measure a pH value of a phthalate buffer. This APMP comparison on pH measurement was proposed by the National Metrology Institute of Japan at the APMP-TCQM meeting held September 22-23, 2014. After approval by TCQM, the comparison has been conducted by NMIJ. The comparison is a key comparison following CCQM-K91. The comparison material was a phthalate buffer of pH around 4.0 and the measurement temperatures were 15 °C, 25 °C and 37 °C. This is the third APMP key comparison on pH measurement and the fifth APMP comparison on pH measurement following APMP.QM-P06 (two phosphate buffers) in 2004, APMP.QM-P09 (a phthalate buffer) in 2006, APMP.QM-K9/APMP.QM-P16 (a phosphate buffer) in 2010-2011 and APMP.QM-K19/APMP.QM-P25 (a borate buffer) in 2013-2014. The results can be used further by any participant to support its CMC claim at least for a phthalate buffer. That claim will concern the pH method employed by the participant during this comparison and will cover the used temperature(s) or the full temperature range between 15°C and 37 °C for the participant which measured pH values at the three temperatures. 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).

  3. Theoretical modelling of biomolecular systems I. Large-scale QM/MM calculations of hydrogen-bonding networks of the oxygen evolving complex of photosystem II

    NASA Astrophysics Data System (ADS)

    Shoji, Mitsuo; Isobe, Hiroshi; Yamanaka, Shusuke; Umena, Yasufumi; Kawakami, Keisuke; Kamiya, Nobuo; Shen, Jian-Ren; Nakajima, Takahito; Yamaguchi, Kizashi

    2015-02-01

    Quantum mechanical (QM)/molecular mechanics (MM) calculations by the use of a large-scale QM model (QM Model V) have been performed to elucidate hydrogen-bonding networks and proton wires for proton release pathways (PRP) of water oxidation reaction in the oxygen evolving complex (OEC) of photosystem II (PSII). Full geometry optimisations of PRP by the QM/MM model have been carried out starting from the geometry of heavy atoms determined by the recent high-resolution X-ray diffraction (XRD) experiment of PSII refined to 1.9 Å resolution. Computational results by the QM/MM calculations have elucidated the hydrogen-bonding O...O(N) and O...H distances and O(N)-H...O angles in PRP, together with the Cl-O(N) and Cl...H distances and O(N)-H...Cl angles for chloride anions. The optimised hydrogen-bonding networks are well consistent with the XRD results and available experiments such as extended X-ray absorption fine structure, showing the reliability of channel structures of OEC of PSII revealed by the XRD experiment. The QM/MM computations have elucidated possible roles of chloride anions in the OEC of PSII. The QM/MM computational results have provided useful information for understanding and explanation of accumulated mutation experiments of key amino acid residues in the OEC of PSII. Implications of the present results are discussed in relation to three steps for theoretical modelling of water oxidation in the OEC of PSII and bio-inspired working hypotheses for developments of artificial water oxidation systems by use of 3d transition-metal complexes.

  4. Efficient approach to include molecular polarizations using charge and atom dipole response kernels to calculate free energy gradients in the QM/MM scheme.

    PubMed

    Asada, Toshio; Ando, Kanta; Sakurai, Koji; Koseki, Shiro; Nagaoka, Masataka

    2015-10-28

    An efficient approach to evaluate free energy gradients (FEGs) within the quantum mechanical/molecular mechanical (QM/MM) framework has been proposed to clarify reaction processes on the free energy surface (FES) in molecular assemblies. The method is based on response kernel approximations denoted as the charge and the atom dipole response kernel (CDRK) model that include explicitly induced atom dipoles. The CDRK model was able to reproduce polarization effects for both electrostatic interactions between QM and MM regions and internal energies in the QM region obtained by conventional QM/MM methods. In contrast to charge response kernel (CRK) models, CDRK models could be applied to various kinds of molecules, even linear or planer molecules, without using imaginary interaction sites. Use of the CDRK model enabled us to obtain FEGs on QM atoms in significantly reduced computational time. It was also clearly demonstrated that the time development of QM forces of the solvated propylene carbonate radical cation (PC˙(+)) provided reliable results for 1 ns molecular dynamics (MD) simulation, which were quantitatively in good agreement with expensive QM/MM results. Using FEG and nudged elastic band (NEB) methods, we found two optimized reaction paths on the FES for decomposition reactions to generate CO2 molecules from PC˙(+), whose reaction is known as one of the degradation mechanisms in the lithium-ion battery. Two of these reactions proceed through an identical intermediate structure whose molecular dipole moment is larger than that of the reactant to be stabilized in the solvent, which has a high relative dielectric constant. Thus, in order to prevent decomposition reactions, PC˙(+) should be modified to have a smaller dipole moment along two reaction paths.

  5. 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 an isosteric heat of adsorption of from 5 to 8.5 kilocalories per mole of CO.sub.2. The invention also provides a carbon sorbent in a powder, a granular or a pellet form for the removal of carbon dioxide from gas streams, comprising: a carbon content of at least 90 weight percent; a nitrogen content of at least 1 weight percent; an oxygen content of at most 3 weight percent; a BET surface area from 50 to 2600 m.sup.2/g; and a DFT micropore volume from 0.04 to 0.8 cc/g.

  6. 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.

  7. Generalized random sequential adsorption

    NASA Astrophysics Data System (ADS)

    Tarjus, G.; Schaaf, P.; Talbot, J.

    1990-12-01

    Adsorption of hard spherical particles onto a flat uniform surface is analyzed by using generalized random sequential adsorption (RSA) models. These models are defined by releasing the condition of immobility present in the usual RSA rules to allow for desorption or surface diffusion. Contrary to the simple RSA case, generalized RSA processes are no longer irreversible and the system formed by the adsorbed particles on the surface may reach an equilibrium state. We show by using a distribution function approach that the kinetics of such processes can be described by means of an exact infinite hierarchy of equations reminiscent of the Kirkwood-Salsburg hierarchy for systems at equilibrium. We illustrate the way in which the systems produced by adsorption/desorption and by adsorption/diffusion evolve between the two limits represented by ``simple RSA'' and ``equilibrium'' by considering approximate solutions in terms of truncated density expansions.

  8. Hybrid adsorptive membrane reactor

    SciTech Connect

    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.

  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 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.

  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.

  12. Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

    NASA Astrophysics Data System (ADS)

    Feng, Qinzhong; Zhang, Zhiyong; Ma, Yuhui; He, Xiao; Zhao, Yuliang; Chai, Zhifang

    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 (Δ H 0 , Δ S 0 , and Δ G 0 ) 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.

  13. Adsorption behavior of some radionuclides on the Chinese weathered coal.

    PubMed

    Wu, Jianfeng; Xu, Qichu; Bai, Tao

    2007-08-01

    The equilibrium and kinetic properties of Am(III), Eu(III) and Cs(I) ions adsorption by three weathered coals (WCs) from China, have been investigated in batch stirred-tank experiments. The effects of contact time, solution acidity and initial sorbate concentration on the adsorption of Am(III), Eu(III) and Cs(I) by Yuxian(YX) Tongchuan (TC) and Pingxiang (PX) WC were evaluated. The radionuclide ions are able to form complex compounds with carboxylic and phenolic groups of WCs and they are also bounded with phenolic groups even at high acidity reaction solution (>0.1 mol/L). Mechanisms including ion exchange, complexation and adsorption to the coal surface are possible in the sorption process. The acidity of the solution played an important role in the adsorption. Even acidity as high as 0.1 mol/L, 60% of Am(III) or Eu(III), 40% of Cs(I) were found to be sorbed on the YX WC, which had the best adsorption capacity for Am(III) and Eu(III). Our batch adsorption studies showed the equilibrium adsorption data fit the linear Langmuir and Freundlich adsorption isotherm. The maximum equilibrium uptake of Eu(III) were 0.412, 3.701, 5.446 mmol/g for JXWC, TCWC and YXWC, respectively.

  14. 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.

  15. [Adsorption of dyes as an indicator of the biological activity of mineral dust].

    PubMed

    Dancheva, N

    1989-01-01

    A study is made on the adsorption capacity of several types silicates and quartz dusts, prepared from pure mineral standards with respect to methylene blue and fuchsin. There are differences in the adsorption capacity of the minerals referring to unit surface. The quantity of the adsorption for samples of the same mineral, broken to pieces of different dispersity, also differs. However, between the adsorption capacity of test samples, divided into 3 groups--quartz, zeolite and mixed from the work environment, with respect to methylene blue, and their biological aggressiveness, tested "in vivo" after intratracheal test and the subcutaneous pocket method and the zeolite dusts on diploid culture, an inverse dependence is established. The adsorption capacity of the test dusts from the work environment is many times higher than the examined quartz and zeolite dusts, because of the presence of mineral components in them, especially argillaceous, which have high affinity toward the dye. The inverse dependence established between the adsorption capacity with respect to methylene blue and the biological effect of the tested dusts give grounds to propose the adsorption capacity as one of the induces for studying and hygienic evaluation of different types dusts, which have no components manifesting specific affinity to the dye.

  16. 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.

  17. 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.

  18. 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.

  19. [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.

  20. 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.

  1. Removal of Pb(II) and Cd(II) from water by adsorption on peels of banana.

    PubMed

    Anwar, Jamil; Shafique, Umer; Waheed-uz-Zaman; Salman, Muhammad; Dar, Amara; Anwar, Shafique

    2010-03-01

    The adsorption of lead(II) and cadmium(II) on peels of banana has been studied in batch mode using flame atomic absorption spectroscopy for metal estimation. Concerned parameters like adsorbent dose, pH, contact time and agitation speed were investigated. Langmuir, Freundlich and Temkin isotherms were employed to describe adsorption equilibrium. The maximum amounts of cadmium(II) and lead(II) adsorbed (qm), as evaluated by Langmuir isotherm, were 5.71 mg and 2.18 mg per gram of powder of banana peels, respectively. Study concluded that banana peels, a waste material, have good potential as an adsorbent to remove toxic metals like lead and cadmium from water.

  2. Synthesization, characterization and adsorption properties of sulfonic cellulose.

    PubMed

    Shi, Wenjian; Zhou, Yan; Zhang, Yuanzhang; Li, Liang; Yang, Qinlin

    2012-01-01

    The synthesization and characterization of a new environmental functional material-sulfonic cellulose - were studied in this paper. The preparation conditions were optimized through an orthogonal experiment. The modified cellulose was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorption rules of cationic organic pollutants and heavy metal ions by this new material were discussed. Regeneration and recycling performances of the sulfonic cellulose were also investigated. At the temperature of 323 K, sulfonic cellulose was prepared by grafting 2-acrylamido-2-methylpropane sulfonic acid (AMPS) onto alkali-treated cellulose for 4 h with the employing of ceric ammonium nitrate as initiator. The mass ratio of AMPS to cellulose was 3:1 and the concentration of ceric ammonium nitrate was 63.8 mmol/L. The sulfur content of sulfonic cellulose was 7.32 wt%. The peaks of 1,303 and 1,159 cm⁻¹ in IR suggested the existence of the sulfonic group in sulfonic cellulose. The XRD and SEM results showed that the crystallinity decreased while the specific surface area increased after modification. Batch adsorption results showed that sulfonic cellulose had a favorable adsorption capacity for model contaminants at pH 6.0-7.0. The adsorption process was endothermic and reached equilibrium in 180 min. The adsorption rules of cationic organic pollutants and heavy metal ions indicated that sulfonic cellulose had high adsorption capacity for the cationic dyes with a coplanar macromolecule structure and organic compounds carrying the amino group. Under room temperature, 1.0 mol/L HCl can be used as a desorption solution and the equilibrium adsorption capacity had little decrease (less than 7%) after six adsorption-desorption cycles.

  3. 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.

  4. TECHNICAL NOTE: ADSORPTION CAPACITY OF GAC FOR SYNTHETIC ORGANICS

    EPA Science Inventory

    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 Ag...

  5. Fixation of the two Tabun isomers in acetylcholinesterase: a QM/MM study.

    PubMed

    Kwasnieski, Ophélie; Verdier, Laurent; Malacria, Max; Derat, Etienne

    2009-07-23

    Dysfunction of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat since AChE is a key enzyme in neurotransmission. To more rigorously design reactivation agents, it is of prime importance to understand the mechanism of inhibition of AChE by OP compounds. Tabun is one of the more potent nerve agents. It is produced as a mixture of two enantiomers, one of them (the levorotatory isomer) being 6.3 times more potent. Could it be that the inhibition mechanism is different for the two enantiomers? To address this critical issue, we used a hybrid quantum mechanics/molecular mechanics (QM/MM) methodology. Calculations were performed using BP86 functional and TZVP basis set. Single points were also done with B3LYP and PBE0 functionals. We studied the four possible attacks of tabun on the oxygen of Ser203 using two crystallographic structures (PDB codes 2C0P and 3DL7): (S) tabun with the cyano group syn to the oxygen of Ser203 and (R) tabun with the cyano group anti, corresponding to the experimental X-ray structure; (S) tabun with the cyano group anti to the oxygen of Ser203 and (R) tabun with the cyano group syn, leading to a different isomer than was experimentally seen. We found that the most active enantiomer is (S) tabun with the cyano group syn to the oxygen of Ser203. Thus it seems that the cyano group does not leave anti to the oxygen of Ser203 due to repulsive polar interactions between cyanide and aromatic residues in the active site.

  6. QM/MM calculations suggest a novel intermediate following the proton abstraction catalyzed by thymidylate synthase

    PubMed Central

    Wang, Zhen; Ferrer, Silvia; Moliner, Vicent; Kohen, Amnon

    2013-01-01

    The cleavage of covalent C-H bonds is one of the most energetically demanding, yet biologically essential, chemical transformations. Two C-H bond cleavages are involved in the reaction catalyzed by thymidylate synthase (TSase), which provides the sole de novo source of thymidylate (i.e. the DNA base T) for most organisms. Our QM/MM free energy calculations show that the C-H→O proton transfer has three transition states that are energetically similar but structurally diverse. These characteristics are different from our previous calculation results on the C-H→C hydride transfer, providing an explanation for differences in temperature dependences of KIEs on these two C-H bond activation steps. The calculations also suggest that the traditionally-proposed covalent bond between the protein and substrate (the C6-S bond) is very labile during the multi-step catalytic reaction. Collective protein motions not only assist cleavage of the C6-S bond to stabilize the transition state of the proton transfer step, but also rearrange the H-bond network at the end of this step to prepare the active site for subsequent chemical steps. These computational results illustrate functionalities of specific protein residues that reconcile many previous experimental observations, and provide guidance for future experiments to examine the proposed mechanisms. The synchronized conformational changes in the protein and ligands observed in our simulations demonstrate participation of protein motions in the reaction coordinate of enzymatic reactions. Our computational findings suggest the existence of new reaction intermediates not covalently bound to TSase, which may lead to a new class of drugs targeting DNA biosynthesis. PMID:23464672

  7. Hunting the human DPP III active conformation: combined thermodynamic and QM/MM calculations.

    PubMed

    Tomić, Antonija; Tomić, Sanja

    2014-11-07

    Multiple choices of the protein active conformations in flexible metalloenzymes complicate study of their catalytic mechanism. We used three different conformations of human dipeptidyl-peptidase III (DPP III) to investigate the influence of the protein environment on ligand binding and the Zn(2+) coordination. MD simulations followed by calculations of binding free energy components accomplished for a series of DPP III substrates, both synthetic and natural, revealed that binding of the β-strand shaped substrate to the five-stranded β-core of the compact DPP III form (in antiparallel fashion) is the preferred binding mode, in agreement with the experimentally determined structure of the DPP III inactive mutant-tynorphin complex (Bezerra et al., Proc. Natl. Acad. Sci. U. S. A., 2012, 109, 6525). Previously it was proposed that the catalytic mechanism of DPP III is similar to that of thermolysin, which assumes exchange of five and four coordinated Zn(2+), and activation of Zn-bound water by a nearby Glu. Our QM/MM calculations, performed for a total of 18 protein structures with different zinc ion environments, revealed that the 5-coordinated metal ion is more favourable than the 6-coordinated one in only the most compact DPP III form. Besides, in this structure E451 is H-bonded to the metal ion coordinating water. Also, our study revealed two constraints for the broad substrate specificity of DPP III. One is the possibility of the substrate adopting the β-strand shape and the other is its charged N-terminus. Altogether, we assume that the human DPP III active conformation would be the most compact form, similar to the "closed X-ray" DPP III structure.

  8. Spore Germination Mediated by Bacillus megaterium QM B1551 SleL and YpeB

    PubMed Central

    Üstok, Fatma Işık; Packman, Len C.; Lowe, Christopher R.

    2014-01-01

    Previous work demonstrated that Bacillus megaterium QM B1551 spores that are null for the sleB and cwlJ genes, which encode cortex-lytic enzymes (CLEs), either of which is required for efficient cortex hydrolysis in Bacillus spores, could germinate efficiently when complemented with a plasmid-borne copy of ypeB plus the nonlytic portion of sleB encoding the N-terminal domain of SleB (sleBN). The current study demonstrates that the defective germination phenotype of B. megaterium sleB cwlJ spores can partially be restored when they are complemented with plasmid-borne ypeB alone. However, efficient germination in this genetic background requires the presence of sleL, which in this species was suggested previously to encode a nonlytic epimerase. Recombinant B. megaterium SleL showed little, or no, activity against purified spore sacculi, cortical fragments, or decoated spore substrates. However, analysis of muropeptides generated by the combined activities of recombinant SleB and SleL against spore sacculi revealed that B. megaterium SleL is actually an N-acetylglucosaminidase, albeit with apparent reduced activity compared to that of the homologous Bacillus cereus protein. Additionally, decoated spores were induced to release a significant proportion of dipicolinic acid (DPA) from the spore core when incubated with recombinant SleL plus YpeB, although optimal DPA release required the presence of endogenous CLEs. The physiological basis that underpins this newly identified dependency between SleL and YpeB is not clear, since pulldown assays indicated that the proteins do not interact physically in vitro. PMID:24375103

  9. Mutational analysis of Bacillus megaterium QM B1551 cortex-lytic enzymes.

    PubMed

    Christie, Graham; Ustok, Fatma Isik; Lu, Qiaozhi; Packman, Len C; Lowe, Christopher R

    2010-10-01

    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.

  10. Spore germination mediated by Bacillus megaterium QM B1551 SleL and YpeB.

    PubMed

    Ūstok, Fatma Işik; Packman, Len C; Lowe, Christopher R; Christie, Graham

    2014-03-01

    Previous work demonstrated that Bacillus megaterium QM B1551 spores that are null for the sleB and cwlJ genes, which encode cortex-lytic enzymes (CLEs), either of which is required for efficient cortex hydrolysis in Bacillus spores, could germinate efficiently when complemented with a plasmid-borne copy of ypeB plus the nonlytic portion of sleB encoding the N-terminal domain of SleB (sleB(N)). The current study demonstrates that the defective germination phenotype of B. megaterium sleB cwlJ spores can partially be restored when they are complemented with plasmid-borne ypeB alone. However, efficient germination in this genetic background requires the presence of sleL, which in this species was suggested previously to encode a nonlytic epimerase. Recombinant B. megaterium SleL showed little, or no, activity against purified spore sacculi, cortical fragments, or decoated spore substrates. However, analysis of muropeptides generated by the combined activities of recombinant SleB and SleL against spore sacculi revealed that B. megaterium SleL is actually an N-acetylglucosaminidase, albeit with apparent reduced activity compared to that of the homologous Bacillus cereus protein. Additionally, decoated spores were induced to release a significant proportion of dipicolinic acid (DPA) from the spore core when incubated with recombinant SleL plus YpeB, although optimal DPA release required the presence of endogenous CLEs. The physiological basis that underpins this newly identified dependency between SleL and YpeB is not clear, since pulldown assays indicated that the proteins do not interact physically in vitro.

  11. 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.

  12. 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.

  13. Microscopic basis for kinetic gating in Cytochrome c oxidase: insights from QM/MM analysis

    PubMed Central

    Goyal, Puja; Yang, Shuo; Cui, Qiang

    2014-01-01

    Understanding the mechanism of vectorial proton pumping in biomolecules requires establishing the microscopic basis for the regulation of both thermodynamic and kinetic features of the relevant proton transfer steps. For the proton pump cytochrome c oxidase, while the regulation of thermodynamic driving force for key proton transfers has been discussed in great detail, the microscopic basis for the control of proton transfer kinetics has been poorly understood. Here we carry out extensive QM/MM free energy simulations to probe the kinetics of relevant proton transfer steps and analyze the effects of local structure and hydration level. We show that protonation of the proton loading site (PLS, taken to be a propionate of heme a3) requires a concerted process in which a key glutamic acid (Glu286H) delivers the proton to the PLS while being reprotonated by an excess proton coming from the D-channel. The concerted nature of the mechanism is a crucial feature that enables the loading of the PLS before the cavity containing Glu286 is better hydrated to lower its pKa to experimentally measured range; the charged rather than dipolar nature of the process also ensures a tight coupling with heme a reduction, as emphasized by Siegbahn and Blomberg. In addition, we find that rotational flexibility of the PLS allows its protonation before that of the binuclear center (the site where oxygen gets reduced to water). Together with our recent study (P. Goyal, et al., Proc. Natl. Acad. Sci. USA, 110:18886-18891, 2013) that focused on the modulation of Glu286 pKa, the current work suggests a mechanism that builds in a natural sequence for the protonation of the PLS prior to that of the binuclear center. This provides microscopic support to the kinetic constraints revealed by kinetic network analysis as essential elements that ensure an efficient vectorial proton transport in cytochrome c ox